Review

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Anode-Free Full Cells: A Pathway to High-Energy Density

Lithium-Metal Batteries
Sanjay Nanda, Abhay Gupta, and Arumugam Manthiram*

layered-oxide cathodes to improve capaci-

The development of high-energy density batteries is critical to the decarboni- ties.[5–7] In contrast, there is still substan-
zation of the transportation and power generation sectors. For any given tial unfulfilled potential for increasing the
lithium-containing cathode system, the anode-free full cell configuration, energy density at the anode. The incum-
bent graphite anode, with a theoretical
which eliminates excess lithium and pairs the fully lithiated cathode with a
capacity of only 372 mAh g−1, has been
bare current collector, can deliver the maximum possible energy density. The used mostly unchanged since the intro-
absence of free lithium metal during cell assembly confers significant practical duction of commercial Li-ion batteries
advantages as well. It is also the ideal framework for developing a thorough by Sony Corporation in 1991.[8–10] Some
understanding of lithium deposition in conjunction with various cathode improvements in capacity have been deliv-
systems. However, the poor efficiencies of lithium plating and stripping ered by the incorporation of silicon into
graphite anodes.[11,12] However, lithium-
lead to rapid lithium inventory loss and poor cycle life. In the last few years, metal anodes show the greatest potential
multiple studies have demonstrated the application of advanced electrolytes, for enabling a quantum leap in the energy
modified current collectors, and optimized formation and cycling parameters density of lithium batteries. It is con-
to stabilize lithium deposition and improve cycle life (80% capacity retention) sidered the ideal anode material due to
to 100 cycles and beyond. This review provides an overview of the various having the lowest redox potential (-3.04 V
vs SHE) and the highest theoretical
strategies toward sustaining lithium inventory in anode-free full cells and sum-
capacity (3860 mAh g−1, 2061 mAh cm−3)
marizes the work undertaken in this nascent field. It is expected that further of all possible anode materials.[13–15] It is
improvement upon these strategies and a combinatorial approach can enable also indispensable for futuristic cathodes
cycle lives far in excess of what has been achieved so far. such as sulfur and oxygen/air. Despite its
advantages, the practical implementation
of lithium-metal anodes has been hin-
dered by the poor reversibility of lithium
1. Introduction plating and stripping.[16,17] The formation of high surface area
“mossy” deposits of lithium leads to its depletion by undesir-
High-energy-density rechargeable batteries have emerged as able side reactions.[18] This can be compensated for by using
one of the most important technologies of the 21st century, excess lithium, but that negates the energy density advantage
indispensable for a wide range of applications ranging from of lithium-metal anodes. Over the last few years, there have
miniaturized electronics to all-electric vehicles to grid storage. been considerable efforts by researchers to stabilize lithium
Many fundamental developments in solid-state chemistry deposition and improve the cyclability of lithium-metal
and physics led to the development of Li-ion batteries, which anodes.[19–21]
are now pre-eminent in most application spaces.[1] Commer- An intriguing and under-explored possibility for realizing lith-
cial Li-ion batteries have a typical energy density of less than ium-metal batteries is the anode-free full cell configuration.[22–25]
250 Wh kg−1 at the cell level.[2] Increasing the energy density of By pairing a fully lithiated cathode with a bare current collector
the batteries, to say 500 Wh kg−1, would enable one or a com- on the anode side, the anode to cathode capacity ratio can be
bination of increased device run-time (e.g., driving range) or kept exactly equal to 1. This enables the maximum possible
decreased device footprint.[3,4] Steady gains in energy density of energy density to be delivered from any given cathode system.
up to 40% have been realized by increasing the nickel content of Since there is no excess lithium to artificially inflate cyclability,
the electrochemical performance of anode-free full cells is lim-
ited almost entirely by the efficiency of lithium plating and
S. Nanda, A. Gupta, Prof. A. Manthiram stripping. This allows a more realistic assessment of the electro-
Materials Science and Engineering Program & Texas Materials Institute chemical performance of lithium-metal batteries. Various strat-
The University of Texas at Austin egies for stabilizing lithium deposition can also be effectively
Austin, TX 78712, USA evaluated using the anode-free configuration. In the last few
E-mail: manth@austin.utexas.edu
years, a number of groups have reported a variety of strategies
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202000804.
for improving the cyclability of anode-free batteries, including
novel electrolyte formulations, artificial SEI layers, modified
DOI: 10.1002/aenm.202000804 current collector substrates, favorable formation procedures,

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and optimized cell testing protocols. This review provides an

overview of the different approaches reported in the literature Sanjay Nanda is currently a
and concludes with an outlook for this nascent and promising PhD candidate in Materials
field. Science and Engineering at
the University of Texas at
Austin. He received his B.Sc.
(2013) degree in Physics
2. Anode-Free Full Cells
from the Indian Institute
The anode-free full cell configuration promises a transforma- of Technology, Kanpur, and
tive enhancement in energy density to 500 Wh kg−1 and his M.Phil (2014) degree in
beyond. Li-ion batteries are typically assembled in the Cu/C6/ Nanotechnology from the
PP/LiXO/Al configuration, where Cu and Al are the current University of Cambridge.
collectors, C6 is the graphite anode, LiXO is the lithiated oxide His research is focused
cathode (LCO, NMC, NCA, LMO, LFP), and PP is the polymer on devising strategies for stabilizing lithium deposi-
separator. Anode-free full cells can be visualized as the same tion in lithium–sulfur batteries and understanding the
configuration as above, but with the C6 graphite anode com- degradation mechanisms that underlie the failure of
pletely eliminated to yield the Cu/PP/LiXO/Al configuration. lithium-metal anodes.
Other unconventional lithiated cathodes such as Li2S, LiI, and
LiMS2, where M is a transition metal, can also be employed. Abhay Gupta is a PhD
Assembled in the discharged state, Li+ ions from the cathode student in Materials Science
in the anode-free full cells are reduced and plated as lithium and Engineering at the
(Li0) metal on the Cu foil current collector during charge. Sub- University of Texas at Austin.
sequently, the plated lithium metal is stripped away during He received his B.S. from the
discharge. In its simplest form, the absence of a host to accom- Hildebrand Department of
modate the lithium deposited on the current collector make Petroleum and Geosystems
it a “hostless” anode. In one embodiment of a Li-ion battery, Engineering at the University
the removal of the graphite host, which occupies 27.8% of the of Texas at Austin in 2016. His
overall stack weight and 46.1% of the overall stack thickness, research primarily focuses
would boost gravimetric energy density by 38.5% and volu- on investigating solution-
metric energy density by 85.5% (at the stack level).[26] Figure 1 coordination behavior in
demonstrates the differences in cell configuration and the lithium–sulfur batteries, with an emphasis on low-tempera-
corresponding increases in both gravimetric and volumetric ture performance.
energy density.
It should be noted here that there are large volume changes in Arumugam Manthiram is
the cell stack associated with charge and discharge of an anode- the Cockrell Family Regents
free full cell. Even accounting for the ≈20% volume expansion Chair in Engineering and the
of the stack with the plating of lithium and assuming negligible Director of Texas Materials
volume contraction at the cathode, the volumetric energy den- Institute and Materials
sity is still boosted by 57.1% compared to a Li-ion battery with a Science and Engineering
graphite anode. Nevertheless, these volume changes will have Program at the University of
to be accommodated by appropriate cell or battery pack designs. Texas at Austin. His research
In regular full cells, an increase in cathode capacity due to interests are in the area
either increased loading or higher electrochemical utilization of batteries and fuel cells,
has to be accompanied by a corresponding increase in anode including new materials
capacity, typically by an increased loading of the anode active development, novel synthesis
material. This requirement is obviated in the anode-free full approaches, and structure–composition–performance
cell configuration. Furthermore, the negative to positive elec- relationships.
