Adv Funct Materials - 2021 - Qin

Review
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Strategies in Structure and Electrolyte Design for

High-Performance Lithium Metal Batteries
Kaiqiang Qin, Kathryn Holguin, Motahareh Mohammadiroudbari, Jinghao Huang,
Eric Young Sam Kim, Rosemary Hall, and Chao Luo*
challenge, a breakthrough in high-energy

Lithium metal is the “holy grail” anode for next-generation high-energy cathode and anode materials for advanced
rechargeable batteries due to its high capacity and lowest redox potential battery technology is anticipated to further
among all reported anodes. However, the practical application of lithium boost the energy density of rechargeable
batteries. Among emerging battery tech-
metal batteries (LMBs) is hindered by safety concerns arising from
nologies, rechargeable batteries beyond
uncontrollable Li dendrite growth and infinite volume change during LIBs such as Li/nickel-rich transition
the lithium plating and stripping process. The formation of stable solid metal oxide, Li–sulfur, and Li–O2 batteries
electrolyte interphase (SEI) and the construction of robust 3D porous current can deliver high energy densities of 440,
collectors are effective approaches to overcoming the challenges of Li metal 650, and 950 Wh kg−1, respectively, repre-
anode and promoting the practical application of LMBs. In this review, four senting promising next-generation high-
energy rechargeable batteries.[7–10] In all
strategies in structure and electrolyte design for high-performance Li metal
these high-energy-density battery systems,
anode, including surface coating, porous current collector, liquid electrolyte, lithium metal is used as an anode. Com-
and solid-state electrolyte are summarized. The challenges, opportunities, pared to the other anode materials in LIBs
perspectives on future directions, and outlook for practical applications of (graphite, lithium titanium oxide (LTO),
Li metal anode, are also discussed. Si, Sn, and Ge), Li metal anode shows a
high theoretical capacity of 3861 mAh g−1,
the lowest redox potential of −3.04 V
1. Introduction versus the standard hydrogen electrode (SHE), high electronic/
ionic conductivity, and comparable cost per energy to other
The rapid growth of the rechargeable battery industry in the anodes, demonstrating great promise for high-energy recharge-
last three decades has played an essential role in the prosperity able batteries (Figure 1). More importantly, lithium metal is
of modern technologies from portable electronics to electric the only anode that can couple with high-energy sulfur- and
vehicles and renewable energies.[1–4] To date, the substantial O2-based cathode because of the presence of lithium source in
demand from the ever-growing electric vehicle market further lithium metal anode. All these merits render Li metal batteries
stimulates the development of rechargeable batteries toward the (LMBs) promising high-energy-density energy storage devices.
direction of high-energy-density and high-power-density energy The research on LMBs can be backdated to the 1970s, when
storage devices. Among all types of commercial rechargeable the first rechargeable lithium-based battery was invented by
batteries, lithium-ion batteries (LIBs) are the “superstars” for Whittingham et al. at ExxonMobil. The first-generation LMBs,
electric vehicles due to their high energy density and long cycle consisting of a lithium-aluminum anode and a TiS2 cathode,
life. However, state-of-the-art LIBs can only reach a specific exhibited high energy density and a fast charging rate.[11,12]
energy density of ≈250 Wh kg−1, which becomes a bottleneck However, the battery system based on a lithium metal anode
for LIBs consisting of a graphite-based anode and a cobalt-rich cannot last long because lithium dendrite growth upon cycling
transition metal oxide-based cathode.[5,6] To circumvent this can trigger battery thermal runaway.[13,14] The uncontrollable
growth of lithium dendrites and infinite relative volume change
are major challenges for the practical application of Li metal
Dr. K. Qin, K. Holguin, M. Mohammadiroudbari, J. Huang, E. Y. S. Kim, anode.[15] Due to the high reactivity of Li metal, the battery
R. Hall, Prof. C. Luo electrolyte spontaneously forms a solid electrolyte interphase
Department of Chemistry and Biochemistry
George Mason University
(SEI) layer on its surface, physically blocking the direct contact
Fairfax, VA 22030, USA between electrolyte and lithium metal.[16,17] The SEI layer can
E-mail: cluo@gmu.edu protect the lithium metal and prevent the continuous decom-
Prof. C. Luo position of the electrolyte. However, the infinite volume change
Quantum Science & Engineering Center and incessant growth of lithium dendrites are detrimental to
George Mason University the SEI layer and trigger the formation of cracks in SEI. Due
Fairfax, VA 22030, USA
to the tip-effect, Li dendrites tend to grow through the cracks,
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202009694.
further damaging the integrity of the SEI layer.[18–20] In addition
to damage of the SEI layer, the uneven plating and stripping of
DOI: 10.1002/adfm.202009694 Li dendrites during long-term cycling peels off the dendrites
Adv. Funct. Mater. 2021, 31, 2009694 2009694 (1 of 36) © 2021 Wiley-VCH GmbH
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Figure 1. Overview of fundamental properties of different types of anode materials in Li batteries.
from the current collector to produce “dead Li”, which becomes chemical stability and high mechanical strength.[27] To gener-
electrochemically inactive and results in severe capacity decay ate a robust SEI layer and inhibit lithium dendrite formation/
(Figure 2a).[21,22] In contrast, the active Li dendrites will penetrate growth, tremendous work has been done to form a LiF-rich
the porous separator and contact with the cathode, leading to the SEI layer for lithium metal anode protection. To date, there
internal short circuit and battery thermal runaway.[23,24] All these are two major strategies to achieve this goal: 1) Pre-formation
challenges impede the practical application of LMBs. To date, of artificial LiF-rich SEI through surface coating is an effective
with the rapid development of nanotechnology and advanced method to construct a stable SEI. 2) The use of high concen-
characterization techniques such as cryo-electron microscopy, tration fluorinated liquid electrolytes, fluorinated solvents,
fundamental insights toward the interfacial chemistry and or fluorinated additives can in situ generate a firm LiF-rich
lithium dendrite formation/growth mechanism have been SEI. In addition to LiF-rich SEI, other organic and inorganic
gained, facilitating the research for high-energy, safe, and stable materials were also used to build a stable SEI layer on lithium
LMBs. In the last decade, considerable efforts were devoted to metal anode to suppress the Li dendrite growth. Moreover,
developing effective strategies for a safe and stable lithium metal SEI also plays an important role in all-solid-state LMBs. The
anode, but there are still two inevitable challenges that need to solid-state electrolyte (SSE) with ultrahigh strength and hard-
be addressed before the commercialization of LMBs. ness can dramatically suppress the growth of Li dendrites,
but a stable and robust SEI layer between SSE and lithium
1) Stability of SEI: The high reactivity and low potential of Li metal is required to enable the intimate contact and reduce
metal anode result in the spontaneous reaction between elec- the interfacial resistance. We will provide a more detailed
trolyte and lithium metal to form the SEI, which is a passiva- discussion in this review.
tion layer that can avoid further contact and reaction between 2) Infinite volume change of Li metal anode during charge/
Li metal and electrolyte.[25,5] According to the mosaic model discharge: Most anode materials suffer from volume change
proposed by Peled et al., the SEI consists of a dual-layer struc- during the battery charge/discharge process. For example, the
ture with an inner inorganic layer and an outer organic layer graphite anode exhibits a volume change of ≈10%, while the Si
(Figure 2b).[26] Compared to the organic layer, the inorganic anode undergoes a volume expansion of ≈400% after full lithia-
layer possesses higher shear modulus, which can maintain tion. For the Li metal anode, the entire Li metal can be stripped
the structural integrity of the SEI layer and suppress the Li from the anode after complete de-lithiation, which causes an
dendrite growth. Among various inorganic species in SEI, infinite volume change. To circumvent this challenge, sta-
LiF has been identified as the key component due to its high ble 3D porous current collectors, such as 3D porous metal,
Figure 2. a) Scheme of the Li dendrite and “dead Li” formation in LMBs. b) Schematic illustration of microstructured SEI films.
Figure 3. The schematic illustration of strategies for Li metal anode in stable and safe LMBs.[30–33]
3D carbon films, organic/inorganic composite films, metal al- new cracks and fractures in the SEI layer, which expose fresh
loys, and vertically oriented metal arrays, have been introduced lithium metal to the liquid electrolyte and generates more SEI.
to pre-store Li through the infusion of molten Li, electrodepo- The continuous formation of new SEI during cycling results
sition process or rolling approach, accommodating the volume in fragile SEI and massive consumption of both Li+ and elec-
change during repeated Li plating/stripping cycles. Addition- trolyte, which remarkably reduce the Coulombic efficiency,
ally, 3D porous current collectors enlarge the surface area and capacity, and cycle life of LMBs. To address this challenge, sur-
lower the areal current density of Li metal anode, which can face coating or fabrication of an artificial SEI as a protective
also suppress the Li dendrite growth.[28,29] Stable 3D porous layer has been extensively studied. The coating of a homog-
current collectors combined with stable SEI can remarkably enous, ion-conductive, chemically and mechanically stable
improve the safety and stability of Li metal anode, which is a protective layer has been proven to be an effective approach
feasible way to fulfill the practical application of LMBs. to mitigating the uncontrollable lithium dendrite growth and
accommodate the infinite volume change of lithium metal.[30–32]
This review aims to provide a thorough and comprehensive Various artificial coating materials such as LiF,[33,34] Al2O3,[35]
overview of the recent development and applications of Li metal graphdiyne,[36] polyethylene oxide,[37] and so on have been inves-
anodes to guide the future study of high-safety, high-stability, tigated to improve the cycling performance in LMBs. All studies
and high-energy LMBs. We summarize recent advances in sta- have attempted to optimize the mechanical strength and Li-ion
bilizing Li metal anodes by four effective strategies, including conductivity of artificial SEI to achieve the high Coulombic
surface coating, porous current collector, liquid electrolyte, efficiency, long lifetime, and low overpotential of LMBs.[38–42]
and SSE (Figure 3). We also discuss the application of Li metal However, it is still challenging to satisfy all the requirements
anodes in Li–S batteries for high-performance energy storage in the construction of the artificial SEI layer by surface coating.
devices. The conclusion and outlook of advanced lithium metal For example, a thin and conductive artificial SEI layer is neces-
anodes for high-energy, safe, and stable LMBs are also provided. sary to facilitate the Li-ion transfer in the electrode-electrolyte
interface, but it may not retain the high shear modulus, which
is vital for the long lifespan and structural integrity of SEI. In
2. Current Strategies to Circumvent the this section, a comprehensive and thorough overview of recent
advances in developing surface coating methods for Li metal
Challenges of Lithium Metal Anode
protection are presented. The electrochemical performances of
2.1. Surface Coating Li metal anodes enhanced by various surface coating methods
are summarized in Figure 4 and Table 1.
The SEI layer plays a critical role in LIBs because it enlarges the Among all coating materials used to alleviate lithium
stability window of organic electrolytes by physically blocking dendrite growth, LiF is one of the best candidates for battery
the direct contact between anode and electrolyte. With a stable application because of its high chemical stability and high
SEI layer, low reaction potential anodes such as graphite, silicon, mechanical strength. Employing LiF as a key component in the
and tin can be used to enhance the battery potential and energy artificial SEI has been demonstrated as an effective approach to
density. To gain fundamental insights into the SEI, interfacial improving the homogenous plating of lithium metal. A low-cost
chemistry has been extensively exploited to understand the and scalable method for fabricating LiF-rich artificial SEI on a
composition, thickness, electrochemical property, and reaction Li metal anode was proposed by Lang et al.[43] The LiF-coated Li
mechanism, which benefits the design and optimization of the metal anode was fabricated by a reaction between PVDF-DMF
SEI layer. However, the infinite volume change and incessant soaked separator and lithium metal, which can be scaled up at
growth of lithium dendrites in LMBs continuously generate a low cost. As shown in Figure 5a, the Li metal anode with a
Figure 4. a) The Coulombic efficiency and b) cycle life of different surface coating methods at various current densities.
uniform, conformal, and high-quality LiF protection layer pre- exposure to ambient atmosphere (RH: 20–35%) for over 24 h
vents side reactions and lithium dendrite formation. In contrast, due to the hydrophobicity of the GF-LiF protection layer. This
the bare Li anode cannot withstand repeated plating/stripping work opens up the door for large-scale fabrication of air-stable
cycles, resulting in uncontrollable lithium dendrite growth. The and dendrite-free Li metal anode.
galvanostatic charge/discharge measurements were conducted A variety of methods have been proposed to fabricate a thin
for the pristine lithium metal and LiF coated lithium metal in and stable artificial SEI layer, which can ultimately suppress
symmetrical cells with a carbonate-based electrolyte. The over- dendrite growth in LMBs. In addition to LiF, recent studies have
potential of LiF coated Li at the current density of 3 mA cm−2 demonstrated that the deposition of a thin layer of Al2O3 on the
remains consistent upon long-term cycling of 200 h, while the lithium metal anode can also alleviate the Li dendrite formation
overpotential of the pristine Li remarkably increases after 60 h and enhance the electrochemical performance of LMBs. Al2O3
of charge and discharge (Figure 5b), demonstrating improved has low binding energy with Li, but it forms a Li-Al-O layer
lithium plating/stripping with LiF coating. This artificial SEI which can remarkably improve the adhesion to Li metal anode.[35]
layer prevents side reactions and mitigates lithium dendrite Atomic layer deposition (ALD) has been used to deposit a thin
growth on the surface of the Li metal anode. Shen et al. pre- layer of Al2O3 on the Li surface. This technique offers a way to
sented another low-cost fabrication method of a LiF-rich arti- deposit the coating layer directly on the ready-to-use electrode
ficial SEI layer by the reaction between molten Li and graphite with precise control of the thickness.[44] Applying Al2O3 coating
fluoride (GF).[34] The hydrophobic and uniform GF-LiF artificial (4 nm) by ALD on the surface of Li metal improves the wettability
SEI formed on the surface of Li metal physically blocks the con- of liquid electrolytes by eliminating voids, yielding a uniform
tact between air and Li metal, protecting the metallic Li from lithium flux during cycling. The resulting Li metal anode was
side reaction with the air and improving the air stability of Li tested for up to 50 charge/discharge cycles at the current density
metal anode (Figure 5c). The density functional theory (DFT) of 1 mA cm−2 and the areal capacity of 1 mAh cm−2 to evaluate
calculation indicates that the GF can be reduced to LiF and gra- the morphology evolution. As shown in Figure 5h,i, SEM images
phene spontaneously after contact with molten Li. The resulting of the bare Li and Al2O3 coated Li display a significant difference
protective layer not only mitigates the Li dendrite growth but in dendrite growth. The bare Li exhibits a rough and dendritic
also enables a moisture- and air-stable lithium metal anode. surface (Figure 5e), while the Al2O3 coating keeps the surface of
Consequently, metallic Li can be uniformly deposited onto lithium metal uniform and smooth (Figure 5f). The Al2O3 coated
the surface of the GF-LiF-Li composite to form a dendrite-free Li metal does not generate lithium dendrite during repeated Li
lithium metal anode at a high current density of 3 mA cm−2. In plating and stripping due to the improved wettability of the liquid
contrast, numerous moss-like Li dendrites are formed on the electrolyte on the lithium metal surface. Furthermore, the Cou-
bare Li anode after electrodeposition (Figure 5d). The GF-LiF- lombic efficiency is measured as a determining factor to define
Li symmetric cells exhibit excellent cyclic stability for 850 000s the battery performance. The lithium metal anodes were tested
with a low overpotential of 70 mV, confirming that the GF-LiF at 1 mA cm−2 and 1 mAh cm−2 with 20 µL ether-based electrolyte.
coating can effectively inhibit side reactions and suppress the The bare Li shows a lower initial Coulombic efficiency than the
Li dendrite growth. More importantly, the GF-LiF-Li composite Al2O3 coated Li. More importantly, the Li coated with 4 nm Al2O3
anode delivers excellent electrochemical performance even after retains the average Coulombic efficiency of 98% for 200 cycles,
Table 1. Summary of electrochemical performances of Li metal anode with various surface coating methods.
Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

−2 −2
[30] Cu3N+SBR coating 1 m LiPF6 in EC/DEC (1:1) + 10 wt% FEC 1 mA cm , 1 mAh cm , 100 cycles, 97.4% ≈100 mV
0.25 mA cm−2, 0.5 mAh cm−2, 150 cycles 98%
[31] PVDF-HFP/LiF layer 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 0.5 mA cm−2, 1 mAh cm−2, 120 cycles, 97.2%
1 mA cm−2, 1 mAh cm−2, 100 cycles, ≈96.3%
2 mA cm−2, 1 mAh cm−2, 200 h ≈175 mV
[34] Graphite fluoride-LiF coating 1 m LiPF6 in EC/DEC (1:1) 1 mA cm−2, 1 mAh cm−2, 222 h, 70 mV
5 mA cm−2, 1 mAh cm−2, 55.5 h, 300 mV
10 mA cm−2, 1 mAh cm−2, 33.4 h 450 mV
[35] Al2O3 sputter coating 1 m LiPF6 in EC/DMC/DEC (1:1:1) 0.5 mA cm−2, 0.5 mAh cm−2, 1200 h ≈400 mV
[36] N-Doped graphdiyne coating 1 m LiPF6 in EC/DMC (1:1) 0.5 mA cm−2 −2
, 1 mAh cm , 300 cycles, 98% 45 mV
1 mA cm−2, 1 mAh cm−2, 200 cycles 97%
[37] Polyethylene oxide (PEO) 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 0.5 mA cm−2, 200 cycles ≈100% ≈30 mV
film coating
[39] LiPON coating 0.35 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 555.5 h, ≈150 mV
2 mA cm−2, 2 mAh cm−2, 222.2 h ≈200 mV
[42] c-PEGDMA coating 1 m LiPF6 in EC/DEC (1:1) 1 mA cm−2, 1 mAh cm−2, 500 h, ≈8.5 mV
5 mA cm−2, 5 mAh cm−2, 500 h ≈51 mV
[43] LiF coating 1 m LiPF6 in EC/DEC (1:1) 1 mA cm−2, 1 mAh cm−2, 600 h, ≈100 mV
3 mA cm−2, 1 mAh cm−2, 200 h ≈500 mV
[44] Al2O3 coating by ALD 1 m LiTFSI in DOL/DME (1:1) + 2 wt% 1 mA cm−2, 1 mAh cm−2, 180 cycles 97% 100 mV
LiNO3 + 0.18 m Li2S8
[45] LiPAA polymer coating 1 m LiPF6 in EC/DMC/DEC (1:1:1) 0.5 mA cm−2, 1 mAh cm−2, 700 h, ≈50 mV
1 mA cm−2, 1 mAh cm−2, 250 h ≈200 mV
[46] Polymer coating 1 m LiPF6 in EC/EMC/FEC (3:7:1) 0.5 mA cm−2, 1 mAh cm−2, 200 cycles 98.3% 30 mV
−2 −2
[47] 18-crown-6/PVDF 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 0.2 mA cm , 1 mAh cm , 200 cycles, 97.38%
polymer film 0.5 mA cm−2, 1 mAh cm−2, 75 cycles, 95.61%
1 mA cm−2, 2 mAh cm−2, 150 h 30 mV
[48] Polymer–inorganic layer coating 1 m LiPF6 in EC/EMC (1:1) + 2% 2 mA cm−2, 2 mAh cm−2, 800 cycles, 99.2%
LiBOB 2 mA cm−2, 4 mAh cm−2, 300 cycles, 99.1%
2 mA cm−2, 8 mAh cm−2, 150 cycles 98.6%
[49] Amorphous Li3PO4 coating 1 m LiTFSI in DOL/DME (1:1) 0.5 mA cm−2, 0.5 mAh cm−2, 900 h, <150 mV
1 mA cm−2, 1 mAh cm−2, 300 h <300 mV
[50] LPON coating 1 m LiTFSI in DOL/DME (1:1) 0.5 mA cm−2, 1 mAh cm−2, 650 h, 55 mV
3 mA cm−2, 1 mAh cm−2, 600 h 150 mV
[51] Sn coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 900 h, ≈15 mV
3 mA cm−2, 1 mAh cm−2, 100 h, 50 mV
5 mA cm−2, 1 mAh cm−2, 70 h, 100 mV
10 mA cm−2, 1 mAh cm−2, 80 h 150 mV
[52] MOF-199 coating 0.6 m LiTFSI + 0.4 m LiNO3 in DME/DOL (2:1) 1 mA cm−2, 1 mAh cm−2, 350 cycles, 97 % 25 mV
[53] Li seeds deposition 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 0.5 mAh cm−2, 140 cycles, 97.2% ≈15 mV
0.5 mA cm−2, 1 mAh cm−2, 100 cycles 97.8%
[54] NH4HF2 coating 1 m LiTFSI in DOL/DME (1:1) 1 mA cm−2, 1 mAh cm−2, 520 cycles 98.5% 81.6 mV
[55] Lithiated Nafion/LiCl interface 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 250 cycles, 98.1%
3 mA cm−2, 1 mAh cm−2, 110 cycles, 96% 50 mV
1 mA cm−2, 1 mAh cm−2, 1000 h, 50 mV
1 mA cm−2, 3 mAh cm−2, 350 h, 50 mV
8 mA cm−2, 1 mAh cm−2, 120 h 200 mV
[56] LiNO3 coating 1 m LiPF6 in EC/DEC (1:1) 1 mA cm−2, 2 mAh cm−2, 500 h ≈80 mV
[57] PDA coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 1 mAh cm−2, 100 cycles, 97% 50 mV
1 mA cm−2, 1 mAh cm−2, 100 cycles, 96%
0.1 mA cm−2, 0.2 mAh cm−2, 800 h
[58] n-terminal alcohols coating 1 m LiPF6 in EC/DMC/DEC (1:1:1) 0.5 mA cm−2, 1 mAh cm−2, 400 h 50 mV
Table 1. Continued.