trode capacity (N/P) ratio, defined for anode-free full cells as the
ratio of lithium inventory to cathode inventory, is exactly equal
to 1. The need to use a slight excess of anode-active material
to prevent undesirable lithium plating is also obviated. Finally, Here, X can be any lithiated or nonlithiated cathode. While
the use of any anode material other than lithium metal would the use of lithium foils is required for nonlithiated cathodes
lower the voltage output of the cell due to the potential asso- such as sulfur, fully lithiated cathodes already carry the stoi-
ciated with lithiation of the anode. The anode-free configura- chiometric amount of lithium necessary for a complete charge/
tion ensures the highest possible voltage output for any cathode discharge cycle. In the example system shown in Figure 1 with
system. All of these factors combine to engender a dramatic a fully lithiated NCA cathode of capacity 6.1 mAh cm−2 and
increase in energy density with anode-free batteries. a N/P ratio of 3, the lithium-metal foil anode would have a
Lithium metal batteries are typically envisioned as employing capacity of 12.2 mAh cm−2, corresponding to a lithium-metal
thin lithium foil anodes, in the Cu/Li/PP/X/Al configuration. foil of thickness 59.2 µm and weight 3.16 mg cm−2. However,

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Figure 1. a) Schematic illustration of an example lithium-ion battery using an NCA cathode of thickness 100 µm and a loading 30.5 mg cm−2, with
the thickness of the various components drawn to scale. b) Schematic illustration of an anode-free full cell using an equivalent NCA cathode, in both
charged and discharged states. The difference in energy density can be clearly visualized. There is a ≈20% volume change associated with the plating
and stripping of lithium, which will have to be accommodated. c) Weight distribution of each stack component in a Li-ion battery, with the graphite
anode occupying 27.8% of the stack weight. d) Weight of each stack component in an equivalent anode-free full cell. The volume and weight distribu-
tions of the example lithium-ion battery were obtained from a 2018 work by Betz et al.[26]

manufacturing thin lithium foils (<100 µm thickness) over
large areas with acceptable control over chemical purity and
microstructure has proven exceedingly challenging and expen-
sive.[27,28] Handling thin lithium foils is also difficult due to
the lack of mechanical robustness and its high reactivity with
moisture and air. Hence, the process of coating the surface of
lithium metal with passivating layers or stabilizing interphases
is quite nontrivial. All of these problems are precluded with the
use of the anode-free full cell configuration due to the absence
of any free lithium metal. The minimal and trivial changes in
cell architecture when compared to existing Li-ion batteries
means that the production of anode-free full cells can be readily
integrated into existing battery manufacturing infrastructure
with minimal disruption. Since anode-free full cells are assem-
bled in the fully discharged condition, they are at a lower-energy
state compared to the charged condition. Hence, they are inher-
ently safer to handle. Furthermore, since the cathode is fully
lithiated, any further reaction in open-circuit conditions is
nonspontaneous (Gibbs free energy ΔG° > 0). Hence, the pos-
sibility of self-discharge, which is an internal energy-lowering
mechanism, is precluded in as-assembled anode-free full cells.
This is a particular advantage over systems assembled in the
charged condition that show considerable self-discharge, such
as conventional lithium–sulfur batteries.
3. Capacity Loss in Anode-Free Full Cells
The advantages of enhanced energy density and design sim-
plicity with anode-free full cells come with a major disadvan-
tage. While lithium can be inserted into and removed from
graphite anodes with minimal loss over thousands of cycles, the
same cannot be said for the plating and stripping of lithium.
In liquid electrolytes, lithium metal undergoes two growth
mechanisms during deposition: i) mossy and ii) dendritic.[18]
The initial “mossy” growth is attributed to a nonuniform flux
of Li+ ions on the current collector and leads to the forma-
tion of a large number of entangled thin filament-like lithium
microstructures. The highly reducing nature of lithium metal
causes the electrolyte to decompose on the lithium surface to
form a solid-electrolyte interphase (SEI). The large surface area
of the porous mossy lithium deposits intensifies these para-
sitic side reactions. The insulating SEI layer is nominally pas-
sivating to further side reactions as it blocks electron transfer
from metallic lithium to the electrolyte. However, since lithium
metal is a “hostless” anode, the plating and stripping of lithium
is accompanied by very large volume changes, which disinte-
grates the SEI layer and leads to continued decomposition of
the electrolyte on the lithium surface. Over many cycles, a thick
layer of electrolyte decomposition products, which are typically
poor Li+ ion conductors, is formed. This blocks electron and
Li+-ion transfer to the unreacted metallic lithium and renders
it electrochemically inaccessible or “dead.”[29] The combina-
tion of parasitic side reactions and formation of “dead” lithium
leads to the irreversible loss of both the lithium inventory and
electrolyte supply. When the electrolyte salt concentration falls
to zero at the lithium surface and the applied current exceeds
diffusion-based transport limitations, rapid dendritic growth
occurs.[30] This further intensifies parasitic side reactions with
the electrolyte and can cause internal short circuits, which
increases the risk of catastrophic cell failure along with the
associated safety concerns.

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The intrinsically low reversibility of lithium plating and strip-
ping leads to rapid loss of lithium inventory with cycling. This
is especially true for lithium deposition on bare planar sub-
strates with unoptimized electrolytes. Since anode-free full cells
(Cu || LiX, where LiX is a fully lithiated cathode) only have a lim-
ited lithium inventory (N/P ratio = 1), the loss of lithium inven-
tory leads to rapid capacity fade. This is particularly evident
when comparing the performance of anode-free full cells to that
of half cells (Li || LiX), which employ a large excess of lithium.
The cyclability of half cells is artificially inflated and does not
truly reflect lithium inventory loss inside the cell, as any lithium
lost due to inefficiencies in cell operation is simply replenished
from the lithium reservoir. In addition, the excess lithium
employed invalidates the energy density advantage of lithium-
metal anodes. In contrast, lithium inventory loss in anode-free
full cells renders an equivalent amount of the cathode material
electrochemically inaccessible, which leads to a corresponding
reduction in deliverable capacity and limits their cyclability.
Improving the cycle life of anode-free full cells requires the
development of strategies for stabilizing lithium deposition and
sustaining the limited lithium inventory with cycling. These
strategies are discussed in detail in Section 4.
Assuming that there is negligible loss of active material at
the cathode, the capacity fade of anode-free full cells can be
attributed entirely to the loss of lithium inventory. It may be
further assumed that lithium inventory loss can be directly pre-
dicted from the measured Coulombic efficiency, i.e., the ratio
of discharge capacity to charge capacity as measured during
electrochemical cycling. This relies on the presumption that
lithium inventory loss occurs during either the charge step or
discharge step, but not both. Under these assumptions, the dis-
charge capacity Qn of an anode-free full cell after n cycles can
be expressed as
n
Q n = Q in * ∏ CE
i=2
i = Q in * GCEn
where Qin is the initial discharge capacity, CEi is the Coulombic
efficiency for cycle number i, and GCE is the geometric mean
of Coulombic efficiency values for n cycles.[24] The amount of
lithium that is recoverable as a fraction of the lithium plated
during the first charge step is typically smaller compared to later
cycles, due to which the initial discharge capacity may be sub-
stantially smaller than the theoretical capacity of the anode-free
full cell. The first cycle capacity loss can be accounted for by con-
sidering the initial discharge capacity for the calculation above.
Nevertheless, it needs to be clearly reported for accurate assess-
ment of electrochemical performance, as a significant first cycle
capacity loss can diminish the realizable energy density, even if
lithium deposition is highly reversible during further cycling.
Further assuming that the value of Coulombic efficiency is
constant for the n cycles at a value CE, the equation reduces
to Qn = Qin *CEn. Figure 2a shows the capacity retention
(Qn/Qin) as a function of cycle number for different values of
CE. It can be seen that cycle life, defined generously as the
number of cycles taken to reach 50% capacity retention, dis-
plays a strong dependence on Coulombic efficiency. The ratio
of cycle lives for cells a and b with Coulombic efficiencies CEa
and CEb can be derived as
na log ( CEb ) (2)
=
nb log ( CEa )
Using the formula, it can be shown that every jump in
Coulombic efficiency from 90% to 99%, and then to 99.9% and
so on leads to a roughly 10-fold improvement in cycle life. At a
Coulombic efficiency of 99.99%, the cycle life becomes compa-
rable to that of commercial cells with graphite anodes. All of
the formulas above apply even if there is loss of active mate-
rial at the cathode, so long as it remains less than the lithium
inventory loss throughout cycling.
In practical systems, however, the measured values of Cou-
lombic efficiency can display significant variations with cycling.
Hence, different capacity fade regimes with significant varia-
(1)
tions in the rates of lithium inventory loss may be observed (for
instance, if an electrolyte additive is depleted in the course of
cycling). It is also possible that Coulombic efficiency could cease
to be a useful predictor of capacity fade. This is particularly

Figure 2. a) Capacity retention with cycle number of an anode-free full cell for different values of average Coulombic efficiency. 50% capacity retention
is generously used to determine the cycle life. b) Capacity retention with cycle number for hypothetical anode-free full cells that show a higher initial
cathode inventory loss (40%) compared to lithium inventory loss (20%). The subsequent cathode inventory loss rate is 0.1% per cycle. A capacity
plateau can be seen that is engendered due to the temporary excess of lithium inventory in the cell. The length of the capacity plateau depends on the
lithium inventory retention rates, as can be seen from the difference between 99% and 99.5%.

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applicable when comparable losses in lithium inventory are
registered during both the plating and stripping steps. Another
important exception to this rule occurs in systems with sol-
uble redox mediators that shuttle between the cathode and the
anode, which are discussed in detail in Section 5.[31,32]
These problems can be circumvented by defining analogous
to Coulombic efficiency a new parameter, the lithium inventory
retention, which for any given cycle number i can be defined
as LIRi = Qi/Qi−1, where Qi is the discharge capacity for cycle
number i. This can be further used to derive another useful
parameter, the lithium inventory retention rate (LIRR), which
can be defined as a percentage
1
 Qn  n
LIRR = 100 *  (3)
 Q in 
Here, the LIRR can be calculated by using a specific capacity
retention (say 80%) and the corresponding number of cycles, or
conversely, by using a specific number of cycles (say 100 cycles)
and the corresponding capacity retention. In either case, the
LIRR, as a proxy for Coulombic efficiency and as a measure of
the “average” loss in lithium inventory per cycle, can be a useful
value for a comparison across different reported anode-free full
cells owing to its simple calculation. In this review, we have
strived to calculate the LIRR for the best reported anode-free
full cell in each work, and used n = 100 or 50 cycles, depending
on the available information, and the corresponding capacity
retention.
For most systems, the overall inventory loss rates for the
cathode active material are generally less than that for lithium.
However, the first cycle inventory loss for the cathode can be
quite significant and can even be greater than that for lithium.
In such cases, there is a partial excess of lithium inventory com-
pared to the cathode inventory after the first charge/discharge
cycle. Since the measured capacity in a full cell is a convolution
of the active inventory for both the cathode and the anode, a
“capacity plateau” is observed until the lithium inventory excess
is depleted and exponential capacity loss is resumed. Figure 2b
shows the predicted capacity retention for two anode-free full
cells with an LIRR equal to 99% and 99.5% respectively, given
a first cycle lithium inventory loss of 20%, first cycle cathode
inventory loss of 40%, and subsequent cathode inventory loss
rate of 0.1% per cycle. In these example systems, the capacity
plateau is observed for 33 cycles at 99% LIRR and 73 cycles at
99.5% LIRR, when the active lithium and cathode inventory
reach parity. This behavior can also be observed when the lithi-
ated cathode is fully charged, but subsequently the delithiated
cathode is only partially discharged.[33] In these cases, the LIRR
has to be extrapolated from the lithium-limited cycling regime,
i.e., beyond the capacity plateau. Therefore, it is critical to
report complete cyclability information for anode-free full cells,
until cell failure, to prevent an overestimation of the lithium
inventory retention rates.
A comparison of capacity fade between a Li || LiX half-cell
and an anode-free Cu || LiX full cell may be instructive here.
Assuming complete replenishment of lost lithium inventory
from the lithium reservoir in a half cell, its capacity is simply
a measure of the active cathode inventory. Hence, its cycling
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profile would directly overlap with the capacity plateau observed
in the anode-free full cell. Therefore, it may be useful to report
electrochemical cycling data for equivalent half cells in con-
junction with anode-free full cells in order to shed light on the
dynamics of inventory loss for both the anode and the cathode.
The dependence of electrochemical performance of anode-
free full cells on the Coulombic efficiencies of plating and strip-
ping lithium imparts them with poor cyclability, but also makes
them excellent diagnostic templates for effectively investigating
the dynamics of lithium deposition. This is especially true in
conjunction with certain cathode systems, such as NMC, LMO,
and sulfur, where active material dissolution at the cathode and
crossover to the anode side has an observable impact on the
characteristics of lithium deposition.[34–37] The commonly uti-
lized Li || Cu half cells or Li || Li symmetric cells are inadequate
for accurately replicating lithium plating and stripping in such
systems and can only provide incomplete information. Various
strategies for stabilizing lithium deposition and improving the
Coulombic efficiencies of lithium plating and stripping, such
as electrolyte additives and artificial SEI layers, can be robustly
and rapidly evaluated in the anode-free framework. Signifi-
cantly, the compatibility of all aspects of such strategies, espe-
cially different electrolyte formulations, with various cathode
systems can be determined. Detailed characterization of the
deposited lithium in anode-free full cells, both before and after
stripping, can generate useful insights into its morphology,
structure, and composition.[38] Considering the absence of
excess metallic lithium typically present in lithium-metal foil
anodes, an accurate picture of the distribution of various SEI
components and deposited lithium metal (both electrochemi-
cally active and “dead”) can be obtained. This can prove particu-
larly useful for detailed quantitative studies on the mechanisms
that lead to lithium inventory loss with cycling.[29]
A major challenge with anode-free full cells is the large
volume expansion of the cell stack that accompanies plating
and stripping of lithium. In the example system shown in
Figure 1b, 6.2 mAh cm−2 of plated lithium capacity corresponds
to a 30 µm increase in stack thickness, or a volume expansion
of nearly 20%. However, this is still an underestimate, as the
actual thickness of porous high-surface area deposited lithium
of a particular capacity would almost certainly exceed the the-
oretical value.[39] The volume expansion of the cell stack with
lithium plating may be partially offset by an accompanying con-
traction of the fully lithiated cathode upon delithiation. This is
especially true for cathodes such as Li2S that undergoes a 43%
volume contraction during charge. However, layered-oxide
NMC and NCA cathodes experience negligible contraction with
lithium extraction. In such cases, novel strategies will have to
be devised to accommodate the large changes in volume of the
cell stack with cycling. Since the problem of volume expansion
is made significantly worse by mossy or dendritic plating of
lithium, it becomes even more critical to stabilize lithium depo-
sition and form compact, dense, and uniform lithium deposits.
The application of pressure, possibly in conjunction with
temperature controls, could also help alleviate this problem.
Another strategy is to devise a 3D host to accommodate the
deposited lithium and contain the extreme volume changes.
However, the extra weight and volume of the 3D current col-
lector will have to be taken into consideration so as to not
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Figure 3. a) An outline of the three broad classes of strategies employed to improve anode-free full cell performance and b) scanning electron micros-
copy image of deposited lithium-metal with high surface area and low surface area morphologies.
invalidate the energy density advantage of anode-free full cells.
They could also compromise energy density by way of the extra
electrolyte needed for acceptable cell operation. Fundamentally
new cell component designs and pack-level innovations could
be necessary to surmount this problem.
4. Strategies for Improving Performance
of Anode-Free Full Cells
The first reported work on anode-free full cells was by Neu-
decker et al.[40] They reported a thin-film battery employing
up to 3 µm thick LiCoO2 cathodes, a LiPON film as the elec-
trolyte, and a sputter deposited Cu current collector. Excellent
cyclability was obtained at current rates up to 5 mA cm−2, but
the capacity of the plated lithium was less than 0.1 mAh cm−2.
This review primarily covers anode-free full cells employing
traditional liquid electrolytes, except for a section on solid-state
anode-free batteries at the end.