−2 −2
[59] Ag/Au coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm , 1 mAh cm , 1000 h ≈200 mV
[60] 2D MXene stacks coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 3 mA cm−2, 3 mAh cm−2,2250 h, 35 mV
5 mA cm−2, 5 mAh cm−2, 2250 h, 80 mV
10 mA cm−2, 10 mAh cm−2, 2200 h 120 mV
[61] Cu2O nanoparticles coating 1 m LiPF6 in EC/DEC (1:1) 2 mA cm−2, 1 mAh cm−2, 140 cycles, 95.6%
1 mA cm−2, 1 mAh cm−2800 h 10 mV
[62] Li polysulfidophosphate/polymer 1 m LiTFSI in DOL/DME (1:1) −2, cm−2, 98.7%
1 mA cm 1 mAh 950 cycles,
film 2 mA cm−2, 2 mAh cm−2, 460 cycles, 98.5%
2 mA cm−2, 3 mAh cm−2, 800 h ≈120 mV
[63] C−N polymer coating 1 m LiTFSI +0.2 m LiNO3 in DOL/DME (1:1) 1 mA cm−2, 2 mAh cm−2, 500 cycles, 98.5%
0.5 mA cm−2, 1.5 mAh cm−2, 1600 h 50 mV
[64] Zn@MXene layers 1 m LiTFSI in DOL/DME (1:1) 1 mA cm−2, 1 mAh cm−2, 1200 h 11.3 mV
[65] ZrO2/PVDF-HFP coating 1 m LiClO4 in EC/PC (1:1) 1 mA cm−2, 1 mAh cm−2, 250 h 100 mV
[66] Al–Li coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 2 mA cm−2,
1 mAh cm−2,
1600 h, 24 mV
10 mA cm−2, 1 mAh cm−2, 200 h, 110 mV
20 mA cm−2, 1 mAh cm−2, 100 h, 202 mV
10 mA cm−2, 5 mAh cm−2, 300 h ≈80 mV
[67] COF coating 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 400 h, 63 mV
2 mA cm−2, 1 mAh cm−2, 200 h 74 mV
[68] Carbonized MOFs coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 300 cycles, 99%
1 mA cm−2, 1 mAh cm−2, 1000 h 30 mV
[69] Li2S/Li2Se layer 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 2 mA cm−2, 1 mAh cm−2, 400 h, 50 mV
1.5 mA cm−2, 3 mAh cm−2, 900 h, 27 mV
3 mA cm−2, 3 mAh cm−2, 300 h ≈45 mV
[70] Organic polyurea coating 1 m LiPF6 in EC/DEC/DMC (1:1:1) 1 mA cm−2, 1 mAh cm−2, 460 h, 110 mV
3 mA cm−2, 1 mAh cm−2, 200 h, 180 mV
1 mA cm−2, 2 mAh cm−2, 400 h 100 mV
[71] β-PVDF film 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 2 mA cm−2, 2 mAh cm−2, 200 cycles, 99%
2 mA cm−2, 4 mAh cm−2, 900 h 50 mV
[72] Li2TiO3 coating 1.3 m LiPF6 in EC/DEC (3:7) 1 mA cm−2, 1 mAh cm−2, 350 h, 120 mV
3 mA cm−2, 1 mAh cm−2, 350 h ≈200 mV
[73] Lithium sulfide layer 1 m LiPF6 in EC/DEC (1:1) 2 mA cm−2, 5 mAh cm−2, 750 h 95 mV
[74] Graphite/SiO2 coating 1 m LiPF6 in EC/DEC (1:1) 0.5 mA cm−2,1 mAh cm−2,
1600 h, 150 mV
1 mA cm−2, 1 mAh cm−2, 800 h 250 mV
[75] C60 and Mg bilayers 1 m LiPF6 in DEC/EC/EMC (2:3:5 by weight) 1 mA cm−2, 1 mAh cm−2, 550 h, 50 mV
3 mA cm−2, 1 mAh cm−2, 180 h 135 mV
[76] Li–Al coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 2 mAh cm−2, 85 cycles, 98.6%
0.5 mA cm−2, 1 mAh cm−2, 1700 h ≈25 mV
[77] Double hydroxide coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 2 mAh cm−2, 200 cycles, 98.5%
[78] PEO/UPy coating 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 20 mA cm−2, 1 mAh cm−2, 400 h, 98.42% 196 mV
1 mA cm−2, 10 mAh cm−2, 1000 h, 94.8% 150 mV
1 mA cm−2, 1 mAh cm−2, 150 cycles, 300 mV
5 mA cm−2, 1 mAh cm−2, 75 cycles 28 mV
[79] Ag/Li coating 1 m LiTFSI in DOL/DME (1:1) 1 mA cm−2, 1 mAh cm−2, 2000 h, 50 mV
5 mA cm−2, 1 mAh cm−2, 500 h 80 mV
[80] GaInSnZn coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 0.5 mAh cm−2, 100 cycles, 96.07%
0.5 mA cm−2, 1 mAh cm−2, 100 cycles, 96.45%
1 mA cm−2, 0.5 mAh cm−2, 100 cycles, 93.81%
0.5 mA cm−2, 0.5 mAh cm−2, 350 h 25 mV
Table 1. Continued.

[81] Electrochemically active 1 m LiPF6 in PC/FEC (8:1) 6 mA cm−2, 6 mAh cm−2 at −15 oC, 250 cycles 98.6%
monolayer coating
[82] AlCl3 modifying 1 m LiPF6 in EC/DEC (1:1) 0.5 mA cm−2, 1 mAh cm−2, 1600 h, 160 mV
5 mA cm−2, 1 mAh cm−2, 500 h 112 mV
[83] PTCDI coating 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1200 h, 40 mV
5 mA cm−2, 1 mAh cm−2, 400 h, 80 mV
10 mA cm−2, 1 mAh cm−2, 300 h 400 mV
[84] Dual-layered coating 1 m LiPF6 in EC/DEC (1:1) 5 mA cm−2, 0.5 mAh cm−2, 20 h 200 mV
[85] CuF2 coating 1 m LiPF6 in EC/DEC (1:1) 2.5 mA cm−2, 0.5 mAh cm−2, 800 h ≈80 mV
which is ≈4 times longer than that of the bare Li. Even though fraction of cyclic ether groups.[46] The polymer is synthesized
reducing the electrolyte volume from 20 to 5 µL, the cycle life of via ring-opening metathesis polymerization while the cyclic
the Al2O3 coated Li is still ≈4 times longer than that of the bare ether group enables the polymer to be grafted onto Li metal.
Li. This result demonstrates that ALD is an effective technique The reaction between Li metal and cyclic carbonate is mitigated
to introduce a thin and dense surface coating layer on Li metal due to the strong affinity of cyclic ether groups to Li metal. The
for mitigating the lithium dendrite growth and prolonging the uniform and rigid polymeric skin acts as a protective layer, sup-
lifetime of LMBs. pressing side reactions between lithium metal and the electrolyte
In addition to inorganic materials, polymers with high (Figure 6a,b). The cycling stability of symmetric Li metal cells
mechanical strength and chemical stability also show promising with an areal capacity of 1.0 mAh cm−2 at a current density of
performance when used as surface coating layers or artificial SEI 0.5 mA cm−2 was measured for 300 h (Figure 6c). The potential
for Li metal anodes.[45] Gao et al. applied a skin-grafting strategy hysteresis of the polymer protected Li is smaller and more con-
to synthesize poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)- sistent than the bare Li, demonstrating that the polymeric layer
5-norbornene-exo-2,3-dicarboximide), containing high volume restricts the lithium dendrite growth. The skin-grafted polymer
Figure 5. a) Illustration of the process for fabricating LiF-coated Li. b) A comparison of the cycling stability of the symmetric LiF-coated Li metal (red)
and bare Li metal (black) cells with carbonate electrolytes at a current density of 3 mA cm−2. Reproduced with permission.[43] Copyright 2018, Published
by Elsevier B.V. c) Schematic illustration of GF–LiF–Li preparation and its protective effect for Li-metal anodes. d) The images from microscopy of
the bare Li (left column) and GF–LiF–Li (right column) electrolyte interface at 0, 10, 15, and 20 min at a current rate of 3 mA cm−2. The scale bars are
200 µm. Reproduced with permission.[34] Copyright 2019, Springer Nature. SEM images of e) bare Li at 5000 magnification; and f) 20 × Al2O3 Li at 5000
magnification. Reproduced with permission.[44] Copyright 2017, The Royal Society of Chemistry.
Figure 6. a) Illustration of the different interfacial chemistries of Li metal with grafted skin in a carbonate electrolyte. b) Chemical structure of the
polymer skin composed of a cyclic ether group (pink) and a polycyclic main chain (blue). c) Voltage profiles of symmetric Li cell over 300 h. Reproduced
with permission.[46] Copyright 2017, American Chemical Society. AFM images of electrode surface after ten cycles: Li deposition on d) bare Cu foil and
e) HICP-coated Cu foil. f) The Coulombic efficiency and the electrochemical performance of batteries with or without HICP coating: a) Li–Cu battery
at a current density of 0.2 mA cm−2. Reproduced with permission.[47] Copyright 2019, Elsevier B.V. g) Design of a polymer–inorganic SEI using the RPC
precursor rather than the electrolyte. The RPC layer first passivates the Li surface by a chemical reaction. h) Efficiency of Li deposition in Li|3D host
cells at a capacity of 4.0 mAh cm−2. Reproduced with permission.[48] Copyright 2019, Springer Nature Limited.
also improves the Coulombic efficiency of lithium plating and (Figure 6e), demonstrating smooth and uniform Li deposition.
stripping on copper to 98.3% upon long-term cycling. The excel- Electrochemical tests for the Coulombic efficiency of the Li–Cu
lent electrochemical performance of this polymer-based artificial half-cell were tested at a current density of 0.2 mA cm−2 and an
SEI layer offers opportunities to optimize the interfacial chem- areal capacity of 0.35 mAh cm−2 for 200 cycles. The Coulombic
istry and prevent lithium dendrite growth in LMBs. Although efficiency of the polymer-coated lithium metal anode retains at
polymeric coatings have been widely studied in LMBs, regulating 97.38% during cycling, while the bare lithium metal electrode
the thickness of the coating is still a major challenge. A thick suffers from fast efficiency loss after 100 cycles (Figure 6f), fur-
artificial SEI layer could hinder the Li-ion transfer, resulting in ther confirming that polymer coating is an effective approach to
poor electrochemical performance. To address this challenge, stabilizing lithium metal anode.
Dong et al. designed a very thin, flexible, and ionic conductive To take the advantage of both organic and inorganic mate-
polymeric layer containing 18-crown-6.[47] The polymeric layer rials, Gao et al. designed an artificial SEI layer for lithium metal
was fabricated via a spin-coating method, which can be scaled up anode, using poly(vinylsulfonyl fluoride-ran-2-vinyl-1,3-diox-
at a low price. The thickness of the coating layer was optimized olane) (P(SF-DOL))/graphene oxide nanosheet composite as a
by controlling the spin rate. In addition, polyvinylidene fluoride reactive polymer composite (RPC).[48] The RPC acts as a SEI pre-
(PVDF) was selected as the flexible skeleton for the stable coating cursor that reacts with lithium metal and forms a surface pas-
layer with a high dielectric constant. The highly conductive and sivating layer, consisting of polymeric Li salts embedded with
flexible polymer composite layer can alleviate the lithium den- nanoparticles of LiF and graphene oxide (GO) nanosheets. The
drite growth and accommodate the infinite volume change of Li unreacted RPC layer on the top of the surface passivating layer
metal anodes during cycling, both of which were confirmed by can conserve the structure of PRC-derived SEI upon cycling.
AFM images of lithium metal anodes cycled at 0.5 mA cm−2 for As illustrated in Figure 6g, this approach employs a reactive
10 cycles (Figure 6d,e). The bare Cu foil showed a non-uniform polymer as the SEI precursor rather than a liquid electrolyte.
deposition of Li metal on the surface with an average rough- The dense polymeric composite layer provides retention of elec-
ness of 188 nm (Figure 6d). With highly conductive polymer trolyte and GO nanosheets to improve the mechanical strength
coating (HICP), the average roughness was dropped to 42.6 nm and flexibility of SEI during cycling. To further investigate
the performance of the RPC-stabilized Li metal anode, the ratio of 6 µL mg−1 in Li–S batteries. Similarly, Ye et al. gener-
Coulombic efficiency was measured at an areal capacity of ated a Li–Al alloy layer on the surface of Li metal through an in
4.0 mAh cm−2 and a current density of 2.0 mA cm−2. An excel- situ electrochemical process to achieve the uniform Li nuclea-
lent average efficiency of 99.1% was retained for 300 cycles in tion and growth.[76] The symmetric Li metal cell delivers high
a Li|3D host cell (Figure 6h). The RPC-stabilized lithium metal cycling stability for 1700 h with a low overpotential of 25 mV
anode was also used to make a Li|NCM 523 cell, which retained at the capacity of 1 mAh cm−2 under a current density of
a high areal capacity of 3.4 mAh cm−2 under lean electrolyte 0.5 mA cm−2. Apart from Sn, Ag, Au, and Al, Ga-based liquid-
(7 µL mAh−1) condition and limited Li excess (1.9-fold access metal alloys have attracted extensive attention due to their high
of Li) for 200 cycles. The superior electrochemical results illus- surface tension, high electronic conductivity and chemical
trate that the reactive polymeric composite is an effective way stability. Wei et al. coated a thin 3 °C GaInSnZn liquid-metal
to achieve a robust SEI layer for lithium metal anode, as well as layer on the surface of Cu current collectors.[80] This liquid-
other metal anodes such as Na and Zn. metal can alloy with metallic Li to form a Li-rich alloy, which
Although inorganic and organic coating layers have shown effectively reduces the nucleation barriers of Li on metallic cur-
promising performance as artificial SEI, the low conduc- rent collectors. Consequently, the liquid-metal coated Cu foil
tivity and high interfacial resistance between the coating shows a low overpotential of 25 mV and high cycling stability
layer and metallic Li restrict their further application at high for 350 h. The success of these lithiophilic metals in stabilizing
current densities. In addition to artificial SEI, other surface Li metal anodes provides another promising surface coating
coating methods using lithiophilic metals were also reported method to mitigate the Li dendrite growth and improve the
for Li dendrite suppression, especially at high current densi- long-term cycling stability of LMBs.
ties. Lithiophilic metals, such as Sn, Ag, Zn, Al, Au, and so
on, possess high conductivity and wettability with metallic Li,
which can effectively inhibit side reactions of Li metal with the 2.2. Porous Current Collector
electrolyte and the growth of Li dendrites. Xia et al. coated a
conformal thin Sn layer with a thickness of ≈250 nm by the Another strategy to circumvent the challenges of lithium metal
thermal evaporation technique to protect the Li metal anode.[51] anode is utilizing 3D porous current collectors to accommo-
After the coating treatment, a Li–Sn alloy interface was formed date the infinite volume change during the Li plating/stripping
between Li metal and Sn due to their large electronegativity process. Porous current collectors are pivotal in LMBs because
differences. The Sn coating layer shows fast Li-ion diffusion, the porous structure and large surface area of the substrate
which can facilitate the uniform Li+ flux and homogeneous influence the morphology evolution of lithium metal anode
Li metal deposition. As a result, the Li metal anode with upon repeated Li plating/stripping.[86] With a smooth surface,
Sn coating delivers a low overpotential of 150 mV and good electrons are uniformly distributed along the lithium surface,
cycling stability for 80 h at a capacity of 1 mAh cm−2 under which can mitigate Li dendrite growth.[87] However, nonuni-
high current density of 10 mA cm−2. Li–S batteries with Sn form sites, such as grain boundaries and slip lines, exist on
coated Li metal anode exhibit superb cycling stability and high the surface of lithium metal, accelerating the local Li dissolu-
Coulombic efficiency of ≈99.5% at 2C over 500 cycles. The Sn tion and dendrite growth. The rough surface of lithium metal
coating layer cannot only suppress the Li dendrite growth, but induces concentrated areas of current densities, leading to
also effectively minimize the loss of the sulfur cathode mate- nonuniform Li dissolution and deposition.[25] These concen-
rial. In addition, Guo et al. and Liu et al. proposed a method trated areas also expose fresh Li to the electrolyte and promote
to coat lithiophilic heterogeneous Ag/Au and pure Ag layers the growth of irregular surface morphologies, such as lithium
on the surface of Li anodes through a simple in situ displace- dendrites, irreversible dead and pulverized lithium. Further-
ment reaction between metallic Li and the metal ion (Ag+ or more, the continuous Li dendrite growth results in the decay
Au3+) solution.[59,79] The lithiophilic Ag/Au or Ag layer evenly of Coulombic efficiency, because it damages the SEI layer and
covers the entire Li surface, enabling uniform Li nucleation generates new cracks and fractures, which expose more fresh
and dendrite-free Li deposition. The lithiophilic Ag coated Li Li to the electrolyte and in turn, generates more SEI. The con-
anodes deliver excellent cycling stability over 500 h with low tinuous generation of new SEI from the irreversible reaction
overpotential under high current density of 5 mA cm−2. Alu- between Li and the electrolyte not only reduces the Coulombic
minum is another ideal coating material for Li metal because efficiency, but also consumes the electrolyte, resulting in slug-
the formation of a Li–Al alloy layer shows high Li ion-conduc- gish reaction kinetics and failure of LMBs.[88–90] More impor-
tivity, high mechanical strength and good flexibility, which sig- tantly, the unrestricted Li dendrite growth is detrimental to the
nificantly eliminate Li dendrite growth. Lu et al. constructed long-term cycling of LMBs by penetrating the porous separator
a Li–Al alloy layer by displacement and alloying reaction and inducing an internal short circuit of the battery. Hence,
between AlCl3-ionic liquid and Li metal.[66] This Li–Al layer protecting the lithium metal anode by porous current collec-
delivers an improved mechanical strength up to 776 MPa, and tors and the formation of a stable lithium/electrolyte interface
the obtained Li metal anode achieves superior cycling stability are critical for LMBs.[91] Porous current collectors show signifi-
for 1600 h under the current density of 2 mA cm−2 and 1000 cant improvements in suppressing the lithium dendrite growth
cycles at the high current density of 20 mA cm−2. Additionally, while maintaining a high electronic and ionic conductivity. The
this dense Li–Al alloy layer prevents direct contact between electrochemical performances of Li metal anodes such as Cou-
metallic Li and polysulfides, enabling excellent cycling perfor- lombic efficiency and cycle life enhanced by various porous cur-
mance at high current density of 4C and low electrolyte/sulfur rent collectors are summarized in Figure 7 and Table 2.
Figure 7. a) The Coulombic efficiency and b) cycle life of different porous current collectors at various current densities.
3D porous metal substrates, such as Cu,[92,93] Ni,[94] Ti,[95] etc., a Li/LixC/LiySn (Li/C/Sn) composite anode by dispersing
are favorable hosts for Li metal due to their abundance, high con- CMK-3/Sn powder inside metallic Li at 270 °C to alloy Li with
ductivity, and high electrochemical stability. However, the cycling C and Sn.[160] The formed LixC and LiySn alloys enable the uni-
performance of Li metal anode based on these 3D metal substrates form Li deposition and inhibit the Li dendrite growth. As a
is inferior due to the weak lithiophilicity of Cu, Ni, and Ti during Li result, the formed composite anode shows an excellent cycling
deposition. To address this challenge, various approaches such as stability with a low overpotential of 10 mV even after 1800 h at a
nano-crystallization and surface coating are employed to improve capacity of 1 mAh cm−2 under a current density of 1 mA cm−2.
the lithiophilicity of these metal substrates. To date, various In addition to Sn, Ag, and Sb were also used for composite
nanoscale metal scaffolds such as nanoporous Cu formed by deal- Li anodes. Jin et al. prepared LixAg (x = 4.7–20) alloys by the
loying,[87] 3D nanoporous Cu derived by hydrogen bubble dynamic solid-solution reaction.[170] The Li is stripped from the alloy
template,[96] 3D Cu current collector with a biporous structure,[97] during the de-alloying process and plated onto the alloy during
free-standing Cu nanowire network formed by a reduction pro- the alloying process. The freshly generated Li atoms transfer
cess,[98] nanoporous Cu film by powder metallurgic approach,[99] inside the composite anode to form an alloy phase rather than
and so on, have been explored for lithium metal anodes. The nano- plate onto the surface, which effectively suppresses the Li
porous surface provides a large number of nanoscale protuberant dendrite growth. The solid-solution reaction involves smaller
tips, which can effectively enhance the Li wettability of 3D metals structural change during the alloying/de-alloying process, effec-
(Figure 8a). These tips also provide a broad/highly electroactive tively accommodating the volume change of Li–Ag alloy anode
area and a controlled electric field that enable a dendrite-free and during the repeated lithiation−de-lithiation process. The unique
high-performance lithium metal anode. inward-growth plating of Li delivers superior cycling stability
Surface coating on 3D metals with lithiophilic materials to over 2000 h with a low overpotential of 20 mV at a capacity of
form stable Li-based alloys and Li-based polymers is another 2 mAh cm−2 under a current density of 1 mA cm−2. Xu et al. pre-
effective strategy to improve the electrochemical performance pared a Li–Sb–Sn composite anode by metallurgically alloying
of Li metal anode. Due to the excellent lithiophilicity, Zn,[100–102] 5 wt%Sb-95 wt%Sn with Li foil, which shows various advan-
Sn,[103] CuxO,[104,105] and ZnO[106–108] are commonly used as tages such as less electrolyte decomposition, smaller volume
coating mediums for the fabrication of Li-based alloys through expansion, and nonflammability.[171] The theoretical calculations
the direct chemical reaction with metallic Li (Figure 8b,c). The and experimental results indicate that the existence of Sb signif-
formed Li-based alloys possess significantly higher strength and icantly reduces the porosity and long cracking damage, granting
modulus than bare metallic Li, which can effectively restrain the LCO/Li–Sb–Sn pouch cell a high initial volumetric energy
the growth of Li dendrites. Moreover, Li-based alloys provide density of 1073 Wg L−1 and an energy density of 909 Wh L−1
uniform nucleation sites during the Li plating process due to after 20 cycles. Furthermore, Cao et al. developed vertically ori-
their high electronic and ionic conductivity. Qiu et al. fabricated ented Li–Cu–Li arrays through traditional rolling and repeated
Table 2. Summary of electrochemical performances of Li metal anode with various porous current collectors.

1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 −2 −2
[87] 3D porous copper 0.5 mA cm , 1 mAh cm , 250 cycles, 97% ≈60 mV
0.2 mA cm−2, 1 mAh cm−2, 1000 h 50 mV
[91] 3D porous nickel LiFSI in DMC (0.51:1.1 by molar) 1 mA cm−2, 1 mAh cm−2, 600 h, 97.5% ≈150 mV
2 mA cm−2, 1 mAh cm−2, 250 h, ≈200 mV
2 mA cm−2, 1 mAh cm−2, 60 cycles
[92] Porous Cu film 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 1 mAh cm−2, 200 cycles, 94.6%
0.5 mA cm−2, 1 mAh cm−2, 700 h, 20 mV
1 mA cm−2, 1 mAh cm−2, 300 h 50 mV
[93] 3D porous Cu frameworks 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 250 h 50 mV
[94] Metallic nitrides modified 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 400 h, 13 mV
Ni foam 2 mA cm−2, 1 mAh cm−2, 300 h, 18 mV
5 mA cm−2, 1 mAh cm−2, 160 h, 39 mV
2 mA cm−2, 1 mAh cm−2, 150 cycles, 98.6%
[95] 3D Ti foam 1 m LiTFSI + 0.1 m Li2S8 in DOL/DME (1:1) + 1 wt% 1 mA cm−2, 1 mAh cm−2, 150 cycles, 95.6%
LiNO3 1 mA cm−2, 3 mAh cm−2, 150 cycles, 98.5%
[96] 3D porous Cu 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 0.5 mA cm−2, 1 mAh cm−2, 250 cycles, 98%
1 mA cm−2, 1 mAh cm−2, 800 h, 10 mV
3 mA cm−2, 1 mAh cm−2, 140 h ≈40 mV
[97] 3D biporous Cu 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 1 mA cm−2, 2 mAh cm−2, 2200 h, 10 mV
[98] Free-standing copper 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 + 5 × 1 mA cm−2, 1 mAh cm−2, 550 h, 40 mV
nanowire network 10−3m Li2S8 2 mA cm−2, 1 mAh cm−2, 200 cycles 98.6%
[99] Porous Cu film by powder 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1600 h ≈100 mV
metallurgic approach
[100] Zn/Sn@Cu foam 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1.5 mA cm−2, 1 mAh cm−2, 300 cycles, 98%
1 mA cm−2, 1 mAh cm−2, 1200 h ≈10 mV
[101] Zn@porous CuZn alloy 1 m LiPF6 in EC/EMC/DMC (1:1:1) 0.5 mA cm−2 −2
, 0.5 mAh cm , 800 cycles, 98.6%
0.5 mA cm−2, 1 mAh cm−2, 500 h 53 mV
−2 −2
[102] 3D porous CuZn current 1 m LiPF6 +0.1 m LiNO3 in EC/DEC (1:1) 0.5 mA cm , 1 mAh cm , 220 cycles, 95% 20 mV
collector 1 mA cm−2, 1 mAh cm−2, 150 cycles, 95% 25 mV
0.5 mA cm−2, 1 mAh cm−2, 450 h 15 mV
[103] Sn@porous Cu mesh 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 240 cycles, 98.25%
1 mA cm−2, 1 mAh cm−2, 800 h 20 mV
[104] Cuprite@Cu foam 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1000 h 15.8 mV
[105] CuO@Ti-mesh 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 500 cycles, 97.3%
10 mA cm−2, 1 mAh cm−2, 3200 h, 50 mV
20 mA cm−2, 1 mAh cm−2, 200 h 100 mV
[106] Aligned ZnO@Ni foam 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 150 cycles, 98.5% 50 mv
[107] ZnO@Ni foam 1 m LiPF6 in EC/DMC (1:1) 1 mA cm−2, 1 mAh cm−2, 300 cycles, 98%
1 mA cm−2, 2 mAh cm−2, 1200 h 20 mV
[108] 3D Cu–Au–ZnO–PAN–ZnO 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 1 mAh cm−2, 120 cycles, 99%
0.5 mA cm−2, 1 mAh cm−2, 1200 h 8 mV
Table 2. Continued.