Given the considerable importance of accounting for and
sustaining lithium inventory in anode-free full cells, the major
aim of anode-free research over the past few years has been
focused on improving Coulombic efficiencies (CE) by miti-
gating irreversible loss of lithium inventory. While cathode opti-
mization is a critical tool for achieving optimal electrochemical
performance, anode-free full cells are primarily limited by the
poor efficiency of plating and stripping lithium at the anode
current collector. Hence, most studies have focused on two
critical aspects for stabilizing lithium deposition and sustaining
lithium inventory: promoting favorable lithium deposition mor-
phology and ensuring a favorable solid-electrolyte interphase
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(SEI), which ensures facile conduction of Li+ ions and pre-
vents decomposition of the liquid electrolyte on the deposited
lithium. The major tools in delivering these aims are i) modi-
fication of the liquid electrolyte, ii) modification of the current
collector substrate upon which the lithium metal is deposited,
and iii) optimization of formation and cycling parameters to
prevent capacity fade. These strategies are outlined in Figure 3.
4.1. Modification of the Electrolyte
The electrolyte is a critical component of any anode-free full
cell, as it plays an essential role in determining the morphology
of the deposited lithium as well as the composition of the
SEI layer formed on the lithium surface. By precisely tuning
the electrolyte to enable uniform and smooth lithium deposi-
tion, the growth of high surface area “mossy” lithium can be
mitigated, inhibiting undesirable side reactions between the
electrolyte and metallic lithium. In the same vein, the electro-
lyte can be tuned to decompose into a favorable SEI on the
surface of the deposited lithium, with high ionic conductivity
to ensure electrochemical accessibility to the enclosed lithium
metal and effective passivation to mitigate further electrolyte
decomposition. Both of these measures can go a long way
toward preserving lithium inventory over the course of cycling.
The seminal work on anode-free full cells with liquid elec-
trolytes, published by Qian et al.,[22] thoroughly investigated the
trade-offs between using a standard carbonate electrolyte, 1 m
LiPF6 in ethylene carbonate (EC)/dimethyl carbonate(DMC)
(1:2, v/v), versus a highly concentrated ether-based electrolyte, 4 m
lithium bis(fluorosulfonyl)imide (LiFSI) in dimethoxyethane
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(DME). These electrolytes were employed in an anode-free bat-
tery with a copper current collector and LiFePO4 (LFP) cathode.
Lithium plating and stripping was effectively stabilized by
the 4 m LiFSI in DME electrolyte, exhibiting both improved
deposition morphology and favorable SEI formation. This
high-concentration electrolyte enabled 60% capacity reten-
tion after 50 cycles (LIRR = 99%), maintaining an average CE
greater than 99%. The initial lithium stripping capacity was
1.7 mAh cm−2, and the current rate was 0.2 mA cm−2. The
improvement in electrochemical performance was attributed
to the greater degree of coordination between solvent and salt
molecules, such that the majority of salt anions, cations, and
solvent molecules exist in contact-ion-pairs or solvate aggregate
states. Volumetrically, there is also a fourfold increase in the
concentration of Li+ ions available to reduce on the surface of
the current collector and form metallic lithium during charge.
Further, the increased concentration of salt anions in the elec-
tric double-layer adjacent to the negatively polarized current
collector surface leads to a more uniform flux of Li+ ions,
leading to uniform lithium deposition. Finally, the reduction of
FSI− anionic species leads to the formation of a favorable SEI
for lithium deposition rich with inorganic components such
as LiF.[17,41] This work outlined the fundamental design princi-
ples and considerations for scientific investigations into anode-
free full cells, and it is these established tenets that have since
guided work on electrolytes for these systems.
Since this initial investigation, a multitude of diverse strat-
egies have been developed and implemented by varying the
composition and concentration of the electrolyte salts and sol-
vents in anode-free full cells. Beyene et al. reported a dual salt
formulation that developed upon the high concentration salt
strategy, but employed an electrolyte containing 2 m LiFSI
and 1 m lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)
in DME/dioxolane (DOL) (1:1, v/v).[42] This work reported 50%
capacity retention after 50 cycles (LIRR = 98.6%) in anode-free
Cu||LFP full cells. The initial lithium stripping capacity was
1.6 mAh cm−2, and the current rate was 0.2 mA cm−2. While
it does not outperform the previous work employing 4 m LiFSI
in DME electrolyte, this strategy does offer the advantage of
reducing the overall salt concentration and utilizing the rela-
tively less expensive LiTFSI salt. Rodriguez et al. investigated
a number of ether-based electrolyte formulations in anode-free
Cu || LFP full cells and found that lowering the LiFSI salt con-
centration in DME from 4 to 1 m only led to a minor reduction
in capacity retention with cycling.[43]
Hagos et al. investigated the use of carbonate electrolytes,
employing an electrolyte consisting of 2 m LiPF6 in EC/diethyl
carbonate (DEC) (1:1, v/v) diluted by 50% with fluoroethylene
carbonate (FEC).[44] This is notable in that the use of carbonate
electrolytes enables the use of higher voltage cathodes such
as high-nickel layered oxides, as carbonate-based electrolytes
generally possess greater electrochemical stability windows
than ether-based electrolytes. The large volume percent of
the fluorinated solvent FEC stabilizes lithium deposition due
to the formation of a LiF-rich SEI layer, while reducing the
overall salt amount and viscosity of the electrolyte compared to
high concentration electrolytes. Anode-free full cells pairing a
LiNi1/3Mn1/3Co1/3O2 (NMC111) cathode with a copper foil cur-
rent collector and evaluated with this electrolyte displayed 40%
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capacity retention after 50 cycles (LIRR = 98.2%). The initial
lithium stripping capacity was ≈2 mAh cm−2, and the current
rate was 0.2 mA cm−2. This work highlighted the use of anode-
free full cells employing carbonate-based electrolytes and high-
voltage cathodes and foreshadowed even greater focus on such
systems. Nilsson et al. reported stabilized lithium deposition
with a highly concentrated electrolyte comprising 1.86 m LiTFSI
in EC solvent.[45] Anode-free Cu || LFP full cells with a rela-
tively high initial lithium stripping capacity of 3.5 mAh cm−2
and applied current of 1 mA cm−2 maintained 50% of their
initial capacity at 30 cycles (LIRR = 97.7%). In comparison to
the formation of lithium globules with ether-based electrolytes,
dense columnar growth was observed with the concentrated
carbonate-based electrolyte containing LiTFSI.
Alvarado et al. introduced a bisalt ether electrolyte that
showed considerable performance improvements when
employed with a high-nickel NMC622 cathode in the anode-free
full cell configuration.[46] This strategy employed a concentrated
dual-salt formulation containing both LiTFSI and LiFSI in
ether-based solvents. This allowed for the use of high-capacity
NMC622 cathodes at high voltages of up to 4.4 V, expanding
upon the voltage window shown to date in anode-free full cells
and increasing the energy density achievable with such sys-
tems. By carefully choosing a blend of 2.3 m LiTFSI and 4.6 m
LiFSI (molality was utilized instead of molarity), a favorable
SEI layer was formed on the deposited lithium. Using careful
computational and experimental studies, it was found that a
complex interplay of the salt anions and their selective decom-
position on the lithium surface was responsible for forming a
SEI layer with a unique chemistry that was well suited for sta-
bilizing lithium deposition. Both half-cells and anode-free full
cells tested with the novel bisalt electrolyte displayed consider-
able performance improvements, the anode-free full cell in par-
ticular demonstrating capacity retention of 55% after 54 cycles
(LIRR = 98.9%), compared to the baseline cells employing car-
bonate-based electrolyte that faded to 0% after 35 cycles. The ini-
tial lithium stripping capacity was 1.44 mAh cm−2, and variable
current rates of 0.144 mA cm−2 for charge and 0.48 mA cm−2
for discharge were used. More so, the authors demonstrated
that the performance improvement was not simply from the
increased lithium content in the highly concentrated elec-
trolyte, but due to the favorable chemistry of the SEI layer
that was engendered by an optimized LiFSI to LiTFSI ratio.