−2 −2
[109] PAA@Cu foam 1 m LiPF6 in EC/DEC (1:1) + 10% FEC 1 mA cm , 1 mAh cm , 800 h, ≈50 mV
5 mA cm−2, 5 mAh cm−2, 350 h 206 mV
[110] PVDF-HFP-Cu 1 m LiTFSI + 0.1 m Li2S8 in 0.25 mA cm−2, 1 mAh cm−2, 100 cycles, 98%
DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 100 cycles, 96%
3 mA cm−2, 1 mAh cm−2, 900 h 100 mV
[111] PDA@laser-punched 3D Cu 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 1 mAh cm−2,
200 cycles, 97.25%
0.5 mA cm−2, 1 mAh cm−2, 1000 h 24 mV
[112] N-doped CNTs@Ni Foam 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2,
200 cycles, 98.2%
2 mA cm−2, 1 mAh cm−2, 100 cycles, 99% 30 mV
1 mA cm−2, 1 mAh cm−2, 1000 h 29 mV
[113] 3D N–carbon anchored 1 m LiTFSI + 0.1 m LiNO3 in DOL/DME (1:1) 0.5 mA cm−2, 2 mAh cm−2, 200 cycles, 97%
Cu arrays 0.5 mA cm−2, 1 mAh cm−2, 1000 h 40 mV
[114] N-Doped graphene@ 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 4 mAh cm−2, 100 cycles 98% 19 mV
3D porous Cu
[115] Carbon nanosheet@ 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 400 cycles, 97% 10 mV
Cu foam 3 mA cm−2, 1 mAh cm−2, 250 cycles, 98.2%
0.5 mA cm−2, 1 mAh cm−2, 1600 h 10 mV
[116] CNF@Cu scaffolds 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2,
250 cycles, ≈20 mV
5 mA cm−2, 1 mAh cm−2, 100 cycles, ≈50 mV
[117] g-C3N4@Ni foam 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 2 mA cm−2, 1 mAh cm−2, 300 cycles, 98%
1 mA cm−2, 1 mAh cm−2, 900 h, 15 mV
2 mA cm−2, 1 mAh cm−2, 500 h 20 mV
[120] 3D CNTs sponge-Al2O3 1 m LiPF6 in EC/DEC (1:1) 1 mA cm−2, 1 mAh cm−2, 100 h, 30 mV
3 mA cm−2, 1 mAh cm−2, 60 h, 36 mV
[121] Hollow carbon fibers film 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 2 mAh cm−2, 350 cycles, 99.5%
1 mA cm−2, 1 mAh cm−2, 1200 h, ≈18 mV
2 mA cm−2, 1 mAh cm−2, 600 h ≈20 mV
[122] Interconnected hollow 1 m LiTFSI in 0.25 mA cm−2, 1 mAh cm−2, 150 cycles, 99%
carbon nanospheres DOL/DME (1:1) + 1 wt% LiNO3 + 0.1 m Li2S8 0.5 mA cm−2, 1 mAh cm−2, 150 cycles, 98.5% 25 mV
[123] Co3O4-NC@carbon fiber 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1000 h, 18 mV
3 mA cm−2, 1 mAh cm−2, 200 h 50 mV
[124] CuxO@carbon felt 1 m LiPF6 in EC/DEC (1:1) 1 mA cm−2, 1 mAh cm−2, 1000 h 30 mV
[125] MOF-hollow carbon fibers 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1050 h 20 mV
[126] Nanoporous 1 m LiPF6 in EC/DEC (1:1) 0.5 mA cm−2, 1 mAh cm−2, 1800 h, 111 mV
Au@carbon fiber 1 mA cm−2, 1 mAh cm−2, 800 h ≈200 mV
[127] Au@carbon fiber paper 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1000 h, 18 mV
10 mA cm−2, 30 mAh cm−2, 1000 h ≈100 mV
[128] Co3O4 nanofiber@carbon 1 m LiTFSI in DOL/DME (1:1) 1 mA cm−2, 1 mAh cm−2, 800 h, 50 mV
sheet 20 mA cm−2, 1 mAh cm−2, 12 h 280 mV
[129] TiN@carbon nanofiber 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 300 cycles, 95.8%
1 mA cm−2, 1 mAh cm−2, 600 h 20 mV
Table 2. Continued.

[130] LiC6 layers on carbon fiber 1 m LiTFSI in DOL/DME (1:1) + 5 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1000 h 25 mV
−2 −2
[131] SiO2–TiO2/porous 1 m LiTFSI + 0.2 m LiNO3 in DOL/DME (1:1) 2 mA cm , 1 mAh cm , 100 cycles, 20 mV
carbon fiber 4 mA cm−2, 1 mAh cm−2, 350 cycles 15 mV
[132] CNTs modifying carbon 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 500 h, 9 mV
cloth film 2 mA cm−2, 1 mAh cm−2, 500 h, 23 mV
5 mA cm−2, 1 mAh cm−2, 500 h, 71 mV
[133] CNT-carbon nanosheets 1 m LiTFSI in TEGDME + 2 wt% LiNO3 0.5 mA cm−2,1 mAh cm−2,
500 cycles, 95.6%
film 0.5 mA cm−2, 1 mAh cm−2, 1500 h ≈100 mV
[134] 3D porous carbon matrix 1 m LiPF6 in EC/DEC (1:1) 3 mA cm−2, 1 mAh cm−2, 100 cycles ≈70 mV
with Si coating
[135] Carbon cloth with 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 500 h, 50 mV
Zn nanoclusters 3 mA cm−2, 1 mAh cm−2200 h 120 mV
[136] N,P co-doped carbon cloth 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 3 mA cm−2, 1 mAh cm−2, 600 h, 30 mV
5 mA cm−2, 1 mAh cm−2, 240 h 70 mV
[137] Vertical graphene @CNFs 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 200 cycles, 97.6%
0.5 mA cm−2, 1 mAh cm−2, 1000 h 13 mV
−2 −2
[138] S-doped carbon nanospheres 1 m LiPF6 in EC/DMC (1:1) + 10 vol% FEC 0.5 mA cm , 1 mAh cm , 220 cycles, 97.5%
0.5 mA cm−2, 1 mAh cm−2, 1600 h, 20 mV
1 mA cm−2, 1 mAh cm−2, 220 h 40 mV
[139] O,N co-doped porous 4 m LiFSI in DME 2 mA cm−2, 2 mAh cm−2, 400 cycles, 99.83%
carbon granules 2 mA cm−2, 6 mAh cm−2, 115 cycles 99.53%
[140] Li4.4Sn@hollow graphene 1 m LiTFSI in DOL/DME (1:1) 0.5 mA cm−2, 1 mAh cm−2, 1000 h, 18 mV
spheres 1 mA cm−2, 1 mAh cm−2, 600 h, 34 mV
[141] Wrinkled graphene cages 10 m LiFSI in DMC 1 mA cm−2, 1 mAh cm−2, 140 cycles, 99%
[142] 3D N-doped graphene 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1400 h, 15 mV
10 mA cm−2, 5 mAh cm−2, 500 h 80 mV
[143] MgF2@porous graphene 1 m LiPF6 in EC/DEC (1:1) + 2% VC + 1 wt% FEC 1 mA cm−2, 1 mAh cm−2, 450 h 20 mV
[144] Vertically aligned graphene 1 m LiPF6 in EC/DEC (1:1) 1 mA cm−2, 1 mAh cm−2, 2000 h, 68 mV
10 mA cm−2, 1 mAh cm−2, 100 h, 400 mV
20 mA cm−2, 1 mAh cm−2, 50 h <1 V
[145] Expanded-graphite film 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1000 h, 75 mV
10 mA cm−2, 1 mAh cm−2, 300 h, 120 mV
1 mA cm−2, 3 mAh cm−2, 800 h 50 mV
[146] Horizonal graphene film 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1000 h, 100 mV
3 mA cm−2, 1 mAh cm−2, 250 h ≈80 mV
[147] Soft lithiophilic graphene 1 m LiTFSI in DOL/DME (1:1) + 0.2 m LiNO3 2 mA cm−2, 2 mAh cm−2, 1800 h ≈20 mV
aerogel
[148] 3D graphene foam 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 320 h, 25 mV
4 mA cm−2, 1 mAh cm−2, 80 h 50 mV
[149] Interconnected 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 10 mA cm−2, 1 mAh cm−2, 500 cycles, 250 mV
channel-Like carbon 1 mA cm−2, 3 mAh cm−2, 200 cycles ≈50 mV
[150] CNTs@melamine sponges 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 5 mA cm−2, 5 mAh cm−2, 40 cycles, 90%
5 mA cm−2, 5 mAh cm−2, 160 h, 60 mV
10 mA cm−2, 5 mAh cm−2, 500 h 100 mV
[151] POF@CNTs networks 1 m LiTFSI in DOL/DME (1:1) + 5 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 750 cycles, 98.5%
1 mA cm−2, 1 mAh cm−2, 450 h, 100 mV
5 mA cm−2, 1 mAh cm−2, 70 h 60 mV
[152] Vertically aligned 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 2 mAh cm−2, 100 cycles, 97%
CNFs@Cu foil 1 mA cm−2, 2 mAh cm−2, 500 h, 20 mV
5 mA cm−2, 5 mAh cm−2, 550 h 200 mV
Table 2. Continued.

−2 −2
[153] MXene framework 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm , 0.5 mAh cm , 250 cycles, 98.22%
1 mA cm−2, 0.5 mAh cm−2, 150 cycles, 97.31%
0.5 mA cm−2, 1 mAh cm−2, 200 cycles, 98.45%
0.5 mA cm−2, 0.5 mAh cm−2, 350 h 15 mV
−2 −2
[154] Ti3C2Tx MXene@melamine 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 5 mA cm , 5 mAh cm , 100 cycles, 98%
foam 50 mA cm−2, 50 mAh cm−2, 100 cycles, 99%
10 mA cm−2, 10 mAh cm−2, 3500 h 13 mV
[155] Ti3C2Tx MXene@Zn paper 0.11 m LiTFSI in DOL/DME (1:1) 1 mA cm−2, 1 mAh cm−2, 400 cycles, 94.13% 41 mV
1 mA cm−2, 1 mAh cm−2, 300 h 37.5 mV
[156] MXene/graphene framework 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 0.5 mA cm−2, 0.5 mAh cm−2, 140 cycles, 98%
0.5 mA cm−2, 2 mAh cm−2, 140 cycles, 99%
0.5 mA cm−2, 5 mAh cm−2, 2700 h, 99%
5 mA cm−2, 1 mAh cm−2, 400 h, 25 mV
20 mA cm−2, 5 mAh cm−2, 117 h 30 mV
[157] S,N co-doped porous 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 250 cycles, 98%
carbon nanosheets 1 mA cm−2, 5 mAh cm−2, 1500 h <20 mV
[158] N-doped carbon matrix 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 200 cycles, 98.8%
[159] PI-coating with vertical 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 0.5 mAh cm−2, 240 cycles, 97.6%
channels 2 mA cm−2, 0.5 mAh cm−2, 150 cycles, 92.9%
3 mA cm−2, 0.5 mAh cm−2, 140 cycles 88.6%
[160] Li/LixC/LiySn composites 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1800 h, 10 mV
2 mA cm−2, 1 mAh cm−2, 1200 h, 20 mV
5 mA cm−2, 1 mAh cm−2, 300 h 50 mV
[161] Carbon-PVDF-LiNO3 1 m LiPF6 in EC/DMC (1:1) 0.25 mA cm−2, 0.5 mAh cm−2, 300 cycles, 98.4% 37.2 mV
mixture 1 mA cm−2, 1 mAh cm−2, 200 cycles 97.9%
[162] Conductive-dielectric 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 0.5 mA cm−2, 1 mAh cm−2, 600 cycles, 97%
gradient framework 5 mA cm−2, 2 mAh cm−2, 90 cycles, 97.1%
1 mA cm−2, 1 mAh cm−2, 800 h 25 mV
[163] 3D printed N-doped 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2,
10 mAh cm−2,
100 cycles, 97.9%
carbon framework 2 mA cm−2, 10 mAh cm−2, 80 cycles, 96.5%
10 mA cm−2, 2 mAh cm−2, 150 h 10 mV
[164] COF-LZU1 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2,1 mAh cm−2,
200 cycles, 99.3% 50 mV
0.5 mA cm−2, 0.5 mAh cm−2, 2000 h ≈40 mV
[165] Coiled Li with glass fiber 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 1000 h, ≈10 mV
2 mA cm−2, 1 mAh cm−2, 250 h, ≈25 mV
5 mA cm−2, 1 mAh cm−2, 150 h, ≈50 mV
[166] Carbon films 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2,1 mAh cm−2,
600 h, 30 mV
3 mA cm−2, 1 mAh cm−2, 150 h 50 mV
[167] Laser-induced silicon oxide 4 m LiFSI in DME 2 mA cm−2, 2 mAh cm−2, 250 cycles, 99.3%
2 mA cm−2, 2 mAh cm−2, 550 h 100 mV
[168] Mg doped Li–LiB alloy 1 m LiPF6 in EC/EMC/DMC (1:1:1) + VC 0.5 mA cm−2, 0.5 mAh cm−2, 400 h, 40 mV
1 mA cm−2, 0.5 mAh cm−2, 300 h 150 mV
[169] Metal fluoride spansules 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 600 cycles, 98.5%
1 mA cm−2, 1 mAh cm−2, 1600 h 20 mV
−2,
[170] Li–Ag alloy 1 m LiTFSI in DOL/DME (1:1) 1 mA cm 2 mAh cm−2,
2000 h, 20 mV
[171] Self-supporting 1 m LiPF6 in EC/DEC (1:1) + 10% FEC + 1% VC 10 mA cm−2, 10 mAh cm−2, 120 h ≈150 mV
Li–Sn–Sb foil anode
[172] PDA@3D Cu 1 m LiPF6 in EC/DEC (1:1) 1 mA cm−2, 1 mAh cm−2, 500 cycles 90%
Table 2. Continued.

[173] Li3N/LiAl and 1 m LiTFSI in DOL/DME (1:1) 0.5 mA cm−2, 1 mAh cm−2, 1800 h, ≈20 mV
3D composite structure 1 mA cm−2, 1 mAh cm−2, 550 h ≈40 mV
[174] Glass fiber modified Cu foil 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiNO3 0.5 mA cm−2, 0.5 mAh cm−2, 90 cycles, 98%
[175] Graphitized carbon fibers 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 8 mAh cm−2, 70 cycles, 98%
2 mA cm−2, 8 mAh cm−2, 300 h ≈30 mV
[176] Copper nitride nanowires 1.3 m LiPF6 in EC/DEC (3:7) + 5 wt% FEC 1 mA cm−2, 1 mAh cm−2, 900 h, 50 mV
3 mA cm−2, 1 mAh cm−2, 250 h 100 mV
[177] 3D TiC/C core/shell nanowire 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 200 cycles, 42.5 mV
[178] 3D printing vertically 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 3000 h, 15 mV
aligned ZnO@CNTs 10 mA cm−2, 10 mAh cm−2, 1500 h 40 mV
[179] Double-shelled C@MoS2 1 m LiTFSI in DOL/DME (1:1) + 1 wt% LiNO3 1 mA cm−2, 1 mAh cm−2, 500 cycles 98%
[180] Mesoporous 1.3 m LiPF6 in EC/DEC (1:1) + 10 wt% FEC 1 mA cm−2, 1 mAh cm−2, 100 cycles, 40 mV
AlF3 framework 10 mA cm−2, 1 mAh cm−2, 100 cycles, 250 mV
[181] Onion-Like Graphitic 1 m LiTFSI in DOL/DME (1:1) 2 mA cm−2, 1 mAh cm−2, 800 h ≈20 mV
Carbon Nanospheres
stacking approaches.[29] These Li–Cu–Li arrays can regulate the metal alloys and arrays is an effective method to mitigate the Li
Li-ion flux and the electric field due to the uniform distribu- dendrite growth and improve the cycle life of Li metal anode.
tion of Cu arrays. It facilitates the formation of a stable SEI In addition to metal and metal oxide composites/alloys,
layer and suppresses the Li dendrite growth. The Cu arrays can polymers such as polyacrylic acid (PAA),[109] polyvinylidene dif-
also act as a “dam” to guide the deposition of Li, achieving a luoride,[110] and polydopamine,[111] can also react with metallic
long cycle life of over 2000 h at a deep stripping and plating Li to form Li-based polymers with high flexibility and ionic con-
capacity up to 50 mAh cm−2 under a high current density of ductivity, regulating the interface and suppressing the forma-
20 mA cm−2. Therefore, these results confirm that developing tion of Li dendrites. Other types of coating materials, including
Figure 8. a) Schematic illustration of the fabrication of LiF-Li–Cu composite anodes. Reproduced with permission.[99] Copyright 2020, WILEY-VCH
GmbH & Co. KGaA. b) The structure evolution from CuZn alloy to 3D porous CuZn, and finally to Li/CuZn composite. Reproduced with permission.[101]
Copyright 2020, American Chemical Society. c) Schematic diagram of the synthetic procedure of LZNF. Reproduced with permission.[106] Copyright
2019, Elsevier Ltd. d) Schematic illustration of the fabrication procedures of the hierarchical N-doped CNTs/Ni Foam scaffold (denoted as NCNT/NF).
Reproduced with permission.[112] Copyright 2020, Elsevier B.V.
heteroatoms-doped carbon,[112–114] carbon nanomaterials with high with metallic Li, so lithiophilic mediums, such as Co3O4-
defects[115,116] and graphitic carbon nitride (g-C3N4),[117] exhibit high carbon nanoflake,[123] CuxO,[124] MOF,[125] nanoporous Au,[126,127]
binding energy and wettability with Li due to the existence of Co3O4 nanofiber,[128] TiN,[129] LiC6 layers,[130] SiO2–TiO2,[131]
defects, which are effective for promoting the uniform plating of CNTs,[132,133] Si,[134] Zn nanoclusters,[135] and vertical graphene
Li and suppressing the growth of Li dendrites (Figure 8d). nanosheets[136,137] are employed to enable the uniform nuclea-
Carbonaceous materials with the advantages of lightweight, tion of Li metal during Li plating process (Figure 9a). In
abundance, high stability, high electronic conductivity, and low addition, carbon allotropes with unique architectures, such
packing cost represent another type of promising porous current as carbon sphere-based materials,[138–140] wrinkled graphene
collectors for lithium metal anode.[25,118] The porous structure and cages,[141] 3D N-doped nanoporous graphene,[142] graphene
exceptional flexibility of carbon accommodate the infinite volume films,[143–148] hollow carbonized eggplant,[149] and CNTs net-
change of lithium metal and mitigate the Li dendrite growth. works,[150–152] provide enhanced wettability with Li metal, exhib-
More importantly, carbonaceous materials are versatile as they iting fast charge transfer for the Li/Li+ redox reaction and a
can be fabricated into different structures and morphologies uniform lithium stripping/plating process (Figure 9b–d). The
while maintaining high electronic conductivity.[119–122] novel 3D carbon substrates can hinder lithium dendrite growth,
Carbon fiber is a type of carbonaceous material widely used reduce side reactions, accommodate infinite volume change,
as a porous current collector for Li metal anode. However, the enhance the stability of the SEI layer, and improve the electro-
surface of the carbon fiber shows unsatisfactory wettability chemical performance of lithium metal anodes.
Figure 9. a) Schematic illustration for the fabrication of CFC/Co-NC@Li anode. Reproduced with permission.[123] Copyright 2019, Elsevier B.V. b) The
graphical illustration of the synthetic process and plating/stripping behavior of MgxLiy/LiF–Li-rGO anode. Reproduced with permission.[143] Copyright
2019, Elsevier B.V. c) Schematic illustration of the fabrication procedure of rAGA-Li. Reproduced with permission.[144] Copyright 2020, WILEY-VCH
GmbH & Co. KGaA. d) Schematic illustration of the synthetic procedure for the Au-GA. Reproduced with permission.[147] Copyright 2020, WILEY-VCH
GmbH & Co. KgaA. e) The schematic diagram of fabricating flexible layered Ti3C2Tx MXene@Zn paper. Reproduced with permission.[155] Copyright
2019, American Chemical Society.
MXene, a 2D transition metal carbide, shows low a Li+ dif- high-energy-density and high-power-density LMBs. Therefore,
fusion barrier and good electronic conductivity, rendering it developing advanced porous current collectors with high con-
an ideal current collector for Li metal deposition. The Ti3C2Tx- ductivity, high flexibility, and high lithiophilicity is a promising
based 3D scaffolds, such as Ti3C2Tx/liquid metal framework,[153] research direction for safe, stable, and high-energy LMBs.
Ti3C2Tx/melamine foam,[154] Ti3C2Tx/Zn paper,[155] and Ti3C2Tx/
graphene framework,[156] all exhibit improved structural sta-
bility and electrochemical performance after compositing with 2.3. Liquid Electrolyte Design
metallic Li. Tian et al. designed and fabricated a freestanding
Ti3C2Tx/Zn paper by combining two methodologies: vacuum Although surface coating and porous current collectors have
filtration and electrodeposition (Figure 9e).[155] The Ti3C2Tx/Zn demonstrated great success in improving the safety and cycle
paper can be used as a 3D current collector for Li metal anode, life of LMBs, challenges for achieving high-Coulombic-effi-
in which Zn is utilized as a nucleation agent to uniformly ciency (>99.2%) and long-cycle-life (>1000 cycles) Li metal
deposit metallic Li and MXene is utilized as a conductive anodes persist. To further improve the performance of LMBs,
backbone to lower the areal current density for the suppres- considerable efforts have been devoted to designing new
sion of Li dendrites growth. The Ti3C2Tx/Zn paper provides organic electrolytes, since the liquid electrolyte plays a critical
an average Coulombic efficiency of 97.69% over 600 cycles at role in the formation of the SEI layer. SEI consists of decom-
the capacity of 1 mAh cm−2 under 1 mA cm−2, exhibiting a sig- position products of the liquid electrolyte, thus the composi-
nificant improvement over Cu foil. Moreover, the Li|MXene@ tion and content of the electrolyte determine the properties of
Zn@Li cells deliver an excellent cyclability for 300 h with a low the SEI layer. To achieve high Li plating/stripping Coulombic
overpotential of 37.5 mV at the capacity of 1 mAh cm−2, which efficiency in LMBs, a uniform and stable SEI layer is indispen-
further proves that this MXene-Zn composite current collector sable.[182–186] A stable and robust SEI layer also facilitates the
can effectively inhibit the formation and growth of Li dendrites. uniform lithium deposition and mitigates Li dendrite growth.
In addition, MXene can also be used as a lithiophilic and con- To date, various new liquid electrolytes have been designed
ductive coating on the surface of lightweight and flexible 3D and synthesized to tune the properties of the SEI layer for
porous organic foam to prepare 3D Li metal anodes. Shi et al. high-efficiency LMBs. For example, fluorinated electrolytes,
proposed a cost-effective, flexible, and conductive 3D MXene- high concentration electrolytes, electrolyte additives, lithium
melamine foam (MF) current collector prepared by soaking MF bis(fluorosulfonyl) imide (LiFSI)-based electrolytes, and so
in Ti3C2Tx MXene ink.[154] Consequently, the 3D MXene-MF on,[33,187,188] have been reported for high-Coulombic-efficiency,
current collector achieves a high Coulombic efficiency of 99% long-cycle-life, and dendrite-free LMBs. The electrochemical
at an areal capacity of 50 mAh cm−2 under the current density performances of Li metal anode enhanced by various liquid
of 50 mA cm−2 for 400 cycles. More importantly, the MXene- electrolytes are summarized in Figure 10 and Table 3.
MF-Li composite anode delivers excellent cycling stability up to LiF with the largest bandgap energy and widest electro-
3800 h with a low overpotential of 13 mV at an areal capacity of chemical stability window is a key component in SEI. To date,
10 mAh cm−2 under the current density of 10 mA cm−2, dem- fluoroethylene carbonate (FEC) has been widely used in elec-
onstrating the high potential of MXene-based materials for trolytes to form a stable and robust LiF-rich SEI layer, which
Figure 10. a) The Coulombic efficiency and b) cycle life of different liquid electrolytes at various current densities.
Table 3. Summary of electrochemical performances of Li metal anode in various liquid electrolytes.

[19] In situ formation of SrF2 layer 2 m LiFSI in DME 1 mA cm−2 −2
, 2 mAh cm , 120 cycles, 60 mV
[183] Bifunctional anionic electrolyte 1 m LiPF6 + 2% Tris (2, 2, 2-trifluoroethyl) 0.1 mA cm−2, 1 mAh cm−2, 100 cycles, 96% 6.3 mV
additive borate (TTFEB) in EC/DMC (1:2) 0.5 mA cm−2, 1 mAh cm−2, 100 cycles, 91%
1 mA cm−2, 2 mAh cm−2, 1000 h, 16 mV
2 mA cm−2, 2 mAh cm−2, 800 h 22 mV
[184] Fluoroethylene carbonate 1 m LiPF6 in FEC/DMC (1:4) 2 mA cm−2, 3.3 mAh cm−2, 3600 h, ≈20 mV
additive 0.5 mA cm−2, 3.3 mAh cm−2, 1800 h, ≈50 mV
[185] (CH3)3Si-N[(FSO2)(n-C4F9SO2)] 1.0 m LiTFSI-DOL/DME (1:1) + 5 wt% 0.25 mA cm−2, 0.5 mAh cm−2, 200 cycles, 98.6%
additive TMS-FNFSI 0.5 mA cm−2, 1 mAh cm−2, 110 cycles, 97.3%
0.5 mA cm−2, 1 mAh cm−2, 1200 h 25 mV
[186] Lithium difluoro(oxalate)borate 1.2 m LiFSI+0.15 m LiDFOB in EC/EMC/BTFE 0.5 mA cm−2, 1 mAh cm−2, 200 cycles 98.5%
additive
[187] PSD additive 1 m LiTFSI+4 wt% LiNO3 in 2 mA cm−2, 1 mAh cm−2, 420 cycles, 99.1%
DOL/DME (1:1) with PSD-90 2 mA cm−2, 2 mAh cm−2, 250 cycles, 99% ≈47 mV
[188] Combinational additives 0.6 m LiTFSI-0.4 m LiBOB in 0.5 mA cm−2, 0.5 mAh cm−2, 800 h ≈10 mV
EC/EMC (7:3 by weight) + 0.6 wt%
LiPF6 + 2 wt% VC + 2 wt% FEC
[190] Non-flammable fluorinated 1 m LiPF6 in FEC/FEMC/HFE (2:6:2) 0.2 mA cm−2, 1 mAh cm−2, 500 cycles, >99.2%
electrolyte 0.5 mA cm−2, 2 mAh cm−2, 600 cycles 99% 39 mV
−2 −2
[191] Molecular design for electrolyte 1 m LiFSI in fluorinated 1,4-dimethoxylbutane 0.5 mA cm , 1 mAh cm , 50 cycles ≈99.52% ≈40 mV
solvents
[192] AlCl3 additive 1 m LiPF6 in EC/DMC/DEC (1:1:1 by weight) 0.5 mA cm−2, 2 mAh cm−2, 150 cycles, 99% 30 mV
+ 8 wt% AlCl3 0.5 mA cm−2, 1 mAh cm−2, 900 h ≈150 mV
[193] SiCl4 additive 1 m LiPF6 + 0.1 m SiCl4 in PC 1 mA cm−2, 1 mAh cm−2, 100 h, ≈150 mV
3 mA cm−2, 1 mAh cm−2, 350 h ≈500 mV
[194] localized high-concentration 1.2 m LiFSI in DMC/BTFE (1:2 by molar) 1 mA cm−2, 1 mAh cm−2, 200 cycles 99%
electrolyte
[195] Fluorine-donating electrolytes 7 m LiFSI in FEC 0.25 mA cm−2, 0.5 mAh cm−2, 400 cycles 99.6% 90 mV
[196] Fluorinated ether and ester 1.2 m LiPF6 + 0.15 m LiDFOB in 1 mA cm−2 −2
, 1 mAh cm , 200 cycles 98% 60 mV
FEC/DMC/HFE (1:1:1)
[197] Highly concentrated electrolytes 4 m LiFSI in DME 0.2 mA cm−2, 1 mAh cm−2, 500 cycles, 99.1%
1 mA cm−2, 1 mAh cm−2, 500 cycles, 98.5% 50 mV
4 mA cm−2, 1 mAh cm−2, 1000 cycles, 98.4% ≈100 mV
10 mA cm−2, 1 mAh cm−2, 500 cycles 97% 300 mV
[198] Cyclic carbonate solvent 1.2 m LiPF6 in DFEC/EMC (3:7) 2 mA cm−2, 1 mAh cm−2, 1000 h, 15 mV
[199] Dual-salt electrolyte 1 m LiPO2F2 and 1 m LiFSI in DME 0.5 mA cm−2, 1 mAh cm−2, 190 cycles 96.4%
[200] Additive-assisted dual-salt 1 m LiTFSI–LiTFPFB + 0.05 m LiPO2F2 2 mA cm−2, 1 mAh cm−2, 300 h ≈200 mV
electrolyte in PC/EC/EMC (1:1:3 by weight)
[201] Liquefied gas electrolytes 0.3 m LiTFSI + 0.3 m THF in FM/CO2 (19:1) 0.5 mA cm−2, 0.5 mAh cm−2, 500 cycles 99.6% ≈70 mV
[202] Liquefied gas electrolytes 1.2 m LiTFSI + 1 m acetonitrile in FM/CO2 (19:1) 3 mA cm−2, 3 mAh cm−2, 200 cycles 99.4% ≈50 mV
[203] Hybrid ionic liquid electrolyte 2 m LiTFSI/Py13TFSI in DOL/DME 1 mA cm−2, 1 mAh cm−2, 360 cycles 99.1%
[204] Hybrid electrolyte 1 m LiPF6 in EC/EMC/DMC + 5 wt% 0.1 mA cm−2, 0.2 mAh cm−2, 400 h 15 mV
TPGDA + 0.1 wt% AIBN
[205] Fluorinated orthoformate 1 m LiFSI in DME/TFEO (1:9 by weight) 0.5 mA cm−2, 1 mAh cm−2, 700 h 99.5%
electrolytes
[206] “Ion−solvent-coordinated” 1 m LiTFSI/triethylphosphate (TEP) (1:1.5) 0.2 mA cm−2, 1 mAh cm−2, 340 cycles 99.3%
nonflammable electrolyte
Table 3. Continued.

[207] High-concentration LiFSI/AN/VC ( 0.52:1:0.09) 0.5 mA cm−2, 1 mAh cm−2, 2500 h, 20 mV
acetonitrile-based electrolytes 2 mA cm−2, 4 mAh cm−2, 2000 h <80 mV
[208] Electrolytes enriched 1 m LiPF6 in EC/DMC (1:1) + 2 wt% crown ether 1 mA cm−2, 0.5 mAh cm−2, 180 h 100 mV
by crown ethers
[209] Concentrated ternary-salts 2 m LiFSI + 1 m LiTFSI in 0.5 mA cm−2, 1 mAh cm−2, 450 cycles 99.6% <20 mV
electrolyte DOL/DME (1:1) + 3 wt% LiNO3
[210] Countersolvent electrolytes LiFSI/DMC/TTE (1:1.5:2.5) 1 mA cm−2, 1 mAh cm−2, 400 cycles 98.6%
[211] Full fluorosulfonyl electrolyte 2.5 m LiFSI + 0.2 m LiPF6 in FSA 0.5 mA cm−2, 0.5 mAh cm−2, 400 cycles, 99.03%
0.5 mA cm−2, 0.5 mAh cm−2, 1100 h 30 mV
[212] Solvent modification 2.0 m LiPF6 in mix THF 3 mA cm−2, 1 mAh cm−2, 200 cycles 99.83% 40 mV
[213] Vinylethylene carbonate 1 m LiPF6 in VEC 1 mA cm−2 −2
, 1 mAh cm , 1000 h, 250 mV
electrolyte 0.5 mA cm−2, 0.5 mAh cm−2, 1400 cycles 98.1% 52.5 mV
[214] Bulky anion lithium salt 0.5 m (Li[B(hfip)4]) in DME 1 mA cm−2, 1 mAh cm−2, 2000 h 270 mV
−2 −2
[215] High-fluorinated electrolytes 1 m LiFSI/OFE + DME5 1 mA cm , 1 mAh cm , 250 cycles 99.3%
[216] Interphases suppressed 1 m LiHFDF in DOL/DME (1:1) + 1 wt% LiNO3 0.5 mA cm−2, 1 mAh cm−2, 1000 h ≈25 mV
lithium salt
[217] Manipulate solvation structure 1 m LiFSI + 0.3 m LiNO3 in FEC/GBL (1:2) 0.5 mA cm−2, 1 mAh cm−2, 200 cycles 98.1%
in ester electrolyte
[218] Solvent molecule cooperation 1 m LiClO4 in EC/ES (1:1) 1 mA cm−2, 2 mAh cm−2, 190 cycles, 97%
0.5 mA cm−2, 0.5 mAh cm−2, 450 cycles, 97%
1 mA cm−2, 2 mAh cm−2, 900 h 200 mV
[219] lithium polysulfide and lithium 1 m LiTFSI in DOL/DME (1:1) + 0.18 m 2 mA cm−2, 2 mAh cm−2, 120 cycles 99.4% ≈150 mV
nitrate additives Li2S8 + 1 wt% LiNO3
[220] Methyl viologen additive 1 m LiTFSI + 5 wt% LiNO3 + 0.5 wt% methyl 1 mA cm−2, 1 mAh cm−2, 400 cycles, 98.2% ≈50 mV
viologen in DOL/DME (1:1) 2 mA cm−2, 1 mAh cm−2, 400 cycles 98.7% ≈100 mV
[221] Fluorinated compounds 3 m LiTFSI in DME/TTE (8:2) + 1 wt% FEC 2 mA cm−2, 1 mAh cm−2, 500 cycles 99.3% 66 mV
additives
[222] LiDFP/VC synergy additives 1 m LiClO4 in EC/EMC (3:7 by weight) + 2 wt% 0.5 mA cm−2, 1 mAh cm−2, 80 cycles, 95%
LiDFP + 2 wt% VC 0.5 mA cm−2, 1 mAh cm−2, 800 h ≈20 mV
[223] Functional electrolyte additive 1 m LiTFSI in DOL/DME (1:1) + 2 wt% LiI 2 mA cm−2, 1 mAh cm−2, 1200 h, 250 mV
[224] SOCl2 additive 1 m LiPF6 in PC/EC/DEC (1:4:5) + 2% SOCl2 3.8 mA cm−2, 1 mAh cm−2, 100 h 115 mV
[225] Nitrofullerene additive 1 m LiPF6 in EC/DEC (1:1) + 5 × 10−3m C60(NO2)5 0.5 mA cm−2, 0.5 mAh cm−2,
600 h, 48 mV
1 mA cm−2, 1 mAh cm−2, 400 h 50 mV
[226] Adiponitrile additive 0.8 m LiTFSI + 0.2 m LiDFOB + 0.05 m 1.8 mA cm−2, 1.8 mAh cm−2, 100 cycles, 97%
LiPF6 in EMC/FEC (3:1) + 1 wt% adiponitrile 1.8 mA cm−2, 1.8 mAh cm−2, 900 h 58 mV
[227] Trimethylsilyl azide additive 1 m LiPF6 in EMC/FEC (3:1) + 0.1 m TSA 2 mA cm−2, 2 mAh cm−2, 1200 h ≈250 mV
[228] High concentration electrolyte 10 m LiFSI in EC/DMC (1:1) 0.2 mA cm−2, 1 mAh cm−2, 250 cycles, 99.3%
1 mA cm−2, 1 mAh cm−2, 1000 h 50 mV
−2,
[229] Long-lasting dual-function 1 m LiTFSI +1 m LiFSI in 1 mA cm 1 mAh cm−2,
400 cycles, 99.1%
electrolyte additive DOL/DME (1:4) + 0.02 m KPBS 2 mA cm−2, 2 mAh cm−2, 250 cycles, 98.7%
2 mA cm−2, 2 mAh cm−2, 1000 h, ≈30 mV
4 mA cm−2, 2 mAh cm−2, 500 h ≈65 mV
[230] Localized high-concentration LiFSI-3TMS-3TTE 0.5 mA cm−2, 1 mAh cm−2, 150 cycles 98.8%
sulfone electrolytes
[231] Metal–organic framework 1 m LiTFSI in DOL/DME (1:1) + MOF 5 mA cm−2, 2.5 mAh cm−2, 1000 h, 35 mV
modified electrolyte 10 mA cm−2, 5 mAh cm−2, 800 h, 80 mV
10 mA cm−2, 10 mAh cm−2, 800 h 114 mV
[232] Dual-additive electrolyte 1 m LiPF6 in EMC/FEC (7:3) + 3 wt% 1 mA cm−2, 1 mAh cm−2, 300 cycles, 98.5%
LiNO3 + 1 wt% TPFPB 1.5 mA cm−2, 3 mAh cm−2, 400 h ≈100 mV
[233] LiPF6 additive 0.6 m LiTFSI + 0.4 m LiBOB in EC/EMC 0.5 mA cm−2, 1 mAh cm−2, 200 h ≈200 mV
(4:6 by weight) + 0.05 m LiPF6
Table 3. Continued.

[234] Non-flammable electrolytes LiFSI-TEP (1:2) + FEC/LiBOB 0.2 mA cm−2, 1 mAh cm−2, 140 cycles 99%
with high salt-to-solvent ratios
[235] Thiophenol additive 1 m LiTFSI in DOL/DME (1:1) + 80 × 10−3m BTB 2 mA cm−2, 2 mAh cm−2, 280 h ≈40 mV
−2 −2
[236] Octaphenyl polyoxyethylene 1 m LiPF6 in PC/EC/DEC (1:4:5) + 5% OP 1 mA cm , 0.5 mAh cm , 400 cycles, ≈100 mV
additive 2 mA cm−2, 1 mAh cm−2, 200 cycles, ≈125 mV
4 mA cm−2, 1 mAh cm−2, 160 cycles ≈200 mV
is pivotal for battery performance. The properties of the SEI collector. It reduces the capacity and lowers the Coulombic
layer determine the interfacial charge transfer. Heterogeneous efficiency of LMBs. In comparison, the uniform Li dissolution
distribution of crystalline grains within the SEI layer can dete- in multilayer SEI was observed in the EC/DEC-based elec-
riorate the morphology of the Li metal surface, resulting in trolyte with 10 vol% FEC additive. The uniform distribution
sluggish Li-ion transport. To understand the SEI formation of crystalline grains on the top of the amorphous matrix is
mechanism in different structures of lithium metal anodes, shown in the multilayer SEI. The amount of inactive Li metal
Cui et al. used cryo-electron microscopy to monitor the Li dis- is one-third of that formed in the EC/DEC-based electrolyte
solution and deposition process upon cycling.[189] The cryo- without FEC additive. The FEC additive is beneficial for the
images and schematic of Li dendrites generated from the formation of the favorable multilayer SEI nanostructure,
EC/DEC-based electrolyte with and without FEC additives which enables the even distribution of crystalline grains and
are shown in Figure 11a,b. Decomposition products from the uniform Li stripping. These fundamental insights of SEI for-
electrolyte without FEC are distributed non-uniformly within mation using the electrolyte with FEC additive facilitate the
the SEI to form a mosaic of both crystalline and amorphous battery material and electrolyte research.
phases. A notched structure shows up on the surface after Li Continuous research in developing new fluorinated elec-
dissolution, which triggers the failure of the Li metal anode. trolytes for LiF-rich SEI layer has been of great interest. The
Furthermore, the inactive Li surrounded by SEI is gener- decomposition of fluorinated electrolytes generates high LiF
ated due to the disconnection of Li residue from the current content in the SEI, increasing the stability and mechanical
Figure 11. a) Cryo-EM image and schematic of a typical Li metal dendrite formed in EC/DEC electrolyte. b) Cryo-EM image and schematic of a typical
Li metal dendrite formed in EC/DEC electrolyte with 10 vol% FEC additive. Reproduced with permission.[189] Copyright 2018, Elsevier Inc. c) Polariza-
tion profiles for Li plating/stripping in 1 m LiPF6 FEC/FEMC/HFE at different current densities. d) Li plating/stripping Coulombic efficiency in different
electrolytes at 0.2 mA cm−2. Capacity: 1 mAh cm−2. e) Cycling stability of Li||LCP cells using FEC/DMC and 1 m LiPF6 FEC/FEMC/HFE electrolyte when
cycled at 1C. Reproduced with permission.[190] Copyright 2018, Springer Nature. f) Design scheme and molecular structures of three liquids studied
in this work. g) Li metal full battery performance (50 µm Li) at room temperature. Reproduced with permission.[191] Copyright 2020, Springer Nature.
strength of the SEI. The combination of LiPF6/LiFSI and In addition to the LiF-rich SEI, the Al2O3 coating has also
fluorinated solvents could form a more stable and robust been extensively studied as a protective layer on Li metal
SEI layer for LMBs. For example, Fan et al. invented a non- anode to stabilize the interphase between Li metal and elec-
flammable fluorinated electrolyte, 1 m LiPF6 in fluoroeth- trolyte.[35] Wan et al. proposed a controllable and efficient
ylene carbonate/3,3,3, -fluoroethylmethyl carbonate/1,1,2,2,- method using AlCl3 as an electrolyte additive to achieve the
tetrafluoroethyl-2’,2’,2’-trifuloroethyl ether (FEC:FEMC:HFE, stable SEI layer, which prevents the Li dendrite growth.[192]
2:6:2 by weight), for high-performance LMBs. This low con- As shown in Figure 12a, the residual water in the carbonate
centration fluorinated electrolyte enables a high Li plating/ electrolyte preferentially reacts with Al3+ ions to form
stripping Coulombic efficiency of 99.2% and mitigates the Al(OH)3. The nanosized Al(OH)3 can further absorb the
Li dendrite growth without sacrificing the anode impedance other Al3+ ions to generate positively charged colloidal par-
(Figure 11c,d).[190] More importantly, high-voltage cathodes ticles (PCCPs). The charge repulsion and steric hindrance of
such as 5 V LiCoPO4 cathode and Ni-rich LiNi0.8Mn0.1Co0.1O2 PCCPs force Li to deposit in the adjacent region. These parti-
cathode are compatible with this fluorinated electrolyte to cles finally form a dense SEI layer on the surface of Li metal
achieve high Coulombic efficiencies of ≈99.81% and ≈99.93%, under an applied voltage. The Coulombic efficiency of Li|Cu
respectively, and retain ≈93% original capacity after 1000 cells was measured in 1.0 m LiPF6 (EC/DMC/DEC) electro-
cycles at an areal capacity of 2.0 mAh cm−2, demonstrating lytes with and without AlCl3 additive. The Coulombic effi-
great promise in high-energy LMBs (Figure 11e). The suc- ciency of the electrolyte with AlCl3 additive is 75% initially
cess of these high-energy LMBs is attributed to the forma- and approaches to 99% after a few cycles, demonstrating a
tion of several-nanometer-thick fluorinated interphase from remarkable improvement in repeated Li stripping/plating
the decomposition of the fluorinated electrolyte. Another cycle. The high Coulombic efficiency retains for 150 cycles
example of a unique fluorinated electrolyte in LMBs is shown due to the formation of a stable SEI layer on the surface of
in Figure 11f,g. Yu et al. extended the alkyl chain of DME to the Li metal anode (Figure 12b). Zhang et al. reported another
form 1,4-dimethoxylbutane (DMB), and then fluorides were method to stabilize lithium metal anode by pre-cycling
introduced into DMB to replace hydrogens and generate fluor- Li metal in a lithium bis(trifluoromethanesulfonyl)imide
inated 1,4-dimethoxylbutane (FDMB), which is a new fluori- (LiTFSI, 1.0 m)-LiNO3 (5.0 wt%)-Li2S5 (0.02 m)-1,3-dioxolane
nated solvent (Figure 11f ).[191] 1 m LiFSI in FDMB electrolyte (DOL)/1,2-dimethoxyethane (DME) ternary salt electrolyte.[40]
was used for Li metal anodes with high Coulombic efficiency The resulting dense and stable SEI enables a dendrite-free
of ≈99.52% and high-voltage cathodes up to 6 V, owing to its lithium metal anode, which can be used to couple with both
unique LiF bonding and high anion/solvent ratio in the sol- sulfur and LiNi0.5Co0.2Mn0.3O2 (NCM) cathodes to improve
vation sheath. A high-performance full cell based on Li metal the battery performance (Figure 12c). This method opens up
anode and NMC532 cathode is achieved with a capacity reten- the door to use implantable ex situ constructed SEI for high-
tion of 90% after 420 cycles and a high average Coulombic energy LMBs.
efficiency of 99.98% (Figure 11g). These results demonstrate To take advantage of both organic compounds and elec-
the success of the synergy of LiPF6/LiFSI and fluorinated sol- trochemically stable inorganic salts, Archer et al. fabricated
vents to form a stable LiF-rich SEI layer for high-performance an organic/inorganic hybrid SEI layer with interlinked oli-
and dendrite-free LMBs. gomers.[193] Silicon tetrachloride (SiCl4) was introduced as a
The combination of Li metal/SEI interface energy (γ) and multidentate cross-linking agent in propylene carbonate (PC)-
Young’s modulus (E) of the SEI plays a dominant role in the based electrolyte. The schematic of SEI formation in the elec-
formation and growth of Li dendrites. A higher γE value indi- trolyte with and without SiCl4 is shown in Figure 12d. SiCl4 is
cates a stronger Li-dendrite suppression ability. Among all the highly soluble in PC and participates in the electrolyte decom-
components in SEI, LiF shows the highest γE value, and thus position reaction to generate a Si-interlinked OC(O)OR organic
the greatest Li-dendrite suppression ability. However, the critical film, which hosts LiCl and stabilizes the interphase. The sym-
current density for LMBs with LiF-rich artificial SEI is below metric lithium cells based on a LiPF6 + SiCl4/PC electrolyte
10 mA cm−2 in most reported literatures. Therefore, it is imper- form a uniform and homogenous SEI (Figure 12e) with a much
ative to search for other artificial SEI components with higher higher exchange current density than that based on a LiPF6 +
Li-dendrite suppression ability than LiF for the development of PC electrolyte. The process of Li plating/stripping at the high
fast-charging LMBs. Herein, Liu et al.[19] discover that SrF2 has current density of 3 mA cm−2 is stable for up to 500 cycles. The
a higher γE value than LiF according to the DFT calculation. A voltage versus time plot exhibits stable overpotentials upon
Li-11 wt% Sr alloy anode is fabricated, which can in situ form a long-term cycling, indicating a stable SEI layer and a dendrite-
SrF2-rich SEI layer on the surface of Li alloy anode in the fluori- free lithium metal anode (Figure 12f). Therefore, the hybrid
nated electrolyte. A high average Coulombic efficiency of 99.42% SEI enables the reversible and dendrite-free Li deposition by
is obtained when cycled at an areal capacity of 1 mAh cm−2 under constructing an ion-conductive organic silicon layer to protect
the current density of 1 mA cm−2. In addition, when the current the lithium metal anode. Though massive progress has been
density is increased to 30 mA cm−2 (1 mAh cm−2), the Li–Sr/ achieved for the design and synthesis of new liquid electrolytes
Li–Sr symmetric cell can be stably cycled for 180 cycles, which in LMBs, there are still challenges to understand the interac-
is a sevenfold improvement compared with the bare Li/Li sym- tions within the solvation sheath and the SEI formation mecha-
metric cell. This strategy offers a new opportunity to suppress Li nism in various new electrolytes. More research is required to
dendrite growth and promote the development of fast-charging exploit the solvation chemistry and interfacial chemistry in new
Li metal anodes for practical applications. electrolyte systems.
Figure 12. a) Schematic diagrams showing the Li plating process in the electrolyte with AlCl3 additive. b) Comparison of the Coulombic efficiency of
the Li plating/stripping process in 1.0 m LiPF6 (EC/DMC/DEC) electrolytes without and with AlCl3 additive at 0.5 mA cm−2 and a Li plating capacity
of 2 mAh cm−2. Reproduced with permission.[192] Copyright 2017, Elsevier Ltd. c) Ex situ SEI construction on the Li plate by electrochemical methods
in 1.0 m LiTFSI-DOL/DME electrolyte with 0.020 m Li2S5-5.0 wt% LiNO3 hybrid additives and its applications in Li-S and Li-NCM batteries. Repro-
duced with permission.[40] Copyright 2017, Elsevier Inc. d) Schematic diagram of the SEI formation process and Li deposition in spontaneously formed
and SiCl4 cross-linked SEI. e) Proposed chemical reaction scheme illustrating the SEI formation process and Li deposition in spontaneously formed
and SiCl4 cross-linked SEI. f) Voltage response from 1/3 h discharge and 1/3 h charge cycles at 3 mA cm−2. The insets are zoomed-in segments of the
voltage profiles. Reproduced with permission.[193] Copyright 2018, Wiley-VCH GmbH & Co. KGaA.
2.4. All-Solid-State Electrolyte Design SSEs. We will discuss the advantages, challenges, development,
and performance of state-of-the-art SSEs in this section. The
Battery thermal runaway, triggered by Li dendrite growth, is a electrochemical performances of LMBs based on SSEs are sum-
major challenge for the commercialization of LMBs. The elec- marized in Figure 13 and Table 4.
tronic and ionic conductive Li dendrite can penetrate the porous Inorganic SSEs are made of solid-state inorganic crystal-
separator and make contact with the cathode, causing the line materials with high ionic conductivity but very low elec-
internal short circuit of LMBs. A straightforward way to address tronic conductivity.[237] Although the high mechanical strength
this challenge is replacing the porous separator and liquid of inorganic SSEs blocks the penetration of Li dendrites, the
electrolyte with high-mechanical-strength and dense solid- interfacial contact between inorganic SSEs and lithium metal is
state electrolytes (SSEs). The nonflammable and dense SSEs poor, leading to high interfacial resistance in all-solid-state bat-
are promising and feasible alternatives to liquid electrolytes in teries. To overcome this challenge, a variety of approaches were
LMBs, since their high shear modulus and dense structure can adopted to decrease the interfacial resistance of inorganic SSEs
block the Li dendrite formation on the anode and improve the and lithium metal anode.
battery safety for long-term cycling. Moreover, SSEs are stable Among the recent achievements of inorganic SSEs, the pre-
in a wide temperature range, whereas liquid electrolytes are dominant material is garnet-type SSE (Li7La3Zr2O12, LLZO) and
unstable at high temperatures (>80 °C) due to the low boiling its analogues. As unveiled by Murugan et al. in 2007, garnet-
point and flash point of organic solvents. Therefore, consider- type SSEs display high Li+ conductivity of >10−4 S cm−1 at room
able research efforts have been devoted to developing advanced temperature and excellent electrochemical stability against Li
SSEs for LMBs. To date, the reported SSEs can be divided into metal.[238] Since then, garnet-type SSEs have been extensively
three categories: inorganic SSEs, organic SSEs, and composite studied as promising electrolyte materials for all-solid-state
Figure 13. The cycle life of various solid-state electrolytes at different current densities.
batteries. Nevertheless, the garnet-type SSEs also face the large remove the surface layer of Li2CO3 and retrieve a lithiophilic SSE
interfacial resistance challenge owing to the inferior wettability. surface. The interfacial resistance of the LLZTO pellet without
Moreover, Sharafi et al. reported that the garnet-type SSEs can Li2CO3 was decreased from 940 to 26 Ω cm2 at 30 °C, and the
react with CO2 and H2O in the air and form a thin Li2CO3 layer Li-ion conductivity was increased to 1.6 × 10−3 S cm−1 at 30 °C.
on the surface,[239] resulting in insufficient interfacial contact. To The favorable interface between LLZTO pellet and lithium metal
address this challenge, massive work has been done to reduce the enabled stable Li plating/stripping for over 700 h at 0.2 mA cm−2,
large interfacial resistance in all-solid-state batteries by manipu- demonstrating that removing the surfacial impurity phase such
lating the interfacial layer between lithium metal and SSEs. as Li2CO3 is an effective strategy to improve the interfacial chem-
Luo et al. deposited a thin layer (20 nm) of Germanium (Ge) on istry and stabilize lithium metal anode.
the garnet-type electrolyte by evaporating Ge on the LLZO pellet Highly conductive garnet-type electrolytes represent prom-
(Figure 14a).[240] Ge can alloy with Li metal anode and forms a ising SSEs for LMBs, but there are also other types of inorganic
more continuous interface to increase the active sites and decrease SSEs, which exhibit excellent performance in all-solid-state
the interfacial resistance. As a result, the interfacial resistance of LMBs. For instance, the solid-state crystal Li7P3S11 (LPS) is
this garnet-type SSE decreases from 900 to 115 Ω cm−2. More another type of promising inorganic SSEs (Figure 14c).[242]
importantly, a stable full cell, consisting of Ge-modified garnet- The interphase between Li metal and highly crystalline LPS
type SSE, lithium metal anode and LiFePO4 cathode, is achieved was investigated, and the densified (sintered) LPS shows high
at room temperature. In addition to introducing a new layer ionic conductivity of 4 mS cm−1 at room temperature, and a low
between lithium metal and SSEs, the elimination of the Li2CO3 interfacial resistance of 45 Ω, representing great promise in all-
layer from the garnet-type electrolyte is another way to decrease solid-state LMBs. Recently, Li1.4Al0.4Ti1.6(PO4)3 (LATP) emerged
the interfacial resistance. Huo et al. employed a rapid acid treat- as another potential inorganic SSE material because of its high
ment (RAT) to manipulate the interfacial chemistry of a garnet- Li-ion conductivity and low cost, but the high interfacial resist-
type electrolyte, tantalum (Ta)-doped garnet LLZTO (Li6.4La3Zr1.4T ance and instability against Li metal are still hurdles for LATP.
a0.6O12, an analogue of garnet) (Figure 14b).[241] The LLZTO pellets To overcome these challenges, magnetron sputtering (MS) is an
were dipped in 1 m HCl for a short time (from 10 s to 30 min) to excellent method to construct artificial SEI between LATP and
Table 4. Summary of electrochemical performances of Li metal anode enhanced by solid-state electrolytes.