Fan et al. reported stabilized lithium deposition with a highly
fluorinated electrolyte comprising 1 m LiPF6 in FEC/3,3,3-
fluoroethylmethyl carbonate/1,1,2,2-tetrafluoroethyl-2’,2’,2’-
trifluoroethylether (FEC/FEMC/HFE, 2:6:2 by wt).[47] An impor-
tant advantage of this electrolyte chemistry is its stability with
high voltage cathodes, such as LiCoPO4 at up to 5 V. Anode-free
Cu || NMC811 full cells with an initial lithium stripping capacity
of 2.75 mAh cm−2 and cycled at 0.5 mA cm−2 maintained 35%
of initial capacity after 30 cycles (LIRR = 96.6%). The improve-
ment over a nonfluorinated electrolyte was attributed to the
formation of a stabilizing LiF-rich SEI layer.
In 2019, Weber et al. reported an anode-free Cu || NMC
full cell consisting of an optimized dual-salt carbonate-
based electrolyte.[23] The electrolyte, consisting of 1 m lithium
difluoro(oxalato)borate (LiDFOB) and 0.2 m LiBF4 in a blend of
FEC/DEC (1:2, v/v), enabled a significant improvement in the
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reversibility of lithium deposition, with 80% capacity reten-
tion at 90 cycles (and ≈90% at 50 cycles, corresponding to an
LIRR of 99.8%). The initial lithium stripping capacity was
2.4 mAh cm−2, and variable current rates of 0.48 mA cm−2 for
charge and 1.2 mA cm−2 for discharge were employed. The per-
formance is even more remarkable when considering that it is
achieved in a practical large-area pouch cell format under lean
electrolyte conditions, with an electrolyte amount to capacity
ratio of 2 g Ah−1. The cells were cycled at 40 °C under 75 kPa
of stack pressure. The effect of pressure on electrochemical
performance is discussed later. The plated lithium in the opti-
mized electrolyte displayed highly favorable morphology, with
large, dense, columnar deposits and minimal surface area
exposed to the electrolyte. Through investigations with XPS,
the authors showed that the SEI layer arising from decomposed
LiDFOB is rich in organic boronated and fluorinated compo-
nents. In contrast, the SEI layer arising from the decomposi-
tion of LiPF6 and LiBF4 is rich in inorganic components, such
as LiF. By employing the dual salt strategy with an optimized
salt ratio, the resultant SEI is rich in both favorable organic and
inorganic components. This is the probable cause of the excel-
lent electrochemical performance obtained with this strategy.
Furthermore, it was found that the major driver of lithium
inventory loss is the consumption of LiDFOB and LiBF4 salts
with cycling, suggesting that optimized dual-salt or even tri-
salt formulations may be able to extend cycle life further. The
electrochemical performance shown in this work is one of the
best reported for anode-free full cells so far, and is even more
impressive due to the use of a pouch cell format with lean-elec-
trolyte conditions.[48]
Beyond modifying the composition and concentration of the
electrolyte salts and solvents, a few studies have focused on sta-
bilizing lithium deposition in anode-free full cells with the use
of electrolyte additives. Sahalie et al. reported using KNO3 as an
additive in a carbonate-based electrolyte, which was employed
in an anode-free Cu || NMC full cell. The use of KNO3 enabled
more favorable nucleation and growth of lithium metal during
charge, allowing for 40% capacity retention after 50 cycles
(LIRR = 98.2%).[49] The initial lithium stripping capacity was
1.7 mAh cm−2, and the current rate was 0.2 mA cm−2. The
same group also reported a dual electrolyte additive strategy
consisting of KPF6 and tris (trimethylsilyl) phosphite, which
moderately enhanced capacity retention compared to a control
cell in Cu||NMC full cells.[50] Brown et al. reported the use of
triethylphosphate as an electrolyte cosolvent to enable the dis-
solution of 0.2 m LiNO3 additive in 1 m LiDFOB in EC/DMC
electrolyte.[51] The high concentration of LiNO3 in the electro-
lyte led to the formation of an SEI rich in nitrogenated species
that allowed effective stabilization of lithium deposition. With
an initial lithium stripping capacity of 1 mAh cm−2 and applied
currents of 0.1 mA cm−2 for charge and 0.4 mA cm−2 for dis-
charge, anode-free Cu || LFP full cells demonstrated roughly
35% capacity retention at 50 cycles (LIRR = 97.9%). The same
group also reported that adding 5% vinylene carbonate (VC) to
1 m LiPF6 in EC/EMC (3:7, vol) electrolyte led to a significant
improvement in the capacity retention of Cu || LFP full cells
(showing a LIRR of 95.1%).[52] The improvement was attrib-
uted to the formation of a polymeric SEI layer on the lithium
surface.
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The role of electrolyte in determining both the morphology
of the deposited lithium as well as the composition of the
SEI layer underscores its importance in anode-free full cells.
While significant headway has been made in this area over the
last few years, there are clear opportunities for progress and
improvement. A thorough understanding needs to be devel-
oped of the relative importance of the different critical proper-
ties of the SEI layer that impact the efficiency of plating and
stripping lithium, including lithium-ion conductivity, elec-
tronic insulation, mechanical stability, chemical passivation,
and interfacial energy. Promising SEI components that meet
the criteria above and stabilize lithium deposition should also
be identified. A considerable number of work in this section
rely on the stabilizing properties of LiF in the SEI layer. Other
SEI layer components might also be considered, including high
ionic-conductivity sulfides such as Li3PS4, halides such as LiI,
polymeric or organic species, and in situ formed lithium–metal
alloys. Capacity retention in anode-free full cells will need to
last beyond the sub-100 cycle range demonstrated so far, par-
ticularly while accounting for practical engineering considera-
tions such as lean-electrolyte conditions, gas generation from
electrolyte decomposition, and nonuniform current densities in
large-area pouch cells.
4.2. Modification of the Current Collector
Another route toward improving the cyclability of anode-free
full cells is through modifying the current collector substrate
upon which the lithium metal is deposited. The current col-
lector plays a key role in determining the initial nucleation
conditions and subsequent growth of the deposited lithium and
is, therefore, an important lever in the development of an opti-
mized anode-free full cell. Modification of the current collector
through pretreatments can help improve the morphology of
lithium deposition, while coatings can function as an artificial
SEI layer and prevent electrolyte decomposition on the depos-
ited lithium. While still a relatively nascent and developing sub-
field, the few investigations that have been conducted in this
area have focused primarily on coatings on the current-collector
or modification/substitution of the underlying current-collector
substrate.
Hwang and co-workers have reported a series of different
current-collector coatings films and artificial SEIs including pol-
yethylene oxide (PEO),[53] multilayer graphene (MLG),[54] garnet
(Li7La2.75Ca0.25Zr1.75Nb0.25O12),[55] and graphene oxide.[56] The
use of PEO and multilayer graphene led to moderate improve-
ments in capacity retention over the control case with LFP cath-
odes and an unoptimized ether-based electrolyte. In particular,
anode-free Cu@PEO || LFP full cells demonstrated 64% capacity
retention at 50 cycles (LIRR = 99.1%), albeit with a low initial
lithium stripping capacity of 0.71 mAh cm−2 and a current rate
of 0.14 mA cm−2. In the investigation into multilayer graphene
(MLG), the authors employed a larger area current collector
relative to the cathode area to reduce the stress encountered at
the interface of the deposited lithium metal. With the improve-
ments from the MLG coating, anode-free Cu@MLG || LFP cells
showed an impressive 78% capacity retention at 50 cycles (LIRR
= 99.5%) with an unoptimized ether-based electrolyte. The
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initial discharge capacity was 1.7 mAh cm−2 and the current rate
was 0.5 mA cm−2. The garnet and graphene oxide coatings were
employed to demonstrate moderate improvements in the elec-
trochemical performance of anode-free Cu || NMC cells with
an unoptimized carbonate-based electrolyte, showing LIRRs of
98.2% and 98.3% respectively. These coatings behave as artifi-
cial SEIs and are thought to enable a uniform Li+ ion flux and
prevent the deposited lithium from reacting with the liquid
electrolyte. However, in the absence of an optimized electrolyte,
these implementations display average Coulombic efficien-
cies ranging from 97% to 99%, which falls short of the values
needed for extending cyclability to the range necessary for prac-
tical consideration.[22] For instance, the authors demonstrated
that even with the use of GO protective layers, the addition of
5% FEC had a dominant impact on the cyclability of anode-free
Cu || NMC full cells with a standard carbonate electrolytes.[56]
While the premise of artificial SEIs and robust protective or
stabilizing layers for lithium deposition has been the focus of
much research attention over the last decade,[20,21,57] their sole
application in anode-free full cells is yet to yield reversible
lithium deposition over hundreds of cycles.