[240] Thin Ge layer Li7La3Zr2O12 −2 −2 25 mV
0.05 mA cm , 0.0083 mAh cm ,
0.1 mA cm−2, 0.0083 mAh cm−2 ≈50 mV
[241] Li2CO3-free garnet Li6.4La3Zr1.4Ta0.6O12 0.1 mA cm−2, 700 h, 19.6 mV
0.2 mA cm−2, 700 h ≈40 mV
[243] ZnO interface Li1.4Al0.4Ti1.6(PO4)3 0.05 mA cm−2, 0.025 mAh cm−2, 2000 h, ≈30 mV
0.2 mA cm−2, 0.1 mAh cm−2, 1000 h 50 mV
[244] Electrolytes with controlled POSS-4PEG2k 0.2 mA cm−2,2600 h ≈80 mV
network 0.5 mA cm−2, 1212 h ≈100 mV
1 mA cm−2, 441 h ≈130 mV
[245] PVDF-based solid electrolytes PVDF-LiFSI 0.05 mA cm−2, 0.0025 mAh cm−2, 1000 h, ≈20 mV
0.1 mA cm−2, 0.05 mAh cm−2, 2000 h, ≈30 mV
0.2 mA cm−2, 0.1 mAh cm−2, 300 h, ≈45 mV
0.1 mA cm−2, 0.2 mAh cm−2, 80 cycles 94% 40 mV
[246] Double-layer polymer electrolyte PEO–LiTFSI/PMA–LiTFSI 0.1 mA cm−2 336 h ≈60 mV
[247] Ceramic/polymer composite Li1.5Al0.5Ge1.5(PO4)3-PEO 0.1 mA cm−2,0.1 mAh cm−2,
200 h, ≈150 mV
electrolyte 0.3 mA cm−2, 0.3 mAh cm−2, 200 h ≈400 mV
[248] Anion-immobilized electrolyte PEO-LiTFSI-LLZTO 0.1 mA cm−2 400 h,0.2 mA cm−2800 h 15 mV
60 mV
[249] Multilayered solid electrolyte PAN-PAN@Li1.4Al0.4Ge1.6(PO4)3-PEFDA 2 mA cm−2, 1 mAh cm−2, 1000 h 40 mV
[250] Al2O3 layer by ALD Li7La2.75Ca0.25Zr1.75Nb0.25O12 0.1 mA cm−2,
0.05 mAh cm−2,
420 h, 15 mV
0.2 mA cm−2, 0.1 mAh cm−2, 90 h 22 mV
[251] Polymer electrolytes 0.5 × 10−3m Al(OTf)3 + 2 m LiTFSI/DOL 1 mA cm−2, 1 mAh cm−2, 300 cycles, >98% ≈40 mV
1 mA cm−2, 1 mAh cm−2, 200 h ≈40 mV
[252] Semiliquid lithium metal anode LLZTO 0.2 mA cm−2, 0.2 mAh cm−2, 280 h, 10 mV
1 mA cm−2, 1 mAh cm−2, 390 h 140 mV
[253] Plastic crystal interlayers Li7La3Zr2O12 0.2 mA cm−2, 0.2 mAh cm−2, 160 h 100 mV
[254] Solid polymer electrolyte LLZTO −2, cm−2, ≈100 mV
0.2 mA cm 0.2 mAh 700 h
interface layer
[255] Single-ion polymer electrolyte P(SSPSILi-alt-MA) in PEO matrixes 0.01 mA cm−2, 0.04 mAh cm−2, 1200 h ≈150 mV
[256] Hybrid polymer electrolyte PVDF-HFP/PEO/LAGP + LiFSI-TEGDME 0.1 mA cm−2, 0.1 mAh cm−2, 800 h ≈25 mV
(1:1 by molar)
[257] Boron nitride coating BN-Li1.3Al0.3Ti1.7(PO4)3-PEO 0.3 mA cm−2, 0.3 mAh cm−2, 500 h 251 mV
[258] BN nanosheet layer LLZTO 0.3 mA cm−2, 0.3 mAh cm−2, 400 h 50 mV
[259] Plastic crystal electrolytes PCE-LGPS-PCE 0.13 mA cm−2, 0.13 mAh cm−2, 400 h 40 mV
[260] Garnet with lithiophilicity Li6.4La3Zr1.4Ta0.6O12 13.3 mA cm−2, 0.4 mAh cm−2,
25 h, 200 mV
2.2 mA cm−2, 0.88 mAh cm−2, 80 h 300 mV
[261] Electron/ion dual-conductive Li6.75La3Zr1.75Ta0.25O12 1 mA cm−2, 1 mAh cm−2, 500 h, ≈30 mV
framework 2 mA cm−2, 2 mAh cm−2, 500 h 50 mV
[262] Lithium–graphite paste Li6.5La3Zr1.5Ta0.5O12 0.3 mA cm−2, 0.3 mAh cm−2, 250 h ≈20 mV
[263] Dual-phase single-Ion pathway Li6.75La3Zr1.75Ta0.25O12 0.5 mA cm−2, 0.5 mAh cm−2, 350 cycles, 98.5%
interfaces 1 mA cm−2, 1 mAh cm−2, 150 cycles, 97.7%
1 mA cm−2, 1 mAh cm−2, 200 h 45 mV
[264] Tape-casting ceramic electrolyte PEO/Li0.34La0.56TiO3-PEO 0.025 mA cm−2, 0.025 mAh cm−2, 125 h 26 mV
[265] Composite polymer electrolyte Ga0.25Li6.25La3Zr2O12-SHP hybrid electrolyte 3 mA cm−2, 1 mAh cm−2, 650 h, 36 mV
10 mA cm−2, 1 mAh cm−2, 100 h, 75 mV
20 mA cm−2, 1 mAh cm−2, 150 h 120 mV
[266] Air-stable and dendrite-free Li3PS4 0.1 mA cm−2, 0.5 mAh cm−2, 2000 h ≈50 mV
Li anode
[267] g-C3N4 interface Li7La3Zr5O12 0.3 mA cm−2, 0.3 mAh cm−2, 300 h ≈50 mV
[268] Conductive garnet/Li interface LLZTO-MCL 0.1 mA cm−2, 0.1 mAh cm−2, 1000 h 30.1 mV
[269] Diatomite derived hierarchical PEO-SPE 0.5 mA cm−2, 0.5 mAh cm−2, 1000 h ≈100 mV
hybrid anode
Table 4. Continued.