Rather than coating the current collector with a film at the
electrode–electrolyte interface, an alternative approach involves
modifying the underlying conductive substrate upon which
lithium metal nucleates. The overpotential for nucleating
metallic lithium is an important parameter as it plays a role
in determining the density and uniformity of lithium deposi-
tion.[57,58] In a 2016 study, Cui and co-workers showed that the
nucleation overpotential for plating lithium metal is highly
dependent on the deposition substrate.[59] A series of metallic
substrates were evaluated for lithium deposition, and it was
found that the substrates with the greatest crystalline mismatch
with lithium metal exhibited the highest nucleation overpoten-
tial. Metallic lithium possesses a body-centered cubic (BCC)
crystal structure and thus deposits favorably on substrates with
BCC structures. Lithium also deposits favorably on “lithio-
philic” materials, which partially solubilize or alloy with lithium
metal. This includes metals such as gold, even though it pos-
sesses a face-centered cubic (FCC) crystal structure. This study
highlights that copper is among the least favorable deposition
substrates for lithium metal, given that it possesses an FCC
crystal structure and allows no solubility of lithium metal.
Hence, there is significant opportunity for improvement
in the electrochemical performance of anode-free full cells
through modification of the current collector substrate. The
vast majority of studies on anode-free full cells employ bare
copper foils as the deposition substrate, but there have been a
few selected studies evaluating other substrates. Zhang et al.
investigated thin layers of tin and lithium metal as deposition
substrates in anode-free full cells.[60,61] These layers are depos-
ited onto copper foil as a pretreatment in the case of tin, or in
situ in the case of lithium. In the case of tin, lithium proceeds
to alloy with the tin layer during initial deposition. This stabi-
lizes subsequent lithium deposition by lowering the interfacial
energy between the substrate and lithium metal. Anode-free
full cells employing NCA cathodes with 1.0 m (molality) LiPF6
in 1:4 FEC/EMC (by wt) as the electrolyte display improved
performance with the tin coating compared to those with bare
Cu foils, and the cycle life extended from 30 cycles to 80 cycles
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(30% capacity retention at 50 cycles, corresponding to an LIRR
of 97.6%).[60] The initial plating capacity was ≈1 mAh cm−2,
and the current rate was 0.5 mA cm−2. In the case of lithium,
a Li2CuO2 additive irreversibly plates lithium metal onto the
current collector during the first cycle and subsequent lithium
deposition occurs upon this thin in situ formed lithium–
metal substrate. A significant improvement in cyclability was
observed with the pre-plating of lithium metal, and the cycle life
increased with an increase in the mount of preplated lithium
from the Li2CuO2 additive. While some of the improvement
can be attributed to the additional reservoir of lithium available
in the cell, it is mostly expected to originate with the minimal
interfacial energy between the cycled lithium and the preplated
lithium.[61] A final study evaluating current collector substrates
for anode-free full cells was published in 2019 by Pande and
Viswanathan.[62] By computationally screening candidates for
reduced activation barriers for nucleation of lithium metal
and surface diffusion of lithium atoms, the authors found
several lithium alloy substrates that could help form com-
pact and dense deposits of lithium. This would feasibly allow
for enhanced electrochemical performance for an extended
number of cycles, even at high charge rates.
The current collector plays an essential role in determining
the morphology of the deposited lithium during cycling and
is thus a key lever for sustaining lithium inventory in anode-
free full cells. There have been important developments in
coatings, pretreatments, and modifications for current collec-
tors, but there is still a large room for improvement. Coating
layers employed as artificial SEIs to stabilize lithium deposition
must be robust, defect-free, and tolerant to the severe volume
changes of the deposited lithium metal during cycling. Addi-
tional opportunities lie in the replacement of copper with more
favorable conductive substrates for lithium nucleation and
diffusion. A crucial factor that needs to be considered in the
context of anode-free full cells is the lithiation capacity of the
“lithiophilic” substrate that is employed, which should be as
low as possible to maximize the fraction of the limited lithium
inventory that is available for plating and stripping. Prelithia-
tion of the current collector substrate could be considered, or
it could be engineered to minimize its lithiation capacity while
still maintaining the promised performance improvements. It
should be ensured that the additional lithiophilic components
on the current collector substrate does not significantly under-
mine the energy density gains with the anode-free configura-
tion. Further work in this area, and possibly several strategies
in conjunction, will allow the development of anode-free full
cells to ascend to a more practically deployable stage.
4.3. Optimization of Cell Formation and Cycling Parameters
A final lever for sustaining lithium inventory in anode-free full
cells is the formation and cycling parameters employed during
operation. Such operational controls, including modified
resting steps, optimized first cycle protocols, and the application
of temperature and pressure can have drastic effects on cycle
life in lithium-ion and lithium metal batteries.[63–66] The initial
formation steps are particularly crucial for forming a stable and
passivating SEI layer on the anode before prolonged cycling.
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As anode-free full cells lack a pre-existing anode, optimal cell
formation procedures may vary considerably from other con-
ventional systems. While optimization of the initial formation
procedure for anode-free full cells is still an emerging area of
research, it has nonetheless garnered considerable efforts from
the research community.
Beyene et al. introduced a resting and cycling protocol for
anode-free full cells, which when combined with a high-
concentration electrolyte, produced a considerably more robust
SEI on the surface of the in situ deposited lithium metal.[67]
They employed a twofold approach, where after cell assembly,
the cell was charged and lithium was deposited at a low rate
of 0.1 mA cm−2. After the first charge, the cell was rested for
24 h in order to allow the formation of a robust SEI layer rich
in fluorinated species, which originates from the LiFSI elec-
trolyte salt. Next, the cell was discharged, and the deposited
lithium stripped away at a higher rate of 0.5 mA cm−2. Finally,
the cell was galvanostatically cycled at up to 2 mA cm−2. The
authors claim that this increases the temperature of the depos-
ited lithium locally and allows uniform and smooth deposition
of lithium. When this approach was applied in anode-free Cu
|| LFP full cells, stable cycling was achieved with an average
Coulombic efficiency of ≈99% and a capacity retention of 64%
after 50 cycles (LIRR = 99.1%). The initial plating capacity
was 1.7 mAh cm−2, and the current rate was 0.5–1 mA cm−2.
This approach is interesting in that it combines an initial low-
rate lithium deposition step, a rest protocol, and a high-rate
conditioning step. This beckons further investigation into ini-
tial formation protocols for other electrolyte systems.
In early 2019, Louli et al. documented the effects of applying
mechanical stack pressure on the cycling stability of anode-free
full cells.[68] They employed large-area anode-free Cu || NMC
pouch full cells with a low electrolyte amount of 3 g Ah−1, which
were cycled while applying a uniaxial stack pressure ranging
from 75 to 2200 kPa. The cyclability of the cells generally
improved with an increase in the applied pressure, although
the extent of this improvement varied with the physical prop-
erties of the electrolyte solvent. As with the previous resting
and cycling protocol outlined by Beyene et. al., favorable opti-
mization of cycling parameters depends significantly on the
electrolyte employed.[67] Genovese et al. reported the effects of
a “hot formation” procedure, where the initial two cycles were
carried out at an elevated temperatures of 40 °C.[69] They found
that the high-temperature formation cycles enable the deposited
lithium metal to form dense, columnar growths, when com-
pared with formation cycles carried out at 20 °C. This optimized
high-temperature formation procedure was applied in anode-
free Cu || NMC pouch full cells in conjunction with 75 kPa of
stack pressure to realize drastically improved performance, with
over 55% capacity retention at 100 cycles compared to the same
retention at only 18 cycles in cells with the formation procedure
carried at room temperature (LIRR = 99.4%). The initial lithium
stripping capacity was 2.5 mA cm−2, and the applied current
was 0.5 mA cm−2 for charge and 1.25 mA cm−2 for discharge.