[270] Triblock copolymer electrolyte PCL-PPC-PCL polymer electrolytes 0.1 mA cm−2, 0.1 mAh cm−2, 750 h ≈80 mV
[271] Ultra-dry polymer electrolytes P(VDF-HFP) −2 −2 ≈60 mV
0.1 mA cm , 0.1 mAh cm , 1000 h,
0.2 mA cm−2, 0.2 mAh cm−2, 800 h ≈170 mV
[272] Open framework fluorinated Li3GaF6 0.1 mA cm−2, 0.1 mAh cm−2, 230 h 600 mV
electrolyte
[273] Salt bonding to perovskite PEO/perovskite 0.1 mA cm−2, 0.1 mAh cm−2, 700 h ≈60 mV
Li3/8Sr7/16Ta3/4Zr1/4O3
[274] Stress self-adapted Li/garnet Li7La3Zr2O12 0.2 mA cm−2, 0.2 mAh cm−2, 300 h, 250 mV
interface 0.1 mA cm−2, 0.025 mAh cm−2, 100 h, 25 mV
0.2 mA cm−2, 0.033 mAh cm−2, 1800 h 25 mV
[275] Fluorinating electrolytes Li6PS5Cl 0.127 mA cm−2, 0.1 mAh cm−2, 1000 h, ≈17 mV
0.127 mA cm−2, 1 mAh cm−2, 1000 h, ≈150 mV
6.37 mA cm−2, 5 mAh cm−2, 250 h 750 mV
[276] Cu6Sn5 Layer coating Li7La2.75Ca0.25Zr1.75Nb0.25O12 0.1 mA cm−2, 0.05 mAh cm−2, 300 h, 30 mV
0.25 mA cm−2, 0.125 mAh cm−2, 300 h 90 mV
[277] Ultrarobust composite Li0.33La0.557TiO3 + bacterial cellulose 0.5 mA cm−2, 0.5 mAh cm−2, 300 h 10 mV
gel electrolyte
[278] Li–Al–O solid-state electrolyte Li–Al–O SSE 0.2 mA cm−2, 0.4 mAh cm−2, 1500 h ≈40 mV
[279] NASCION-based electrolyte Li1.5Al0.5Ge1.5(PO4)3 + ionic liquid 0.5 mA cm−2, 0.5 mAh cm−2, 300 h, ≈50 mV
0.1 mA cm−2, 0.1 mAh cm−2, 1500 h 30 mV
[280] Hierarchical electrolyte LLZTO/PEO 0.2 mA cm−2, 0.2 mAh cm−2, 400 h 400 mV
[281] Sn-substituted argyrodite sulfide LPSI-xSn SSEs 0.1 mA cm−2, 0.1 mAh cm−2, 700 h, 60 mV 300 mV
electrolyte 1.26 mA cm−2, 1 mAh cm−2, 200 h
[282] Bifunctional interlayer Li6.5La3Zr1.5Ta0.5O12/MoS2 0.2 mA cm−2, 0.1 mAh cm−2, 40 h 10 mV
[283] Fluorinated solid electrolyte LiFSI@Li3PS4 0.1 mA cm−2, 0.1 mAh cm−2, 100 cycles, 98%
interphase 0.3 mA cm−2, 0.3 mAh cm−2, 350 h ≈400 mV
Li metal due to the low cost, facile operation, and relatively low ZnO layer can react with Li to form a SEI layer (Zn@Li2O),
working temperatures. Hao et al. constructed an ultrathin ZnO which effectively reduces the impedance from 80554 to 353 Ω.
layer on the surface of LATP pellets via MS (Figure 14d).[243] The The Li-ion conductivity of this SSE was 2–4 × 10−4 S cm−2 at the
Figure 14. a) Illustration of Ge layer evaporation on the garnet electrolyte. Reproduced with permission.[240] Copyright 2017, WILEY-VCH GmbH & Co.
KGaA. b) The process of rapid acid treatment (RAT) of LLZTO pellet. Reproduced with permission.[241] Copyright 2019, Elsevier Ltd. c) The structure of
LPS crystal. Reproduced with permission.[242] Copyright 2015, Elsevier B.V. d) Schematic of ZnO layer addition with magnetron sputtering. Reproduced
with permission.[243] Copyright 2019, WILEY-VCH GmbH & Co. KGaA.
Figure 15. a) Galvanostatic cycling profiles of the cells with PVDF-LiX at current rates of 0.05, 0.1, and 0.2 mA cm−2. Reproduced with permission.[245]
Copyright 2019, WILEY-VCH GmbH & Co. KGaA. b) Schematic of double-layer polymer solid electrolyte (DLPSE). c) Molecular structure of PMA. Repro-
duced with permission.[246] Copyright 2018, WILEY-VCH GmbH & Co. KGaA. d) Fabrication of vertical aligned LAGP/PEO composite. Reproduced with
permission.[247] Copyright 2019, Elsevier Ltd. e) Comparison of Li dendrite inhibition of PLL electrolyte and normal liquid electrolyte. Reproduced with
permission.[248] Copyright 2017, National Academy of Sciences. f) Schematic of HMSE. g) Voltage profiles of the Li/HMSE/Li and Li/liquid electrolyte/
Li symmetric batteries at a current density of 2 mA cm−2. The red curve represents the performance for HMSE and the black curve represents the
performance for liquid electrolyte. Reproduced with permission.[249] Copyright 2019, WILEY-VCH GmbH & Co. KGaA.
room temperature. Therefore, exploring new highly ionic con- (Figure 15a). There was a mosaic interface layer formed on the
ductive and low-cost inorganic SSEs based on transition metal interface between the PVDF-LiFSI electrolyte and Li anode
oxides, sulfides (like LPS), chlorides, and fluorides are critical to self-suppress the Li dendrite growth. As another example,
for the development of all-solid-state LMBs. To circumvent the Zhou et al. proposed a double-layer polymer solid electrolyte
high interfacial resistance challenge, manipulating the interfa- (DLPSE) for LMBs (Figure 15b) to suppress the Li dendrite
cial chemistry by thin layer deposition is a feasible strategy. growth and enlarge the redox potential window of the SPE.[246]
In addition to inorganic SSEs, organic SSEs containing poly- As shown in the schematic illustration, the low-voltage polymer
meric materials and lithium salts are also promising for all- electrolyte contacts with Li metal anode to enable dendrite-free
solid-state LMBs. Organic SSEs are primarily solid polymers plating, while the high-voltage polymer electrolyte contacts
electrolytes (SPEs). Due to their soft texture, SPEs have good with the cathode to extract Li+ from it and avoid oxidation of
interfacial contact with Li metal anode and good flexibility. More- the electrolyte. In this work, PEO was chosen as the low-voltage
over, the facile fabrication and low cost of SPEs are beneficial for polymer and poly(N-methyl-malonic amide) (PMA) (Figure 15c)
large-scale production.[6] Nonetheless, SPEs have relatively lower was used as the high-voltage polymer. The DLPSE showed a
ionic conductivity and lower mechanical strength than reported very stable cycling performance due to the effective limitation of
inorganic SSEs.[244] To address these challenges, Zhang et al. the Li dendrite growth. The Li-ion conductivity of DLPSE was
studied several poly(vinylidene difluoride) (PVDF)-based SSEs 2.05 × 10−4 S cm−1 at 65 °C. To further improve the performance
for their electrochemical performances in LMBs. The PVDF-LiX of SPE-based all-solid-state LMBs, the important research direc-
(X = FSI−, TFSI−, and ClO4−) electrolytes were tested and ana- tions are 1) developing polymer materials with higher ionic
lyzed to compare their electrochemical behaviors.[245] Among conductivity and lower cost; 2) design and synthesis of new poly-
them, PVDF-LiFSI has the best overall performance: it has mers and structures that are capable to suppress the Li dendrite
high Li-ion conductivity of 1.18 × 10−4 S cm−1 at room tempera- growth; 3) improving the interfacial contact, multiple layers, and
ture, and it has much better stability than the other two SPEs SEI formation between SPEs and lithium metal anode.
To take advantage of both inorganic and organic SSEs, the anode, lithium dendrite formation and growth present a
a new structure of composite SSEs with both polymer major challenge. With uncontrollable dendrite growth and con-
electrolytes and inorganic SSEs has been designed and syn- tinuous cycling, Li dendrite can pierce through the porous sep-
thesized for all-solid-state LMBs. Wang et al. synthesized arator, resulting in an internal short circuit and battery thermal
a composite of ceramic nanoparticles and polymer as the runaway.[287] Considerable research efforts have been devoted
SSE.[247] The inorganic vertically aligned template was pro- to overcoming these two challenges. In the cathode, control-
duced with Li1.5Al0.5Ge1.5(PO4)3 (LAGP) ceramic nanoparti- ling the shuttle reactions of LiPSs has been a priority for stabi-
cles, and then it was combined with the polymer, polyethylene lizing LSBs. To prevent the dissolution of LiPSs and resultant
oxide (PEO), and LiTFSI (Figure 15d). The LAGP walls facili- shuttle reactions, three strategies were adopted. 1) modifying
tate Li-ion transport by providing continuous channels, and the concentration and composition of the liquid electrolyte to
the PEO matrix makes the electrolyte flexible and improves reduce the solubility of LiPSs and form stable SEI to avoid the
the interface contact. This composite SSE has an ionic con- shuttle reaction; 2) encapsulating sulfur with insoluble hosts
ductivity of 1.67 × 10−4 S cm−1 at room temperature. Zhao et al. such as graphene, carbon nanotube, porous carbon, porous/
made another composite electrolyte composed of a ceramic- mesoporous silica oxide, titanium oxide, manganese oxide, con-
polymer.[248] The composition was made of Li6.75La3Zr1.75Ta0.25O12 ducting polymers, and so on; 3) Replacing the liquid electrolyte
(LLZTO, a garnet analogue), polyethylene oxide (PEO), and with SSEs to ultimately solve the dissolution challenge. To date,
LiTFSI, denoted as PLL. The feature of PLL is that the TFSI− the electrochemical performance of the sulfur cathode has been
anion is immobilized to achieve uniform ion distribution, remarkably improved, but the safety and stability of the lithium
thus reducing the Li dendrite deposition. The ionic conduc- metal anode remains a challenge.
tivity of this composite SSE was 1.12 × 10−5 S cm−1 at 25 °C To overcome the challenge of lithium metal anode and
(Figure 15e). Duan et al. proposed a heterogeneous multilay- achieve stable LSBs, Yang et al. developed an intrinsic flame-
ered solid electrolyte (HMSE) to expand the electrochemical retardant organic electrolyte consisting of 1.1 m LiFSI in a sol-
window to 0–5 V to overcome the challenge of interfacial insta- vent mixture of flame-retardant triethyl phosphate and high
bility.[249] In the HMSE, poly(acrylonitrile) (PAN) is connected flashpoint solvent 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoro-
with the cathode since PAN is oxidation-tolerant. Polyethylene propyl (1:3, v/v) (Figure 16a).[288] This nonflammable electro-
glycol diacrylate (PEGDA) contacts with Li metal anode and lyte enables high Coulombic efficiency of >99% for lithium
the interlayer is the PAN@Li1.4Al0.4Ge1.6(PO4)3 (LAGP, 80 wt%) metal anode and retains stable Li plating/stripping for over
composite. The high mechanical strength of this composite 500 h even at 60 °C. In addition, the Li3PO4 and LiF-rich
SSE prevents Li dendrite growth, and its ionic conductivity is interphase generated from the nonflammable electrolyte
3.7 × 10−4 S cm−1 (Figure 15f), which endows the Li/HMSE/ suppresses the shuttle reaction in the sulfurized pyrolyzed
Li symmetric cell with excellent cycle stability over 1000 h poly(acrylonitrile) cathode, resulting in a high capacity and
at the current density of 2 mA cm−2 (Figure 15g). To further stable sulfur cathode. LSBs based on the nonflammable elec-
improve the performance of SSEs in LMBs, composite SSEs trolyte deliver a high specific capacity of 840.1 mAh g−1 with
with the combination of inorganic and organic SSEs could be high sulfur utilization of 95.6%, demonstrating excellent elec-
a potential direction. First, a better combination of inorganic trochemical performance (Figure 16b). To further facilitate the
and organic materials can be explored to improve electrochem- practical application of LSBs, Luo, et al. synthesized a small-
ical performance. Second, the fabrication of composite SSEs is sulfur/carbon composite (SSCC) by annealing the mixture
complicated. A facile and cost-effective approach is demanded of perylenetetracarboxylic dianhydride, poly(acrylonitrile),
to accelerate the development and application of composite and sulfur in a sealed vacuum glass tube. By using these
SSEs. oxygen- and nitrogen-rich precursors, the sulfur content in
the carbon framework can be increased to 60 wt% due to the
increased SO bonds.[289,290] Combining this novel SSCC
3. Applications of Lithium Metal Anode with an all-fluorinated organic electrolyte (1 m LiPF6 in a
mixture of fluoroethylene carbonate/3,3,3-fluoroethylmethyl
in Li–Sulfur Batteries
carbonate/1,1,2,2-tetrafluoroethyl-2′,2′,2′-trifluoroethyl ether)
Interests in lithium-sulfur batteries (LSBs) have continued to and lithium metal anode results in high-performance LSBs
grow due to the low cost, abundance, non-toxicity, high capacity that are stable for 200 cycles with a reversible capacity of
(1672 mAh g−1), and high energy density (2600 Wh kg−1) of 541 mAh g−1 and high Coulombic efficiency of ≈100% under
sulfur.[284] LSBs rely on a reversible redox reaction between lean electrolyte condition (<5 mLE gS−1), corresponding to
S8 and Li-ions, yielding linear high-order lithium polysulfides a high energy density of 974 Wh kg−1. These results demon-
(Li2S8, Li2S6, and Li2S4), low-order polysulfides (Li2S3 and Li2S2), strate that the fluorinated electrolyte together with a carbon
and lithium polysulfide (Li2S).[285] The development of these stabilized sulfur cathode is promising for the practical appli-
promising next-generation rechargeable batteries using sulfur cation of LSBs with lithium metal anode.
cathodes and lithium metal anodes has been plagued by two To further improve the electrochemical performance of
major challenges. For the cathode, the dissolution of high-order LSBs, it is of great importance to understand the lithium inven-
lithium polysulfides (LiPSs) in the organic electrolyte leads to tory loss and interphasial evolution upon cycling. Nanda, et al.
a polysulfide shuttle reaction. It causes severe sulfur loss from used anode-free Ni||Li2S full cells, pairing a Li2S cathode with a
the cathode, which in turn, reduces the capacity, cycle life, rate bare Ni foil anode, for accurate assessment of lithium inventory
performance, and Coulombic efficiency of the battery.[284,286] For depletion and interphasial evolution by time-of-flight secondary
Figure 16. a) Illustration of Li@S batteries using STD electrolyte and IFR electrolyte. b) Cyclic performance comparison with S@pPAN (52.6 wt%) at
60 °C. Reproduced with permission.[288] Copyright 2019, Wiley-VCH GmbH & Co. KGaA. c) Schematic illustration of a Li||Li2S half cell with 2750% excess
lithium, whose measured discharge capacity Qn, for any cycle number n, is simply the active sulfur inventory in the system Sn. d) Lithium degradation
in Li–S batteries with cycling. In the initial stages of cycling, the deposited lithium is covered by a thin surface interphasial layer composed of partially
reduced electrolyte decomposition products. Reproduced with permission.[291] Copyright 2020, The Royal Society of Chemistry.
ion mass spectrometry measurements (Figure 16c).[291] In the state-of-the-art lithium metal anode is still far away from the
absence of excess lithium metal, Li and S capacity ratio is con- practical application, because more fundamental insights and
trolled at 1. The electrolyte is 1 m LiTFSI + 0.1 m LiNO3 in DOL/ technical challenges need to be gained and addressed:
DME (1:1 VOL). Under this circumstance, the electrochemical
performance of the anode-free system is limited by the lithium 1) The safety challenge caused by Li dendrite growth on the
plating/stripping during cycling.[292] This unique system allows lithium metal anode is the main hurdle for practical appli-
for a quantitative understanding of lithium degradation and the cations of LMBs. To overcome this challenge, it is of great
depletion of active lithium metal during cycling. Experimental importance to gain fundamental insights into the Li dendrite
results indicate the loss of cyclable lithium stems from metallic formation and growth mechanism in various current collec-
“dead” lithium, being trapped in a layer of electrolyte decom- tors and new electrolytes. In addition, the interfacial chemis-
position products rather than parasitic side reactions with the try, including the SEI formation and growth mechanism, also
electrolyte to form SEI compounds.[14] The gas (H2, CH4, and plays a critical role in suppressing Li dendrite growth. To un-
C2H4) evolution upon cycling is also detrimental to the elec- derstand these mechanisms, advanced characterization tech-
trochemical performance of lithium metal anode (Figure 16d). niques such as cryogenic electron microscopy, time-of-flight
Therefore, the future work on improving the performance of secondary ion mass spectrometry, in situ SEM/TEM/AFM,
LSBs should focus on retaining the lithium inventory in the and so forth, are demanded to monitor Li dendrite growth
anode upon long-term cycling. and interphase evolution. The new knowledge obtained from
these advanced techniques can guide future structure design
and electrolyte optimization for high-energy LMBs.
4. Conclusions and Perspectives 2) Electrochemical deposition is a facile and common method
to deposit the uniform and controllable metallic Li on 2D or
Li metal possesses great promise as the anode for next-gen- 3D current collectors. However, the Li metal is electrochemi-
eration high-energy rechargeable Li batteries. However, the cally deposited in a half-cell system, using the Li foil as a refer-
uncontrollable Li dendrite growth, infinite volume change, low ence/counter electrode and the current collector as a working
Coulombic efficiency, and fast capacity loss upon long-term electrode. The cell will be disassembled after the Li deposition,
cycling impede its practical application. In the last decade, and then the current collector/Li composite electrode will be
considerable efforts were devoted to improving the safety and used as an anode to assemble a new battery paired with differ-
stability of Li metal, and tremendous progress was achieved ent kinds of cathode materials, such as transition metal oxide,
by using the surface coating, porous current collectors, novel sulfur and O2. Although most current collectors in LMBs can
liquid electrolytes, and SSEs. The in situ or ex situ formation of be fabricated for practical application (pouch cells or cylindri-
stable and robust SEI suppresses Li dendrites growth and ena- cal cells), the equipment for electrochemical deposition is still
bles high Coulombic efficiency, while porous current collectors restricted, because the Li metal needs to be deposited in a glove
accommodate the infinite volume change and reduce the areal box. New engineering technology is needed to optimize the
current density. Though great success has been achieved, the electrochemical deposition for large-scale practical applications.
3) The infusion of molten Li into porous current collectors is the energy density of LMBs. However, the SEI formation and
another facile and efficient method to fabricate the 3D com- Li dendrite growth consume a large amount of electrolyte,
posite Li metal anode. Although Cu, Ni, and carbon-based which can desiccate the lean electrolyte LMBs and cause bat-
materials are commonly used for the fabrication of porous tery failure. Hence, exploiting new structure and electrolyte
current collectors, the high overpotential during Li deposi- for high-performance lean electrolyte LMBs is vital for practi-
tion and the lithiophobic nature of these substrates increase cal applications.
the risk of Li dendrite growth during the Li plating process. 7) Long-term cycling Coulombic efficiency is used to determine
Hence, some lithiophilic elements, such as Al, Mg, Zn, Ag, the stability of SEI and the growth of Li dendrites. Although
Au, Si, Sn, and Pt, were used to composite with Cu or carbon various effective approaches have been employed to enhance
to increase their wettability with metallic Li. Also, the pore the Coulombic efficiency of Li metal anodes, such as surface
size of current collectors is crucial for the stability of the Li coating, porous current collector, and modification of elec-
metal anode. For example, in a current collector with very trolyte, the highest Coulombic efficiency achieved so far is
small pore size, such as nanoporous Cu film, the molten Li ≈99.52%, which can only retain 38.2% of the initial Li after
can infuse into the nanopores of the current collector, but 200 cycles. The fast Li loss during repeated stripping/plating
during the repeated plating/stripping process, the Li metal processes reduces the stability and energy density of LMBs.
will be preferentially deposited on its surface, blocking the Therefore, excess Li is always used in LMBs to achieve long-
nanopores and leading to the formation of Li dendrites on cycle-life and high-energy-density cathodes, at a price of the
the surface. For current collectors with large pore sizes, such low energy density for full cells. Developing new strategies to
as Cu foam or Ni foam, the Li metal in the center of the pores further improve the Coulombic efficiency of Li metal anode
will lose connection with the porous backbone to form “dead is pivotal for the practical application of LMBs.
Li” due to the uneven current distribution. Hence, precise 8) To date, the Li metal anode can achieve a high areal capacity
control for the pore size of porous current collectors is signif- up to 50 mAh cm−2, but the areal capacity of the sulfur cath-
icant, and novel characterization techniques and simulations ode is still lower than 4 mAh cm−2 due to the low sulfur mass
are also needed to understand Li plating/stripping process, loading in the cathode. The use of highly conductive carbon
Li dendrite growth, and “dead Li” formation mechanism in host materials, such as mesoporous carbon, graphene, and
porous current collectors. carbon nanotubes, dramatically enhanced the mass loading