Moreover, when the pressure was increased to 1200 kPa, anode-
free full cells employing the hot formation procedure exhibited
85% capacity retention at 100 cycles (LIRR = 99.8%). It is pos-
sible that this hot formation procedure stabilizes lithium depo-
sition in a manner similar to the high-rate conditioning steps
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Figure 4. A summary of the investigations into anode-free lithium-ion
cells and affiliated LIRR that have been conducted since 2016.
employed by Hwang’s group,[67] although the hot formation
procedure also leads to considerable gas generation in the cell.
This work utilized a highly optimized LiDFOB/LiBF4 dual-salt
electrolyte in FEC:DEC (1:2, v/v) solvent, with varying concen-
trations of LiDFOB and LiBF4. It is expected that the optimal
formation procedures will vary with the electrolyte. Neverthe-
less, the hot formation procedure was further applied under a
1200 kPa of pressure with a concentrated salt electrolyte formu-
lation consisting of 1.8 m LiDFOB and 0.4 m LiBF4 in FEC:DEC
(1:2, v/v). The anode-free Cu || NMC pouch full cell employing
this electrolyte retained 80% of its initial capacity at a remark-
able 195 cycles (95% retention at 100 cycles, or a LIRR = 99.9%),
with an average Coulombic efficiency of 99.67%. The initial
lithium stripping capacity was 2.5 mA cm−2, and the applied
current was 0.5 mA cm−2 for charge and 1.25 mA cm−2 for dis-
charge. This represents one of the best achievements of elec-
trochemical performance not just in anode-free full cells, but
even in cells employing lithium-metal anodes. This milestone
in the development of anode-free batteries represents a combi-
nation of an optimized electrolyte with high salt concentration,
optimized formation procedure, and favorable cycling protocols.
The development of anode-free full cells has brought about
a great deal of engineering efforts and innovation toward
improving LIRR and sustaining lithium inventory over the
course of cycling. The diversity of approaches, ranging from
optimized electrolyte composition to modification of the current
collector and formation and cycling protocols, have advanced
our understanding of anode-free systems and the critical con-
siderations necessary for high Coulombic efficiency stripping
and plating of lithium metal. As Figure 4 shows, the research
progress to date in improving LIRR has been very promising,
with some of the best-performing systems displaying retention
rates much greater than 99%. The retention rates plotted in this
figure were calculated based on the number of cycles taken to
reach a given percentage of capacity retention, as described
in Section 3 of this review. Given that LIRR directly describes
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Figure 5. a) Electrochemical performance of a Li || Li2S half-cell and an anode-free Cu || Li2S full cell, with a 4 mg cm−2 cathode. c) Coulombic efficiencies
of plating and stripping lithium on Cu foil from a Li2S cathode and a lithium-metal counter-electrode. Reproduced with permission.[24] Copyright 2018,
Wiley-VCH.
retention rate of lithium inventory in anode-free full cells and
determines overall cyclability, this metric gives the most holistic
and comprehensive evaluation of the work on anode-free full
cells conducted thus far.
5. Anode-Free Sulfur Batteries
Lithium–sulfur batteries have attracted a great deal of attention
in the last decade because of the high theoretical gravimetric
capacity of sulfur (1675 mAh g−1) and its low cost and abun-
dance compared to the transition metals employed in incum-
bent Li-ion batteries. As a nonlithiated cathode, the sulfur
cathode has to be paired with a lithium-metal anode for opera-
tion. Alternatively, fully lithiated Li2S can be used as cathodes
and paired with lithium-free anodes.
In 2018, our group reported an anode-free full cell pairing
a Li2S/CNT cathode with a bare Cu foil.[24] To the best of our
knowledge, this is the first and only report of a Li–S battery in
the anode-free full cell configuration. When compared with
a Li || Li2S half-cell containing a large excess of lithium, the
anode-free Cu || Li2S full cell clearly demonstrated the impact
of a limited lithium inventory on electrochemical performance
(Figure 5a). Nevertheless, the Cu || Li2S full cell employing a
regular 2 m LiCF3SO3 + 0.1 m LiNO3 in DOL/DME (1:1 v/v)
electrolyte showed remarkable cycling stability, maintaining
51.5% of its initial capacity over 100 cycles (LIRR = 99.35%). In
contrast, the Li || Li2S half-cell with a large excess of lithium
retained 70% of its initial capacity over 100 cycles. The initial
lithium stripping capacity was 2.33 mA cm−2 and the current
rate was 0.47 mA cm−2. Thus, restricting the initial lithium
inventory in Li–S batteries has only a limited impact on elec-
trochemical performance. The performance of the unoptimized
anode-free Cu || Li2S full cell is comparable to some of the best
performing anode-free full cells reported in the literature that
employ NMC/LFP cathodes with highly optimized electrolytes.
This indicates an intrinsic stabilization of lithium deposition in
Li–S batteries.
Lithium deposition in Li–S batteries is uniquely affected by
the soluble polysulfide intermediates (Li2Sx, 2 < x ≤ 8), which
are formed during the charge/discharge process of the sulfur/
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Li2S cathode. These polysulfide species diffuse to the anode side,
where they reduce on the lithium surface to form Li2S and Li2S2.
The formation of these reduced sulfur species on the lithium
surface, which exist in a dynamic equilibrium with the dissolved
polysulfide species, is believed to have a stabilizing effect on
lithium deposition, as demonstrated by multiple investigations
on this topic.[36,37,70,71] In particular, a synergistic effect of poly-
sulfides and the LiNO3 electrolyte additive is thought to form a
passivating SEI layer that is favorable for reversible lithium dep-
osition. Some of this effect can be attributed to the sulfide ani-
onic framework of the reduced sulfur species in the SEI layer,
which leads to intrinsically lower Li+ ion diffusion barriers, when
compared to an oxide anionic framework that dominates many
SEI components.[72–74] Figure 5b compares the Coulombic effi-
ciencies of plating and stripping lithium metal on Cu foil from
a Li2S counter electrode (Cu || Li2S) and a bare lithium metal
counter electrode (Cu || Li). While the Cu || Li control cell shows
CE values with a geometric mean of 62.01% over 50 cycles, the
Cu || Li2S control cell shows CE values with a geometric mean
of 97.14% over 50 cycles. The difference can be attributed to the
stabilizing effect of polysulfides forming reduced sulfur species
on the lithium surface on the reversibility of lithium deposition.
Notwithstanding other issues, this effect bodes very well for the
commercial potential for Li–S batteries.
It is important to note here that the Coulombic efficiencies
obtained for the anode-free Cu || Li2S full cell are not a useful
predictor of the lithium inventory loss rate. CE values with a
geometric mean of 97.14% over 50 cycles would correspond to
23.4% lithium inventory retention. However, the actual capacity
retention obtained is 59.4%, corresponding to a lithium inven-
tory retention rate of almost 99% per cycle over 50 cycles. The
deviation between measured values of Coulombic efficiencies
and the actual values of lithium inventory retention rates can be
attributed to the presence of polysulfide intermediates, which
behave as soluble redox mediators that shuttle and “leak” charge
and active material between the two electrodes, effectively
behaving as an internal short. In systems with soluble redox
mediators that shuttle between the cathode and the anode, the
lithium inventory loss rate is significantly lower than what the
measured value of Coulombic efficiency would suggest and has
to be estimated from capacity fade.[31,32,75–77] This phenomenon
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is not observed in anode-free full cells with cathodes such as
LFP or LCO, which do not generate soluble redox mediators.
Future work on anode-free full cells based on any cathode that
displays shuttle phenomena such as Li2S or LiI should account
for this discrepancy.