4) To date, vertically oriented Li-X-Li laminated anode (X: con- and rate capability of S cathode. However, the high content of
ductive films that can maintain structural integrity after Li carbon materials in sulfur cathodes lowers the entire capac-
stripping) is a promising direction, which enables large-scale ity and energy density of LSBs. The 3D porous current col-
production by a roll-to-roll process. Although Cu foil is the lectors with lightweight, high conductivity, and high stability
commonly used material for laminating with Li metal, its can be ideal hosts for the sulfur cathode. The molten sulfur
lithiophobicity and high mass density restrict the Li plating/ can be infused into the small pores of 3D current collectors
stripping performance and gravimetric capacity of the Li–Cu– to stabilize sulfur and make binder-free and carbon black-free
Li laminated anode. The exploration of porous alloy films cathodes. The 3D porous current collector can accommodate
containing both lithiophilic and lithiophobic components is a the high content of sulfur to achieve an ultrahigh areal capac-
feasible approach to solving these challenges. The lithiophilic ity. The architecture of this 3D current collector needs to be
component shows a strong connection with Li to enable uni- designed elaborately to restrain the “shutting effect” of sulfur
form Li plating even after the deep stripping condition, while under high sulfur content.
the lithiophobic component possesses high stability to retain 9) The dense SSEs are ideal to suppress the Li dendrite growth
structural stability of the porous alloy film, avoiding the vol- in LMBs because of their high ionic conductivity and high me-
ume change of the entire composite Li metal anode. chanical strength. The development of new SSEs is another im-
5) For the practical application of LMBs, the thickness of the Li portant direction for LMBs. However, poor interfacial contact
metal anode needs to be controlled in the range of 25–50 µm between SSEs and lithium metal is a major challenge. Future
(5–10 mAh cm−2) to achieve the high energy density of research on solid-state LMBs should focus on increasing the
400 Wh kg−1 for full cells. However, most reported 3D porous ionic conductivity while simultaneously reducing the electronic
current collectors show a thickness much higher than 50 µm, conductivity of SSEs and enabling stable and intimate interpha-
decreasing the energy density of full cells. Therefore, reduc- sial contact between SSEs and lithium metal anode.
ing the thickness of 3D current collectors to <50 µm without
sacrificing their porous structure and structural integrity is As summarized in Figure 17a,b, the surface coating, porous
an important direction for the practical application of 3D po- current collectors, and modification of liquid electrolyte are
rous current collectors. three effective approaches to enhancing the average Cou-
6) Flooded electrolyte conditions are always used to measure lombic efficiency of Li metal anode to >99% at current densities
the electrochemical performance of Li metal anodes in lit- ≤3 mA cm−2 and retain a long cycle life of ≥1000 h. However,
eratures. For example, over 40 µL of electrolyte per mAh is none of these strategies enables high Coulombic efficiency and
used to test the symmetric performance of Li metal anode in long cycle life at high current densities >3 mA cm−2, which is
the coin cell system, which is much more than that (<5 µL important for the practical application of high-energy and fast-
mAh−1) in commercialized pouch cells and cylinder cells.[293] charging LMBs. This challenge of Li metal anode should be
The flooded electrolyte is not suitable in practical application solved by the synergy of various approaches rather than a single
because the extra electrolyte increases the cost and decreases strategy. For example, the combination of artificial/in situ
Figure 17. The summary of a) Coulombic efficiency and b) cycle life versus current density for lithium metal anodes stabilized by surface coating, porous
current collector, liquid electrolyte, and solid-state electrolyte.
formed SEI and porous current collectors will optimize the [9] X. Shen, H. Liu, X. B. Cheng, C. Yan, J. Q. Huang, Energy Storage
interphase and accommodate the infinite volume change of Mater. 2018, 12, 161.
Li metal anode, improving the Coulombic efficiency and cycle [10] C. Fang, X. Wang, Y. S. Meng, Trends Chem. 2019, 1, 152.
[11] M. S. Whittingham, Chem. Rev. 2004, 104, 4271.
life at high current densities. With the emergence of more
[12] M. Armand, Nature 2001, 414, 359.
advanced characterization techniques and material produc-
[13] K. Brandt, Solid State Ionics 1994, 69, 173.
tion methods, fundamental insights and new strategies will [14] X.-B. Cheng, J.-Q. Huang, Q. Zhang, J. Electrochem. Soc. 2018, 165,
be gained to promote the development of high-safety, high- A6058.
stability, high-energy, and fast-charging LMBs for smart tech- [15] R. Xu, X. B. Cheng, C. Yan, X. Q. Zhang, Y. Xiao, C. Z. Zhao,
nologies, electric vehicles, and renewable energies. J. Q. Huang, Q. Zhang, Matter 2019, 1, 317.
[16] T. Li, X. Q. Zhang, P. Shi, Q. Zhang, Joule 2019, 3, 2647.
[17] S. S. Zhang, ACS Appl. Energy Mater. 2018, 1, 910.
[18] C. Yang, K. Fu, Y. Zhang, E. Hitz, L. Hu, Adv. Mater. 2017, 29,
Acknowledgements 1701169.
This research was supported by the George Mason University, College of [19] S. Liu, X. Ji, J. Yue, S. Hou, P. Wang, C. Cui, J. Chen, B. Shao, J. Li,
Science Postdoctoral Fellowship and COS-VSE Seed Award No. 183904. F. Han, J. Tu, C. Wang, J. Am. Chem. Soc. 2020, 142, 2438.
The authors also acknowledge the support from the George Mason [20] F. Wu, Y. X. Yuan, X. B. Cheng, Y. Bai, Y. Li, C. Wu, Q. Zhang,
University Quantum Science & Engineering Center. Energy Storage Mater. 2018, 15, 148.
[21] Z. A. Ghazi, Z. Sun, C. Sun, F. Qi, B. An, F. Li, H. M. Cheng, Small
2019, 15, 1900687.
[22] K. N. Wood, M. Noked, N. P. Dasgupta, ACS Energy Lett. 2017, 2,
Conflict of Interest 664.
The authors declare no conflict of interest. [23] X. Q. Zhang, X. B. Cheng, Q. Zhang, Adv. Mater. Interfaces 2018,
5, 1701097.
[24] R. Zhang, N. W. Li, X. B. Cheng, Y. X. Yin, Q. Zhang, Y. G. Guo,
Adv. Sci. 2017, 4, 1600445.
Keywords [25] H. Ye, S. Xin, Y. X. Yin, Y. G. Guo, Adv. Energy Mater. 2017, 7,
liquid electrolytes, lithium metal batteries, porous current collector, 1700530.
solid-state electrolytes, surface coating [26] E. Peled, D. Golodnitsky, G. Ardel, J. Electrochem. Soc. 1997, 144,
L208.
Received: November 12, 2020 [27] D. Lin, Y. Liu, A. Pei, Y. Cui, Nano Res. 2017, 10, 4003.
Revised: December 3, 2020 [28] J. Ding, R. Xu, C. Yan, Y. Xiao, L. Xu, H. Peng, H. S. Park, J. Liang,
Published online: February 8, 2021 J. Huang, Nano Sel. 2020, 1, 94.
[29] Z. Cao, B. Li, S. Yang, Adv. Mater. 2019, 1901310.
[30] Y. Liu, D. Lin, P. Y. Yuen, K. Liu, J. Xie, R. H. Dauskardt, Y. Cui,
Adv. Mater. 2017, 29, 1605531.
[1] B. Dunn, H. Kamath, J. M. Tarascon, Science 2011, 334, 928. [31] R. Xu, X. Q. Zhang, X. B. Cheng, H. J. Peng, C. Z. Zhao, C. Yan,
[2] M. Winter, B. Barnett, K. Xu, Chem. Rev. 2018, 118, 11433. J. Q. Huang, Adv. Funct. Mater. 2018, 28, 1705838.
[3] J. B. Goodenough, K. S. Park, J. Am. Chem. Soc. 2013, 135, 1167. [32] D. Wang, W. Zhang, W. Zheng, X. Cui, T. Rojo, Q. Zhang, Adv. Sci.
[4]X. B. Cheng, R. Zhang, C. Z. Zhao, Q. Zhang, Chem. Rev. 2017, 117, 10403. 2017, 4, 1600168.
[5] X. Zeng, M. Li, D. Abd El-Hady, W. Alshitari, A. S. Al-Bogami, J. Lu, [33] X. Q. Zhang, X. B. Cheng, X. Chen, C. Yan, Q. Zhang, Adv. Funct.
K. Amine, Adv. Energy Mater. 2019, 9, 1900161. Mater. 2017, 27, 1605989.
[6] D. Lin, Y. Liu, Y. Cui, Nat. Nanotechnol. 2017, 12, 194. [34] X. Shen, Y. Li, T. Qian, J. Liu, J. Zhou, C. Yan, J. B. Goodenough,
[7] S. Li, M. Jiang, Y. Xie, H. Xu, J. Jia, J. Li, Adv. Mater. 2018, 30, Nat. Commun. 2019, 10, 900.
1706375. [35] L. Wang, L. Zhang, Q. Wang, W. Li, B. Wu, W. Jia, Y. Wang, J. Li,
[8] L. Wang, Z. Zhou, X. Yan, F. Hou, L. Wen, W. Luo, J. Liang, H. Li, Energy Storage Mater. 2018, 10, 16.
S. X. Dou, Energy Storage Mater. 2018, 14, 22. [36] H. Shang, Y. Gu, Y. Wang, Z. Zuo, Chem. – Eur. J. 2020, 26, 5434.
[37] A. A. Assegie, J. H. Cheng, L. M. Kuo, W. N. Su, B. J. Hwang, [70] Y. Sun, Y. Zhao, J. Wang, J. Liang, C. Wang, Q. Sun, X. Lin,
Nanoscale 2018, 10, 6125. K. R. Adair, J. Luo, D. Wang, R. Li, M. Cai, T. K. Sham, X. Sun,
[38] F. Hao, A. Verma, P. P. Mukherjee, J. Mater. Chem. A 2018, 6, 19664. Adv. Mater. 2019, 31, 1806541.
[39] A. C. Kozen, C. F. Lin, O. Zhao, S. B. Lee, G. W. Rubloff, M. Noked, [71] J. Xiang, Z. Cheng, Y. Zhao, B. Zhang, L. Yuan, Y. Shen, Z. Guo,
Chem. Mater. 2017, 29, 6298. Y. Zhang, J. Jiang, Y. Huang, Adv. Sci. 2019, 6, 1901120.
[40] X. B. Cheng, C. Yan, X. Chen, C. Guan, J. Q. Huang, H. J. Peng, [72] J. I. Lee, M. Shin, D. Hong, S. Park, Adv. Energy Mater. 2019, 9,
R. Zhang, S. T. Yang, Q. Zhang, Chem 2017, 2, 258. 1803722.
[41] J. Zhu, P. Li, X. Chen, D. Legut, Y. Fan, R. Zhang, Y. Lu, X. Cheng, [73] H. Chen, A. Pei, D. Lin, J. Xie, A. Yang, J. Xu, K. Lin, J. Wang,
Q. Zhang, Energy Storage Mater. 2019, 16, 426. H. Wang, F. Shi, D. Boyle, Y. Cui, Adv. Energy Mater. 2019, 9,
[42] H. Kim, Y. S. Kim, J. Yoo, Sustainable Energy Fuels 2020, 4, 522. 1900858.
[43] J. Lang, Y. Long, J. Qu, X. Luo, H. Wei, K. Huang, H. Zhang, L. Qi, [74] R. Pathak, K. Chen, A. Gurung, K. M. Reza, B. Bahrami, F. Wu,
Q. Zhang, Z. Li, H. Wu, Energy Storage Mater. 2019, 16, 85. A. Chaudhary, N. Ghimire, B. Zhou, W. H. Zhang, Y. Zhou,
[44] L. Chen, J. G. Connell, A. Nie, Z. Huang, K. R. Zavadil, K. C. Klavetter, Q. Qiao, Adv. Energy Mater. 2019, 9, 1901486.
Y. Yuan, S. Sharifi-Asl, R. Shahbazian-Yassar, J. A. Libera, A. U. Mane, [75] Q. Xu, J. Lin, C. Ye, X. Jin, D. Ye, Y. Lu, G. Zhou, Y. Qiu, W. Li,
J. W. Elam, J. Mater. Chem. A 2017, 5, 12297. Adv. Energy Mater. 2020, 10, 1903292.
[45] N. W. Li, Y. Shi, Y. X. Yin, X. X. Zeng, J. Y. Li, C. J. Li, L. J. Wan, [76] H. Ye, Z. Zheng, H. Yao, S. Liu, T. Zuo, X. Wu, Y. Yin, N. Li, J. Gu,
R. Wen, Y. G. Guo, Angew. Chem., Int. Ed. 2018, 57, 1505. F. Cao, Y. Guo, Angew. Chem. 2019, 131, 1106.
[46] Y. Gao, Y. Zhao, Y. C. Li, Q. Huang, T. E. Mallouk, D. Wang, J. Am. [77] Z. Li, K. Liu, K. Fan, Y. Yang, M. Shao, M. Wei, X. Duan, Angew.
Chem. Soc. 2017, 139, 15288. Chem., Int. Ed. 2019, 58, 3962.
[47] H. Dong, X. Xiao, C. Jin, X. Wang, P. Tang, C. Wang, Y. Yin, [78] G. Wang, C. Chen, Y. Chen, X. Kang, C. Yang, F. Wang, Y. Liu,
D. Wang, S. Yang, C. Wu, J. Power Sources 2019, 423, 72. X. Xiong, Angew. Chem., Int. Ed. 2020, 59, 2055.
[48] Y. Gao, Z. Yan, J. L. Gray, X. He, D. Wang, T. Chen, Q. Huang, [79] T. Liu, Q. Hu, X. Li, L. Tan, G. Yan, Z. Wang, H. Guo, Y. Liu, Y. Wu,
Y. C. Li, H. Wang, S. H. Kim, T. E. Mallouk, D. Wang, Nat. Mater. J. Wang, J. Mater. Chem. A 2019, 7, 20911.
2019, 18, 384. [80] C. Wei, H. Fei, Y. An, Y. Tao, J. Feng, Y. Qian, J. Mater. Chem. A
[49] L. Wang, Q. Wang, W. Jia, S. Chen, P. Gao, J. Li, J. Power Sources 2019, 7, 18861.
2017, 342, 175. [81] Y. Gao, T. Rojas, K. Wang, S. Liu, D. Wang, T. Chen, H. Wang,
[50] W. Wang, X. Yue, J. Meng, J. Wang, X. Wang, H. Chen, D. Shi, J. Fu, A. T. Ngo, D. Wang, Nat. Energy 2020, 5, 534.
Y. Zhou, J. Chen, Z. Fu, Energy Storage Mater. 2019, 18, 414. [82] B. Xu, Z. Liu, J. Li, X. Huang, B. Qie, T. Gong, L. Tan, X. Yang,
[51] S. Xia, X. Zhang, C. Liang, Y. Yu, W. Liu, Energy Storage Mater. D. Paley, M. Dontigny, K. Zaghib, X. Liao, Q. Cheng, H. Zhai,
2020, 24, 329. X. Chen, L. Q. Chen, C. W. Nan, Y. H. Lin, Y. Yang, Nano Energy
[52] J. Qian, Y. Li, M. Zhang, R. Luo, F. Wang, Y. Ye, Y. Xing, W. Li, W. Qu, 2020, 67, 104242.
L. Wang, L. Li, Y. Li, F. Wu, R. Chen, Nano Energy 2019, 60, 866. [83] P. Zhao, Y. Feng, T. Li, B. Li, L. Hu, K. Sun, C. Bao, S. Xiong,
[53] Z. Huang, G. Zhou, W. Lv, Y. Deng, Y. Zhang, C. Zhang, F. Kang, A. Matic, J. Song, Energy Storage Mater. 2020, 33, 158.
Q. H. Yang, Nano Energy 2019, 61, 47. [84] C. Yan, X. B. Cheng, Y. Tian, X. Chen, X. Q. Zhang, W. J. Li,
[54] Y. Yuan, F. Wu, Y. Bai, Y. Li, G. Chen, Z. Wang, C. Wu, Energy J. Q. Huang, Q. Zhang, Adv. Mater. 2018, 30, 1707629.
Storage Mater. 2019, 16, 411. [85] C. Yan, X. B. Cheng, Y. X. Yao, X. Shen, B. Q. Li, W. J. Li, R. Zhang,
[55] S. Li, L. Fan, Y. Lu, Energy Storage Mater. 2019, 18, 205. J. Q. Huang, H. Li, Q. Zhang, Adv. Mater. 2018, 30, 1804461.
[56] K. Chen, R. Pathak, A. Gurung, E. A. Adhamash, B. Bahrami, [86] W. Xu, J. Wang, F. Ding, X. Chen, E. Nasybulin, Y. Zhang,
Q. He, H. Qiao, A. L. Smirnova, J. J. Wu, Q. Qiao, Y. Zhou, Energy J. G. Zhang, Energy Environ. Sci. 2014, 7, 513.
Storage Mater. 2019, 18, 389. [87] Q. Yun, Y. B. He, W. Lv, Y. Zhao, B. Li, F. Kang, Q. H. Yang,
[57] Y. He, H. Xu, J. Shi, P. Liu, Z. Tian, N. Dong, K. Luo, X. Zhou, Adv. Mater. 2016, 28, 6932.
Z. Liu, Energy Storage Mater. 2019, 23, 418. [88] Y. Guo, H. Li, T. Zhai, Adv. Mater. 2017, 29, 1700007.
[58] D. Kang, N. Hart, J. Koh, L. Ma, W. Liang, J. Xu, S. Sardar, [89] H. K. Kang, S. G. Woo, J. H. Kim, S. R. Lee, Y. J. Kim, Electrochim.
J. P. Lemmon, Energy Storage Mater. 2020, 24, 618. Acta 2015, 176, 172.
[59] F. Guo, C. Wu, H. Chen, F. Zhong, X. Ai, H. Yang, J. Qian, Energy [90] X. B. Cheng, C. Yan, J. Q. Huang, P. Li, L. Zhu, L. Zhao, Y. Zhang,
Storage Mater. 2020, 24, 635. W. Zhu, S. T. Yang, Q. Zhang, Energy Storage Mater. 2017, 6, 18.
[60] X. Chen, M. Shang, J. Niu, Nano Lett. 2020, 20, 2639. [91] L. Yu, N. L. Canfield, S. Chen, H. Lee, X. Ren, M. H. Engelhard,
[61] Y. Liu, S. Zhang, X. Qin, F. Kang, G. Chen, B. Li, Nano Lett. 2019, Q. Li, J. Liu, W. Xu, J. G. Zhang, ChemElectroChem 2018, 5, 761.
19, 4601. [92] Y. Shi, Z. Wang, H. Gao, J. Niu, W. Ma, J. Qin, Z. Peng, Z. Zhang,
[62] Y. Zhao, G. Li, Y. Gao, D. Wang, Q. Huang, D. Wang, ACS Energy J. Mater. Chem. A 2019, 7, 1092.
Lett. 2019, 4, 1271. [93] J. Yun, B.-K. Park, E.-S. Won, S. H. Choi, H. C. Kang, J. H. Kim,
[63] Q. Yang, M. Cui, J. Hu, F. Chu, Y. Zheng, J. Liu, C. Li, ACS Nano M.-S. Park, J.-W. Lee, ACS Energy Lett. 2020, 5, 3108.
2020, 14, 1866. [94] J. Zhu, J. Chen, Y. Luo, S. Sun, L. Qin, H. Xu, P. Zhang, W. Zhang,
[64] J. Gu, Q. Zhu, Y. Shi, H. Chen, D. Zhang, Z. Du, S. Yang, W. Tian, Z. Sun, Energy Storage Mater. 2019, 23, 539.
ACS Nano 2020, 14, 891. [95] X. Zhang, A. Wang, R. Lv, J. Luo, Energy Storage Mater. 2019, 18, 199.
[65] E. K. Jang, J. Ahn, S. Yoon, K. Y. Cho, Adv. Funct. Mater. 2019, 29, [96] H. Qiu, T. Tang, M. Asif, X. Huang, Y. Hou, Adv. Funct. Mater.
1905078. 2019, 29, 1808468.
[66] Z. Lu, W. Li, Y. Long, J. Liang, Q. Liang, S. Wu, Y. Tao, Z. Weng, [97] L. M. Wang, Z. F. Tang, J. Lin, X. D. He, C. S. Chen, C. H. Chen,
W. Lv, Q. H. Yang, Adv. Funct. Mater. 2020, 30, 1907343. J. Mater. Chem. A 2019, 7, 17376.
[67] D. Chen, S. Huang, L. Zhong, S. Wang, M. Xiao, D. Han, Y. Meng, [98] L. L. Lu, J. Ge, J. N. Yang, S. M. Chen, H. Bin Yao, F. Zhou,
Adv. Funct. Mater. 2020, 30, 1907717. S. H. Yu, Nano Lett. 2016, 16, 4431.
[68] T. S. Wang, X. Liu, X. Zhao, P. He, C. W. Nan, L. Z. Fan, Adv. Funct. [99] K. Qin, J. Baucom, D. Liu, W. Shi, N. Zhao, Y. Lu, Small 2020, 16,
Mater. 2020, 30, 2000786. 2000794.
[69] F. Liu, L. Wang, Z. Zhang, P. Shi, Y. Feng, Y. Yao, S. Ye, H. Wang, [100] Y. Cheng, X. Ke, Y. Chen, X. Huang, Z. Shi, Z. Guo, Nano Energy
X. Wu, Y. Yu, Adv. Funct. Mater. 2020, 30, 2001607. 2019, 63, 103854.
[101] S. Sen Chi, Q. Wang, B. Han, C. Luo, Y. Jiang, J. Wang, C. Wang, [133] C. Zhao, Z. Wang, X. Tan, H. Huang, Z. Song, Y. Sun, S. Cui,
Y. Yu, Y. Deng, Nano Lett. 2020, 20, 2724. Q. Wei, W. Guo, R. Li, C. Yu, J. Qiu, X. Sun, Small Methods 2019,
[102] D. Zhang, A. Dai, M. Wu, K. Shen, T. Xiao, G. Hou, J. Lu, Y. Tang, 3, 1800546.
ACS Energy Lett. 2020, 5, 180. [134] Z. Liang, D. Lin, J. Zhao, Z. Lu, Y. Liu, C. Liu, Y. Lu, H. Wang,
[103] Z. Luo, C. Liu, Y. Tian, Y. Zhang, Y. Jiang, J. Hu, H. Hou, G. Zou, K. Yan, X. Tao, Y. Cui, Proc. Natl. Acad. Sci. USA 2016, 113, 2862.
X. Ji, Energy Storage Mater. 2020, 27, 124. [135] S. Xia, X. Zhang, H. Zhao, J. Xie, L. Y. Chou, Y. Yu, W. Liu, Small
[104] X. Y. Yue, W. W. Wang, Q. C. Wang, J. K. Meng, X. X. Wang, Y. Song, 2020, 16, 2001257.
Z. W. Fu, X. J. Wu, Y. N. Zhou, Energy Storage Mater. 2019, 21, 180. [136] K. Li, Z. Hu, J. Ma, S. Chen, D. Mu, J. Zhang, Adv. Mater. 2019, 31,
[105] K. Huang, Z. Li, Q. Xu, H. Liu, H. Li, Y. Wang, Adv. Energy Mater. 1902399.
2019, 9, 1900853. [137] Q. Song, H. Yan, K. Liu, K. Xie, W. Li, W. Gai, G. Chen, H. Li,
[106] F. Zhao, X. Zhou, W. Deng, Z. Liu, Nano Energy 2019, 62, 55. C. Shen, Q. Fu, S. Zhang, L. Zhang, B. Wei, Adv. Energy Mater.
[107] C. Sun, Y. Li, J. Jin, J. Yang, Z. Wen, J. Mater. Chem. A 2019, 7, 7752. 2018, 8, 1800564.
[108] H. Zheng, Q. Zhang, Q. Chen, W. Xu, Q. Xie, Y. Cai, Y. Ma, [138] F. Zhang, X. Liu, M. Yang, X. Cao, X. Huang, Y. Tian, F. Zhang,
Z. Qiao, Q. Luo, J. Lin, L. Wang, B. Qu, B. Sa, D. L. Peng, J. Mater. H. Li, Nano Energy 2020, 69, 104443.
Chem. A 2020, 8, 313. [139] Y. Liu, X. Qin, S. Zhang, Y. Huang, F. Kang, G. Chen, B. Li, Energy
[109] Y. Feng, C. Zhang, X. Jiao, Z. Zhou, J. Song, Energy Storage Mater. Storage Mater. 2019, 18, 320.
2020, 25, 172. [140] Y. Jiang, J. Jiang, Z. Wang, M. Han, X. Liu, J. Yi, B. Zhao, X. Sun,
[110] B. Xu, H. Zhai, X. Liao, B. Qie, J. Mandal, T. Gong, L. Tan, X. Yang, J. Zhang, Nano Energy 2020, 70, 104504.
K. Sun, Q. Cheng, M. Chen, Y. Miao, M. Wei, B. Zhu, Y. Fu, A. Li, [141] H. Wang, Y. Li, Y. Li, Y. Liu, D. Lin, C. Zhu, G. Chen, A. Yang,
X. Chen, W. Min, C. W. Nan, Y. H. Lin, Y. Yang, Energy Storage K. Yan, H. Chen, Y. Zhu, J. Li, J. Xie, J. Xu, Z. Zhang, R. Vilá, A. Pei,
Mater. 2019, 17, 31. K. Wang, Y. Cui, Nano Lett. 2019, 19, 1326.
[111] J. Jiang, Z. Pan, Z. Kou, P. Nie, C. Chen, Z. Li, S. Li, Q. Zhu, [142] G. Huang, J. Han, F. Zhang, Z. Wang, H. Kashani, K. Watanabe,
H. Dou, X. Zhang, J. Wang, Energy Storage Mater. 2020, 29, 84. M. Chen, Adv. Mater. 2019, 31, 1805334.
[112] Z. Zhang, J. Wang, X. Yan, S. Zhang, W. Yang, Z. Zhuang, [143] Q. Xu, X. Yang, M. Rao, D. Lin, K. Yan, R. A. Du, J. Xu, Y. Zhang, D. Ye,
W. Q. Han, Energy Storage Mater. 2020, 29, 332. S. Yang, G. Zhou, Y. Lu, Y. Qiu, Energy Storage Mater. 2020, 26, 73.
[113] D. Yin, G. Huang, S. Wang, D. Yuan, X. Wang, Q. Li, Q. Sun, [144] L. Dong, L. Nie, W. Liu, Adv. Mater. 2020, 32, 1908494.
H. Xue, L. Wang, J. Ming, J. Mater. Chem. A 2020, 8, 1425. [145] Q. Zhao, X. Hao, S. Su, J. Ma, Y. Hu, Y. Liu, F. Kang, Y. B. He,
[114] R. Zhang, S. Wen, N. Wang, K. Qin, E. Liu, C. Shi, N. Zhao, J. Mater. Chem. A 2019, 7, 15871.
Adv. Energy Mater. 2018, 8, 1800914. [146] A. Wang, X. Zhang, Y. W. Yang, J. Huang, X. Liu, J. Luo, Chem 2018,
[115] F. Pei, A. Fu, W. Ye, J. Peng, X. Fang, M. S. Wang, N. Zheng, 4, 2192.
ACS Nano 2019, 13, 8337. [147] T. Yang, L. Li, F. Wu, R. Chen, Adv. Funct. Mater. 2020, 30, 2002013.
[116] S. H. Hong, D. H. Jung, J. H. Kim, Y. H. Lee, S. J. Cho, S. H. Joo, [148] A. M. Hafez, Y. Jiao, J. Shi, Y. Ma, D. Cao, Y. Liu, H. Zhu,
H. W. Lee, K. S. Lee, S. Y. Lee, Adv. Funct. Mater. 2020, 30, 1908868. Adv. Mater. 2018, 30, 1802156.
[117] Z. Lu, Q. Liang, B. Wang, Y. Tao, Y. Zhao, W. Lv, D. Liu, C. Zhang, [149] H. Wang, D. Lin, J. Xie, Y. Liu, H. Chen, Y. Li, J. Xu, G. Zhou,
Z. Weng, J. Liang, H. Li, Q. H. Yang, Adv. Energy Mater. 2019, 9, Z. Zhang, A. Pei, Y. Zhu, K. Liu, K. Wang, Y. Cui, Adv. Energy Mater.
1803186. 2019, 9, 1802720.
[118] B. Li, S. Li, J. Liu, B. Wang, S. Yang, Nano Lett. 2015, 15, 3073. [150] J. Xie, J. Ye, F. Pan, X. Sun, K. Ni, H. Yuan, X. Wang, N. Shu,
[119] B. Liu, J. G. Zhang, W. Xu, Joule 2018, 2, 833. C. Chen, Y. Zhu, Adv. Mater. 2019, 31, 1805654.
[120] Y. Zhang, B. Liu, E. Hitz, W. Luo, Y. Yao, Y. Li, J. Dai, C. Chen, [151] X. R. Chen, B. Q. Li, C. Zhu, R. Zhang, X. B. Cheng, J. Q. Huang,
Y. Wang, C. Yang, H. Li, L. Hu, Nano Res. 2017, 10, 1356. Q. Zhang, Adv. Energy Mater. 2019, 9, 1901932.
[121] L. Liu, Y. X. Yin, J. Y. Li, N. W. Li, X. X. Zeng, H. Ye, Y. G. Guo, [152] Y. Chen, A. Elangovan, D. Zeng, Y. Zhang, H. Ke, J. Li, Y. Sun,
L. J. Wan, Joule 2017, 1, 563. H. Cheng, Adv. Funct. Mater. 2020, 30, 1906444.
[122] G. Zheng, S. W. Lee, Z. Liang, H. W. Lee, K. Yan, H. Yao, H. Wang, [153] C. Wei, H. Fei, Y. Tian, Y. An, H. Guo, J. Feng, Y. Qian, Energy
W. Li, S. Chu, Y. Cui, Nat. Nanotechnol. 2014, 9, 618. Storage Mater. 2020, 26, 223.
[123] G. Jiang, N. Jiang, N. Zheng, X. Chen, J. Mao, G. Ding, Y. Li, [154] H. Shi, M. Yue, C. J. Zhang, Y. Dong, P. Lu, S. Zheng, H. Huang,
F. Sun, Y. Li, Energy Storage Mater. 2019, 23, 181. J. Chen, P. Wen, Z. Xu, Q. Zheng, X. Li, Y. Yu, Z. S. Wu, ACS Nano
[124] X. Y. Yue, X. L. Li, W. W. Wang, D. Chen, Q. Q. Qiu, Q. C. Wang, 2020, 14, 8678.
X. J. Wu, Z. W. Fu, Z. Shadike, X. Q. Yang, Y. N. Zhou, Nano Energy [155] Y. Tian, Y. An, C. Wei, B. Xi, S. Xiong, J. Feng, Y. Qian, ACS Nano
2019, 60, 257. 2019, 13, 11676.
[125] Z. J. Zheng, Q. Su, Q. Zhang, X. C. Hu, Y. X. Yin, R. Wen, H. Ye, [156] H. Shi, C. J. Zhang, P. Lu, Y. Dong, P. Wen, Z. S. Wu, ACS Nano
Z. B. Wang, Y. G. Guo, Nano Energy 2019, 64, 103910. 2019, 13, 14308.
[126] Y. Chen, X. Ke, Y. Cheng, M. Fan, W. Wu, X. Huang, Y. Liang, [157] M. Chen, J. Zheng, O. Sheng, C. Jin, H. Yuan, T. Liu, Y. Liu,
Y. Zhong, Z. Ao, Y. Lai, G. Wang, Z. Shi, Energy Storage Mater. Y. Wang, J. Nai, X. Tao, J. Mater. Chem. A 2019, 7, 18267.
2020, 26, 56. [158] Y. Sun, J. Zhou, H. Ji, J. Liu, T. Qian, C. Yan, ACS Appl. Mater. Interfaces
[127] Y. Liao, L. Yuan, J. Xiang, W. Zhang, Z. Cheng, B. He, Z. Li, 2019, 11, 32008.
Y. Huang, Nano Energy 2020, 69, 104471. [159] W. Liu, D. Lin, A. Pei, Y. Cui, J. Am. Chem. Soc. 2016, 138, 15443.
[128] S. Li, Q. Liu, J. Zhou, T. Pan, L. Gao, W. Zhang, L. Fan, Y. Lu, [160] H. Qiu, T. Tang, M. Asif, W. Li, T. Zhang, Y. Hou, Nano Energy
Adv. Funct. Mater. 2019, 29, 1808847. 2019, 65, 103989.
[129] K. Lin, X. Qin, M. Liu, X. Xu, G. Liang, J. Wu, F. Kang, G. Chen, [161] H. Liu, X. Yue, X. Xing, Q. Yan, J. Huang, V. Petrova, H. Zhou,
B. Li, Adv. Funct. Mater. 2019, 29, 1903229. P. Liu, Energy Storage Mater. 2019, 16, 505.
[130] P. Shi, T. Li, R. Zhang, X. Shen, X. B. Cheng, R. Xu, J. Q. Huang, [162] J. Li, P. Zou, S. W. Chiang, W. Yao, Y. Wang, P. Liu, C. Liang,
X. R. Chen, H. Liu, Q. Zhang, Adv. Mater. 2019, 31, 1807131. F. Kang, C. Yang, Energy Storage Mater. 2020, 24, 700.
[131] P. Xue, C. Sun, H. Li, J. Liang, C. Lai, Adv. Sci. 2019, 6, 1900943. [163] Z. Lyu, G. J. H. Lim, R. Guo, Z. Pan, X. Zhang, H. Zhang, Z. He,
[132] F. Liu, R. Xu, Z. Hu, S. Ye, S. Zeng, Y. Yao, S. Li, Y. Yu, Small 2019, S. Adams, W. Chen, J. Ding, J. Wang, Energy Storage Mater. 2020,
15, 1803734. 24, 336.
[164] Y. Xu, Y. Zhou, T. Li, S. Jiang, X. Qian, Q. Yue, Y. Kang, Energy [196] S. Lin, J. Zhao, ACS Appl. Mater. Interfaces 2020, 12, 8316.
Storage Mater. 2020, 25, 334. [197] J. Qian, W. A. Henderson, W. Xu, P. Bhattacharya, M. Engelhard,
[165] Y. Chen, M. Yue, C. Liu, H. Zhang, Y. Yu, X. Li, H. Zhang, O. Borodin, J. G. Zhang, Nat. Commun. 2015, 6, 6362.
Adv. Funct. Mater. 2019, 29, 1806752. [198] C. C. Su, M. He, R. Amine, Z. Chen, R. Sahore, N. Dietz Rago,
[166] L. Tao, A. Hu, Z. Yang, Z. Xu, C. E. Wall, A. R. Esker, Z. Zheng, K. Amine, Energy Storage Mater. 2019, 17, 284.
F. Lin, Adv. Funct. Mater. 2020, 30, 2000585. [199] N. Dong, G. Yang, H. Luo, H. Xu, Y. Xia, Z. Liu, J. Power Sources
[167] W. Chen, R. V. Salvatierra, M. Ren, J. Chen, M. G. Stanford, 2018, 400, 449.
J. M. Tour, Adv. Mater. 2020, 32, 2002850. [200] X. Shangguan, G. Xu, Z. Cui, Q. Wang, X. Du, K. Chen, S. Huang,
[168] C. Wu, H. Huang, W. Lu, Z. Wei, X. Ni, F. Sun, P. Qing, Z. Liu, G. Jia, F. Li, X. Wang, D. Lu, S. Dong, G. Cui, Small 2019, 15, 1900269.
J. Ma, W. Wei, L. Chen, C. Yan, L. Mai, Adv. Sci. 2020, 7, 1902643. [201] Y. Yang, D. M. Davies, Y. Yin, O. Borodin, J. Z. Lee, C. Fang,
[169] H. Yuan, J. Nai, H. Tian, Z. Ju, W. Zhang, Y. Liu, X. Tao, X. W. Lou, M. Olguin, Y. Zhang, E. S. Sablina, X. Wang, C. S. Rustomji,
Sci. Adv. 2020, 6, eaaz3112. Y. S. Meng, Joule 2019, 3, 1986.
[170] S. Jin, Y. Ye, Y. Niu, Y. Xu, H. Jin, J. Wang, Z. Sun, A. Cao, X. Wu, [202] Y. Yang, Y. Yin, D. M. Davies, M. Zhang, M. Mayer, Y. Zhang,
Y. Luo, H. Ji, L.-J. Wan, J. Am. Chem. Soc. 2020, 142, 8818. E. S. Sablina, S. Wang, J. Z. Lee, O. Borodin, C. S. Rustomji,
[171] H. Xu, S. Li, X. Chen, C. Zhang, Z. Tang, H. Fan, Y. Yu, W. Liu, Y. S. Meng, Energy Environ. Sci. 2020, 13, 2209.
N. Liang, Y. Huang, J. Li, Nano Energy 2020, 74, 104815. [203] N. W. Li, Y. X. Yin, J. Y. Li, C. H. Zhang, Y. G. Guo, Adv. Sci. 2017,
[172] L. Ye, P. Feng, X. Chen, B. Chen, K. Gonzalez, J. Liu, I. Kim, X. Li, 4, 1600400.
Energy Storage Mater. 2020, 26, 371. [204] P. Yang, X. Gao, X. Tian, C. Shu, Y. Yi, P. Liu, T. Wang, L. Qu,
[173] T. Zhang, H. Lu, J. Yang, Z. Xu, J. Wang, S. I. Hirano, Y. Guo, B. Tian, M. Li, W. Tang, B. Yang, J. B. Goodenough, ACS Energy
C. Liang, ACS Nano 2020, 14, 5618. Lett. 2020, 5, 1681.
[174] X. B. Cheng, T. Z. Hou, R. Zhang, H. J. Peng, C. Z. Zhao, [205] X. Cao, X. Ren, L. Zou, M. H. Engelhard, W. Huang, H. Wang,
J. Q. Huang, Q. Zhang, Adv. Mater. 2016, 28, 2888. B. E. Matthews, H. Lee, C. Niu, B. W. Arey, Y. Cui, C. Wang, J. Xiao,
[175] T. T. Zuo, X. W. Wu, C. P. Yang, Y. X. Yin, H. Ye, N. W. Li, Y. G. Guo, J. Liu, W. Xu, J. G. Zhang, Nat. Energy 2019, 4, 796.
Adv. Mater. 2017, 29, 1700389. [206] L. Xiao, Z. Zeng, X. Liu, Y. Fang, X. Jiang, Y. Shao, L. Zhuang, X. Ai,
[176] D. Lee, S. Sun, J. Kwon, H. Park, M. Jang, E. Park, B. Son, Y. Jung, H. Yang, Y. Cao, J. Liu, ACS Energy Lett. 2019, 4, 483.
T. Song, U. Paik, Adv. Mater. 2020, 32, 1905573. [207] Z. Peng, X. Cao, P. Gao, H. Jia, X. Ren, S. Roy, Z. Li, Y. Zhu, W. Xie,
[177] S. Liu, X. Xia, Y. Zhong, S. Deng, Z. Yao, L. Zhang, X. B. Cheng, D. Liu, Q. Li, D. Wang, W. Xu, J. G. Zhang, Adv. Funct. Mater. 2020,
X. Wang, Q. Zhang, J. Tu, Adv. Energy Mater. 2018, 8, 1702322. 30, 2001285.
[178] X. Gao, X. Yang, K. Adair, X. Li, J. Liang, Q. Sun, Y. Zhao, R. Li, [208] H. Wang, J. He, J. Liu, S. Qi, M. Wu, J. Wen, Y. Chen, Y. Feng,
T. K. Sham, X. Sun, Adv. Energy Mater. 2020, 10, 1903753. J. Ma, Adv. Funct. Mater. 2020, 2002578.
[179] H. Yuan, J. Nai, Y. Fang, G. Lu, X. Tao, X. W. (David) Lou, [209] F. Qiu, X. Li, H. Deng, D. Wang, X. Mu, P. He, H. Zhou,
Angew. Chem. 2020, 132, 15973. Adv. Energy Mater. 2019, 9, 1803372.
[180] H. Wang, D. Lin, Y. Liu, Y. Li, Y. Cui, Sci. Adv. 2017, 3, 1701301. [210] N. Piao, X. Ji, H. Xu, X. Fan, L. Chen, S. Liu, M. N. Garaga,
[181] S. Ha, J. C. Hyun, J. H. Kwak, H. D. Lim, Y. S. Yun, Small 2020, 16, S. G. Greenbaum, L. Wang, C. Wang, X. He, Adv. Energy Mater.
2003918. 2020, 10, 1903568.
[182] C. Yan, Y. X. Yao, X. Chen, X. B. Cheng, X. Q. Zhang, J. Q. Huang, [211] W. Xue, Z. Shi, M. Huang, S. Feng, C. Wang, F. Wang, J. Lopez,
Q. Zhang, Angew. Chem., Int. Ed. 2018, 57, 14055. B. Qiao, G. Xu, W. Zhang, Y. Dong, R. Gao, Y. Shao-Horn,
[183] Y. Ma, Z. Zhou, C. Li, L. Wang, Y. Wang, X. Cheng, P. Zuo, C. Du, J. A. Johnson, J. Li, Energy Environ. Sci. 2020, 13, 212.
H. Huo, Y. Gao, G. Yin, Energy Storage Mater. 2018, 11, 197. [212] J. Chen, Q. Li, T. P. Pollard, X. Fan, O. Borodin, C. Wang,
[184] E. Markevich, G. Salitra, F. Chesneau, M. Schmidt, D. Aurbach, Mater. Today 2020, 39, 118.
ASC Energy Lett. 2017, 2, 1321. [213] Q. Zhang, S. Liu, Z. Lin, K. Wang, M. Chen, K. Xu, W. Li,
[185] B. Tong, J. Wang, Z. Liu, L. Ma, P. Wang, W. Feng, Z. Peng, Nano Energy 2020, 74, 104860.
Z. Zhou, J. Power Sources 2018, 400, 225. [214] K. Tang, A. Du, S. Dong, Z. Cui, X. Liu, C. Lu, J. Zhao, X. Zhou,
[186] L. Yu, S. Chen, H. Lee, L. Zhang, M. H. Engelhard, Q. Li, S. Jiao, G. Cui, Adv. Mater. 2020, 32, 1904987.
J. Liu, W. Xu, J. G. Zhang, ACS Energy Lett. 2018, 3, 2059. [215] J. Zheng, G. Ji, X. Fan, J. Chen, Q. Li, H. Wang, Y. Yang,
[187] D. Wang, G. Li, Q. Huang, X. He, Y. Gao, D. Wang, S. H. Kim, K. C. DeMella, S. R. Raghavan, C. Wang, Adv. Energy Mater. 2019,
ACS Nano 2018, 12, 1500. 9, 1803774.
[188] X. Li, J. Zheng, X. Ren, M. H. Engelhard, W. Zhao, Q. Li, [216] Y. Xiao, B. Han, Y. Zeng, S. Sen Chi, X. Zeng, Z. Zheng, K. Xu,
J. G. Zhang, W. Xu, Adv. Energy Mater. 2018, 8, 1703022. Y. Deng, Adv. Energy Mater. 2020, 10, 1903937.
[189] Y. Li, W. Huang, Y. Li, A. Pei, D. T. Boyle, Y. Cui, Joule 2018, 2, 2167. [217] X. Dong, Y. Lin, P. Li, Y. Ma, J. Huang, D. Bin, Y. Wang, Y. Qi,
[190] X. Fan, L. Chen, O. Borodin, X. Ji, J. Chen, S. Hou, T. Deng, Y. Xia, Angew. Chem. 2019, 131, 5679.
J. Zheng, C. Yang, S. C. Liou, K. Amine, K. Xu, C. Wang, [218] Y. Zhang, Y. Zhong, Z. Wu, B. Wang, S. Liang, H. Wang,
Nat. Nanotechnol. 2018, 13, 715. Angew. Chem., Int. Ed. 2020, 59, 7797.
[191] Z. Yu, H. Wang, X. Kong, W. Huang, Y. Tsao, D. G. Mackanic, [219] W. Li, H. Yao, K. Yan, G. Zheng, Z. Liang, Y. M. Chiang, Y. Cui,
K. Wang, X. Wang, W. Huang, S. Choudhury, Y. Zheng, Nat. Commun. 2015, 6, 7436.
C. V. Amanchukwu, S. T. Hung, Y. Ma, E. G. Lomeli, J. Qin, Y. Cui, [220] H. Wu, Y. Cao, L. Geng, C. Wang, Chem. Mater. 2017, 29, 3572.
Z. Bao, Nat. Energy 2020, 5, 526. [221] Y. Lee, T. K. Lee, S. Kim, J. Lee, Y. Ahn, K. Kim, H. Ma, G. Park,
[192] H. Ye, Y. X. Yin, S. F. Zhang, Y. Shi, L. Liu, X. X. Zeng, R. Wen, S. M. Lee, S. K. Kwak, N. S. Choi, Nano Energy 2020, 67, 104309.
Y. G. Guo, L. J. Wan, Nano Energy 2017, 36, 411. [222] G. Zheng, Y. Xiang, S. Chen, S. Ganapathy, T. W. Verhallen, M. Liu,
[193] Q. Zhao, Z. Tu, S. Wei, K. Zhang, S. Choudhury, X. Liu, L. A. Archer, G. Zhong, J. Zhu, X. Han, W. Wang, W. Zhao, M. Wagemaker,
Angew. Chem. 2018, 130, 1004. Y. Yang, Energy Storage Mater. 2020, 29, 377.
[194] S. Chen, J. Zheng, D. Mei, K. S. Han, M. H. Engelhard, W. Zhao, [223] G. Wang, X. Xiong, D. Xie, X. Fu, X. Ma, Y. Li, Y. Liu, Z. Lin,
W. Xu, J. Liu, J. G. Zhang, Adv. Mater. 2018, 30, 1706102. C. Yang, M. Liu, Energy Storage Mater. 2019, 23, 701.
[195] L. Suo, W. Xue, M. Gobet, S. G. Greenbaum, C. Wang, Y. Chen, [224] S. Li, H. Dai, Y. Li, C. Lai, J. Wang, F. Huo, C. Wang, Energy Storage
W. Yang, Y. Li, J. Li, Proc. Natl. Acad. Sci. USA 2018, 115, 1156. Mater. 2019, 18, 222.
[225] Z. Jiang, Z. Zeng, C. Yang, Z. Han, W. Hu, J. Lu, J. Xie, Nano Lett. [255] C. Cao, Y. Li, Y. Feng, C. Peng, Z. Li, W. Feng, Energy Storage Mater.
2019, 19, 8780. 2019, 19, 401.
[226] S. H. Lee, J. Y. Hwang, S. J. Park, G. T. Park, Y. K. Sun, Adv. Funct. [256] Q. Liu, Y. Liu, X. Jiao, Z. Song, M. Sadd, X. Xu, A. Matic, S. Xiong,
Mater. 2019, 29, 1902496. J. Song, Energy Storage Mater. 2019, 23, 105.
[227] S. J. Park, J. Y. Hwang, Y. K. Sun, J. Mater. Chem. A 2019, 7, 13441. [257] Q. Cheng, A. Li, N. Li, S. Li, A. Zangiabadi, T. De Li, W. Huang,
[228] X. Fan, L. Chen, X. Ji, T. Deng, S. Hou, J. Chen, J. Zheng, F. Wang, A. C. Li, T. Jin, Q. Song, W. Xu, N. Ni, H. Zhai, M. Dontigny,
J. Jiang, K. Xu, C. Wang, Chem 2018, 4, 174. K. Zaghib, X. Chuan, D. Su, K. Yan, Y. Yang, Joule 2019, 3, 1510.
[229] D. Wang, H. Liu, M. Li, D. Xia, J. Holoubek, Z. Deng, M. Yu, [258] J. Wen, Y. Huang, J. Duan, Y. Wu, W. Luo, L. Zhou, C. Hu, L. Huang,
J. Tian, Z. Shan, S. P. Ong, P. Liu, Z. Chen, Nano Energy 2020, 75, X. Zheng, W. Yang, Z. Wen, Y. Huang, ACS Nano 2019, 13, 14549.
104889. [259] C. Wang, K. R. Adair, J. Liang, X. Li, Y. Sun, X. Li, J. Wang, Q. Sun,
[230] X. Ren, S. Chen, H. Lee, D. Mei, M. H. Engelhard, S. D. Burton, F. Zhao, X. Lin, R. Li, H. Huang, L. Zhang, R. Yang, S. Lu, X. Sun,
W. Zhao, J. Zheng, Q. Li, M. S. Ding, M. Schroeder, J. Alvarado, Adv. Funct. Mater. 2019, 29, 1900392.
K. Xu, Y. S. Meng, J. Liu, J. G. Zhang, W. Xu, Chem 2018, 4, 1877. [260] H. Zheng, S. Wu, R. Tian, Z. Xu, H. Zhu, H. Duan, H. Liu,
[231] S. Bai, Y. Sun, J. Yi, Y. He, Y. Qiao, H. Zhou, Joule 2018, 2, 2117. Adv. Funct. Mater. 2020, 30, 1906189.
[232] S. Li, W. Zhang, Q. Wu, L. Fan, X. Wang, X. Wang, Z. Shen, Y. He, [261] C. Yang, H. Xie, W. Ping, K. Fu, B. Liu, J. Rao, J. Dai, C. Wang,
Y. Lu, Angew. Chem., Int. Ed 2020, 59, 14935. G. Pastel, L. Hu, Adv. Mater. 2019, 31, 1804815.
[233] J. Zheng, M. H. Engelhard, D. Mei, S. Jiao, B. J. Polzin, J. G. Zhang, [262] J. Duan, W. Wu, A. M. Nolan, T. Wang, J. Wen, C. Hu, Y. Mo,
W. Xu, Nat. Energy 2017, 2, 17012. W. Luo, Y. Huang, Adv. Mater. 2019, 31, 1807243.
[234] Z. Zeng, V. Murugesan, K. S. Han, X. Jiang, Y. Cao, L. Xiao, X. Ai, [263] R. Xu, Y. Xiao, R. Zhang, X. B. Cheng, C. Z. Zhao, X. Q. Zhang,
H. Yang, J. G. Zhang, M. L. Sushko, J. Liu, Nat. Energy 2018, 3, 674. C. Yan, Q. Zhang, J. Q. Huang, Adv. Mater. 2019, 31, 1808392.
[235] J. Y. Wei, X. Q. Zhang, L. P. Hou, P. Shi, B. Q. Li, Y. Xiao, C. Yan, [264] Z. Jiang, S. Wang, X. Chen, W. Yang, X. Yao, X. Hu, Q. Han,
H. Yuan, J. Q. Huang, Adv. Mater. 2020, 32, 2003012. H. Wang, Adv. Mater. 2020, 32, 1906221.
[236] H. Dai, X. Gu, J. Dong, C. Wang, C. Lai, S. Sun, Nat. Commun. [265] S. Xia, J. Lopez, C. Liang, Z. Zhang, Z. Bao, Y. Cui, W. Liu, Adv. Sci.
2020, 11, 643. 2019, 6, 1802353.
[237] H. Che, S. Chen, Y. Xie, H. Wang, K. Amine, X. Z. Liao, Z. F. Ma, [266] J. Liang, X. Li, Y. Zhao, L. V. Goncharova, W. Li, K. R. Adair,
Energy Environ. Sci. 2017, 10, 1075. M. N. Banis, Y. Hu, T. K. Sham, H. Huang, L. Zhang, S. Zhao,
[238] R. Murugan, V. Thangadurai, W. Weppner, Angew. Chem., Int. Ed. S. Lu, R. Li, X. Sun, Adv. Energy Mater. 2019, 9, 1902125.
2007, 46, 7778. [267] Y. Huang, B. Chen, J. Duan, F. Yang, T. Wang, Z. Wang, W. Yang,
[239] A. Sharafi, S. Yu, M. Naguib, M. Lee, C. Ma, H. M. Meyer, C. Hu, W. Luo, Y. Huang, Angew. Chem., Int. Ed. 2020, 59, 3699.
J. Nanda, M. Chi, D. J. Siegel, J. Sakamoto, J. Mater. Chem. A 2017, [268] H. Huo, Y. Chen, R. Li, N. Zhao, J. Luo, J. G. Pereira Da Silva, R. Mücke,
5, 13475. P. Kaghazchi, X. Guo, X. Sun, Energy Environ. Sci. 2020, 13, 127.
[240] W. Luo, Y. Gong, Y. Zhu, Y. Li, Y. Yao, Y. Zhang, K. K. Fu, G. Pastel, [269] F. Zhou, Z. Li, Y. Y. Lu, B. Shen, Y. Guan, X. X. Wang,
C. F. Lin, Y. Mo, E. D. Wachsman, L. Hu, Adv. Mater. 2017, 29, 1606042. Y. C. Yin, B. S. Zhu, L. L. Lu, Y. Ni, Y. Cui, H. Bin Yao, S. H. Yu,
[241] H. Huo, Y. Chen, N. Zhao, X. Lin, J. Luo, X. Yang, Y. Liu, X. Guo, Nat. Commun. 2019, 10, 2482.
X. Sun, Nano Energy 2019, 61, 119. [270] B. Zhang, Y. Liu, X. Pan, J. Liu, K. Doyle-Davis, L. Sun, J. Liu,
[242] S. Wenzel, D. A. Weber, T. Leichtweiss, M. R. Busche, J. Sann, X. Jiao, J. Jie, H. Xie, X. Sun, Nano Energy 2020, 72, 104690.
J. Janek, Solid State Ionics 2016, 286, 24. [271] W. Yu, C. Xue, B. Hu, B. Xu, L. Li, C. W. Nan, Energy Storage Mater.
[243] X. Hao, Q. Zhao, S. Su, S. Zhang, J. Ma, L. Shen, Q. Yu, L. Zhao, 2020, 27, 244.
Y. Liu, F. Kang, Y. B. He, Adv. Energy Mater. 2019, 9, 1901604. [272] J. Hu, Z. Yao, K. Chen, C. Li, Energy Storage Mater. 2020, 28, 37.
[244] Q. Pan, D. M. Smith, H. Qi, S. Wang, C. Y. Li, Adv. Mater. 2015, 27, [273] H. Xu, P. H. Chien, J. Shi, Y. Li, N. Wu, Y. Liu, Y. Y. Hu,
5995. J. B. Goodenough, Proc. Natl. Acad. Sci. USA 2019, 116, 18815.
[245] X. Zhang, S. Wang, C. Xue, C. Xin, Y. Lin, Y. Shen, L. Li, C. W. Nan, [274] X. Zhang, Q. Xiang, S. Tang, A. Wang, X. Liu, J. Luo, Nano Lett.
Adv. Mater. 2019, 31, 1806082. 2020, 20, 2871.
[246] W. Zhou, Z. Wang, Y. Pu, Y. Li, S. Xin, X. Li, J. Chen, [275] F. Zhao, Q. Sun, C. Yu, S. Zhang, K. Adair, S. Wang, Y. Liu, Y. Zhao,
J. B. Goodenough, Adv. Mater. 2019, 31, 1805574. J. Liang, C. Wang, X. Li, X. Li, W. Xia, R. Li, H. Huang, L. Zhang,
[247] X. Wang, H. Zhai, B. Qie, Q. Cheng, A. Li, J. Borovilas, B. Xu, S. Zhao, S. Lu, X. Sun, ACS Energy Lett. 2020, 5, 1035.
C. Shi, T. Jin, X. Liao, Y. Li, X. He, S. Du, Y. Fu, M. Dontigny, [276] W. Feng, X. Dong, Z. Lai, X. Zhang, Y. Wang, C. Wang, J. Luo,
K. Zaghib, Y. Yang, Nano Energy 2019, 60, 205. Y. Xia, ACS Energy Lett. 2019, 4, 1725.
[248] C. Z. Zhao, X. Q. Zhang, X. B. Cheng, R. Zhang, R. Xu, P. Y. Chen, [277] C. Ding, X. Fu, H. Li, J. Yang, J. L.e Lan, Y. Yu, W. H. Zhong,
H. J. Peng, J. Q. Huang, Q. Zhang, Proc. Natl. Acad. Sci. USA 2017, X. Yang, Adv. Funct. Mater. 2019, 29, 1904547.
114, 11069. [278] M. Xie, X. Lin, Z. Huang, Y. Li, Y. Zhong, Z. Cheng, L. Yuan, Y. Shen,
[249] H. Duan, M. Fan, W. P. Chen, J. Y. Li, P. F. Wang, W. P. Wang, X. Lu, T. Zhai, Y. Huang, Adv. Funct. Mater. 2020, 30, 1905949.
J. L. Shi, Y. X. Yin, L. J. Wan, Y. G. Guo, Adv. Mater. 2019, 31, [279] S. Xiong, Y. Liu, P. Jankowski, Q. Liu, F. Nitze, K. Xie, J. Song,
1807789. A. Matic, Adv. Funct. Mater. 2020, 30, 2001444.
[250] X. Han, Y. Gong, K. Fu, X. He, G. T. Hitz, J. Dai, A. Pearse, B. Liu, [280] H. Huo, Y. Chen, J. Luo, X. Yang, X. Guo, X. Sun, Adv. Energy
H. Wang, G. Rubloff, Y. Mo, V. Thangadurai, E. D. Wachsman, Mater. 2019, 9, 1804004.
L. Hu, Nat. Mater. 2017, 16, 572. [281] F. Zhao, J. Liang, C. Yu, Q. Sun, X. Li, K. Adair, C. Wang, Y. Zhao,
[251] Q. Zhao, X. Liu, S. Stalin, K. Khan, L. A. Archer, Nat. Energy 2019, S. Zhang, W. Li, S. Deng, R. Li, Y. Huang, H. Huang, L. Zhang,
4, 365. S. Zhao, S. Lu, X. Sun, Adv. Energy Mater. 2020, 10, 1903422.
[252] S. Li, H. Wang, J. Cuthbert, T. Liu, J. F. Whitacre, K. Matyjaszewski, [282] J. Fu, P. Yu, N. Zhang, G. Ren, S. Zheng, W. Huang, X. Long, H. Li,
Joule 2019, 3, 1637. X. Liu, Energy Environ. Sci. 2019, 12, 1404.
[253] Z. Lu, J. Yu, J. Wu, M. B. Effat, S. C. T. Kwok, Y. Lyu, M. M. F. Yuen, [283] X. Fan, X. Ji, F. Han, J. Yue, J. Chen, L. Chen, T. Deng, J. Jiang,
F. Ciucci, Energy Storage Mater. 2019, 18, 311. C. Wang, Sci. Adv. 2018, 4, eaau9245.
[254] S. Sen Chi, Y. Liu, N. Zhao, X. Guo, C. W. Nan, L. Z. Fan, Energy [284] C. Luo, E. Hu, K. J. Gaskell, X. Fan, T. Gao, C. Cui, S. Ghose,
Storage Mater. 2019, 17, 309. X. Q. Yang, C. Wang, Proc. Natl. Acad. Sci. USA 2020, 117, 14712.
[285] A. G. Simmonds, J. J. Griebel, J. Park, K. R. Kim, W. J. Chung, [289] J. Song, M. L. Gordin, T. Xu, S. Chen, Z. Yu, H. Sohn, J. Lu, Y. Ren,
V. P. Oleshko, J. Kim, E. T. Kim, R. S. Glass, C. L. Soles, Y. E. Sung, Y. Duan, D. Wang, Angew. Chem., Int. Ed. 2015, 54, 4325.
K. Char, J. Pyun, ACS Macro Lett. 2014, 3, 229. [290] W. Zhou, C. Wang, Q. Zhang, H. D. Abruña, Y. He, J. Wang,
[286] W. Hua, Z. Yang, H. Nie, Z. Li, J. Yang, Z. Guo, C. Ruan, X. Chen, S. X. Mao, X. Xiao, Adv. Energy Mater. 2015, 5, 1401752.
S. Huang, ACS Nano 2017, 11, 2209. [291] S. Nanda, A. Manthiram, Energy Environ. Sci. 2020, 13, 2501.
[287] R. Zhang, X. B. Cheng, C. Z. Zhao, H. J. Peng, J. L.e Shi, [292] H. Ye, S. Xin, Y. X. Yin, J. Y. Li, Y. G. Guo, L. J. Wan, J. Am. Chem.
J. Q. Huang, J. Wang, F. Wei, Q. Zhang, Adv. Mater. 2016, 28, 2155. Soc. 2017, 139, 5916.
[288] H. Yang, C. Guo, J. Chen, A. Naveed, J. Yang, Y. Nuli, J. Wang, [293] H. Li, D. Chao, B. Chen, X. Chen, C. Chuah, Y. Tang, Y. Jiao,
Angew. Chem., Int. Ed. 2019, 58, 791. M. Jaroniec, S. Z. Qiao, J. Am. Chem. Soc. 2020, 142, 2012.
Kaiqiang Qin obtained his Ph.D. from Tianjin University (China) in 2018. He joined the University
of California, Los Angeles (UCLA, USA) as a postdoc from 2018 to 2020. He is currently a postdoc
in Prof. Luo’s lab at George Mason University (USA). His current research interests focuses on
next-generation energy storage materials.
Kathryn Holguin received her Bachelor’s degree in 2009 and Master’s degree in 2011 from George
Mason University. She is currently a Ph.D. candidate under the supervision of Prof. Chao Luo in
the Chemistry and Biochemistry Department, George Mason University. Her research interests
focuses on organic electrode materials for next-generation energy storage devices.
Motahareh Mohammadiroudbari received her B.S. and M.S. in Polymer Engineering from
Amirkabir University of Technology and Sahand University of Technology, respectively. She is
currently a Ph.D. student in the Department of Chemistry and Biochemistry at George Mason
University. Her research interests focuses on polymeric structure engineering for sodium-ion and
multivalent metal batteries.
Jinghao Huang received his Bachelor’s degree in chemistry from University of California, Irvine
(UCI). He is currently a Ph.D. student under the supervision of Prof. Chao Luo in the Department
of Chemistry and Biochemistry, George Mason University. His current research interests focuses
on organic electrode materials for sodium-ion batteries.
Eric Young Sam Kim holds bachelor’s degree in Chemistry from Liberty University, VA, USA. He is
a master student in Department of Chemistry and Biochemistry at George Mason University. He
performs his research under the supervision of Prof. Chao Luo. His research interest focuses on
developing new materials and electrolytes for lithium-sulfur batteries.
Rosemary Hall graduated from George Mason University in 2020 with a Bachelor of Science in
Chemistry and a minor in Korean Studies. As an undergraduate student, she conducted research
that focused on organic electrode materials for lithium-ion and sodium-ion batteries. She is
interested in applying her chemistry knowledge to solve environmental, health, and production
issues related to synthetic materials and energy storage devices.
Chao Luo received his Bachelor’s degree from Wuhan University in 2008. Then, he entered
Technical Institute of Chemistry and Physics, Chinese Academy of Sciences and received his
Master’s degree in 2011. After that, he obtained Ph.D. degree at University of Maryland, College
Park in 2015 and worked as a postdoc at University of Maryland, College Park from 2016 to 2019.
He is currently an assistant professor at George Mason University. His research interests focuses
on developing new materials and new chemistries for high-performance and sustainable energy
storage devices.

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Review

Strategies in Structure and Electrolyte Design for

challenge, a breakthrough in high-energy

Figure 1. Overview of fundamental properties of different types of anode materials in Li batteries.

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Table 3. Summary of electrochemical performances of Li metal anode in various liquid electrolytes.

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Table 4. Summary of electrochemical performances of Li metal anode enhanced by solid-state electrolytes.

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

Ref. Method Electrolyte Cycle Life Coulombic Efficiency Over-potential

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