The presence of polysulfide species in the electrolyte of Li–S
batteries also means that lithium deposition in such systems is
very difficult to model extrinsically. The exact composition and
concentration of the in situ generated polysulfide species in
the electrolyte, which exist in a dynamic equilibrium with each
other, the sulfur/Li2S cathode, and the reduced sulfur species
on the lithium surface, are unknown and depend on a number
of factors, including the amount of electrolyte, sulfur loading,
cycle number, and state of charge.[78–84] Hence, lithium deposi-
tion in Li–S batteries cannot be accurately modeled using poly-
sulfide additives of a fixed composition and concentration, for
instance 0.1 m Li2S6, in Cu || Li half cells or Li || Li symmetric
cells. Furthermore, polysulfide species are highly reactive and
the compatibility of various strategies for lithium stabilization
(such as lithium alloy substrates) with the polysulfide-rich elec-
trolyte is not guaranteed. These factors combine to make the
anode-free Cu || Li2S full cell configuration an excellent tem-
plate for i) developing a thorough understanding of lithium
deposition in Li–S batteries and ii) effectively evaluating var-
ious approaches toward improving the reversibility of lithium
plating/stripping in Li–S batteries.
Recently, our group discovered that the addition of a small
amount of tellurium to the Li2S cathode can have a dramatic
effect on the reversibility of lithium plating and stripping in
anode-free Ni || Li2S full cells (nickel was used instead of copper
as the anode current collector).[85] Polysulfides (Li2Sn) gener-
ated during cell operation react with the elemental tellurium
to form polytellurosulfide species (Li2TexSy) that migrate to the
anode side and reduce on the lithium surface to form Li2TeS3
as a component of the SEI layer. Due to its higher ionic con-
ductivity, Li2TeS3 is much more effective at stabilizing lithium
deposition compared to Li2S, which is formed in a control
cell without any additive. The initial discharge capacity of the
anode-free Ni || Li2S full cells was 2.5 mAh cm−2, and they were
cycled at C/5 rate or 1 mA cm−2. The addition of tellurium to
the cathode enabled the anode-free full cell to retain 50% of its
initial capacity for 240 cycles, whereas the control cell cycled
for only 34 cycles at 50% retention. Thus, the lithium inventory
retention rate was improved from 97.98% per cycle to 99.72%
per cycle. It was verified with half cells that the addition of tel-
lurium has no impact on cathode electrochemical performance.
This work demonstrates that stabilizing lithium deposition in
anode-free sulfur batteries requires the development of novel
strategies that account for the unique chemistry of the system.
A major challenge with Li–S batteries is the self-discharge
phenomena inherent to the system.[86–89] When assembled cells
in the Li || S configuration are rested before any current has
been applied, the S8 cathode gets partially reduced by Li+ ions
in the electrolyte. This generates soluble polysulfide species,
which diffuse to the lithium anode and reduce on its surface.
The generated lower-order polysulfide species shuttle back to
the cathode and catalyze further reduction of the S8 cathode.
This self-catalyzing process severely affects the shelf life of Li–S
batteries and limits their deliverable capacities. Anode-free full
Adv. Energy Mater. 2020, 2000804 2000804 (12 of 18)
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cells based on Li2S cathodes and bare current collectors enable
complete circumvention of this problem. As-assembled cells
before any current has been applied are expected to show zero
self-discharge since the Li2S cathode is already fully discharged
and there is no free lithium metal in the system. This aspect
is a major practical advantage of anode-free Li2S batteries and
merits further exploration.
6. Anode-Free Sodium Batteries
Sodium is an attractive replacement for lithium in various
rechargeable battery technologies due to its high gravimetric
capacity (1165 mAh g−1), low redox potential (-2.71 V vs
SHE),[90,91] and significantly higher earth-abundance and much
lower cost compared to lithium. Using sodium as the charge
carrier ion instead of lithium also confers other advantages,
including the use of cobalt-free sodium-ion cathodes, replacing
the copper anode current collector with cheaper and lighter alu-
minum, and better flame resistance compared to lithium bat-
teries.[92–94] One disadvantage of sodium batteries is the lack
of a suitable anode host material with low redox potential and
good cycling stability.[95,96] Using metallic sodium as the anode
can be a good circumvention to this problem. However, sodium
metal shows very high reactivity to air and moisture, even
more so than lithium. It would be particularly advantageous to
assemble full cells without any free sodium metal. The anode-
free full cell configuration, pairing a fully sodiated cathode with
a bare current collector for sodium plating and stripping, would
yield significant gains in energy density and resolve both of the
challenges described above.
Sodium-metal anodes suffer from many of the same issues
as lithium-metal anodes described earlier. The deposition of
sodium metal leads to the growth of highly reactive porous
mossy deposits with large surface areas, which leads to poor
efficiencies of sodium plating and stripping. Dendritic growth
of sodium metal can similarly occur when sodium ions get
depleted at the electrode surface and diffusion-based charge
transport limitations are reached. There has been much less
work on improving the reversibility of sodium-metal anodes
compared to their lithium metal counterparts. Nevertheless,
the solutions proposed to improve the Coulombic efficiencies
of sodium-metal batteries are similar in spirit to those pro-
posed for lithium-metal batteries: optimized electrolyte for-
mulations to form favorable interphasial components, coating
layers to homogenize Na+ ion flux, and modified current col-
lector substrates with low nucleation overpotentials for sodium
deposition. However, there are significant differences in the
chemical and physical properties of sodium and lithium such
that sodium deposition cannot be considered a direct analogue
of lithium deposition.[97] Sodium ions are larger than lithium
ions (116 pm vs 90 pm) but are less polarizing due to the lower
charge density. This is expected to have an impact on the energy
barrier for sodium ion migration through different SEI compo-
nents. Sodium metal is also less reducing than lithium metal.
The melting point of sodium (98 °C) is significantly lower than
lithium (181 °C), leading to the possibility of restricting mossy
growths with a combination of pressure and temperature con-
trols. Sodium metal exhibits significantly higher reactivity with
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
the commonly used carbonate electrolyte solvents compared
to lithium.[98] At the same time, simple low salt concentra-
tion ether-based electrolytes, such as 1 m NaPF6 in diglyme
and 1 m NaTFSI in diglyme, have been identified that show
excellent Coulombic efficiencies for sodium plating and strip-
ping.[99] These electrolytes behave quite distinctly from their
lithium counterparts, and comparable Coulombic efficiencies
for lithium plating and stripping can typically only be achieved
with highly optimized high-concentration electrolytes.[100] The
retention of sodium ions during cycling can be accounted for
by the sodium inventory retention rate (NIRR), defined identi-
cally to LIRR.
In 2017, Cohn et al. demonstrated an anode-free sodium bat-
tery employing a sodiated iron pyrite cathode (Na1.5FeS2) paired
with an aluminum foil coated with a thin layer of carbon to
provide a low interfacial energy surface for sodium deposi-
tion.[25] The thin layer of carbon is shown to have a low sodia-
tion capacity of 0.05 mA cm−2, and enables the sodium metal
to plate as large, flat, and smooth hexagonal islands. With a 1 m
NaPF6 in diglyme electrolyte, the authors demonstrated stable
capacities for 40 cycles. The initial sodium plating capacity was
1.7 mAh cm−2, although the applied currents were quite low at
0.125 mA cm−2. Tang et al. have demonstrated that coating a
thin 50 nm “sodiophilic” gold layer on the Cu foil current col-
lector has a beneficial impact on the reversibility of sodium
deposition. By forming Au2Na alloy upon initial sodiation, the
nucleation energy for subsequent sodium plating could be signif-
icantly reduced.[101] The initial sodium plating capacity was about
0.5 mAh cm−2 and the current rate was 0.2 mA cm−2 for charge
and 2 mA cm−2 for discharge. In an anode-free full cell with a
sodiated iron pyrite cathode paired with the Au/Cu current col-
lector and using 1 m NaCF3SO3 in diglyme electrolyte, 55% of the
initial capacity was maintained after 50 cycles (NIRR = 98.8%).
Rudola et al. demonstrated an anode-free Cu || Na2Fe2(CN)6
full cell with an initial sodium plating capacity of 1.14 mAh cm−2
and an applied current of 0.18 mA cm−2 during charge and
0.9 mA cm−2 during discharge.[102] The cell delivered 76% capacity
retention at 100 cycles with a 1 m NaBF4 in tetraglyme electrolyte
(NIRR = 99.7%). The cell was subject to initial formation cycling
in a shallow voltage window of 3.25–2.0 V for 20 cycles to elimi-
nate irreversible losses, before starting regular cycling between
3.9 and 2.0 V. Mazzali et al. demonstrated an anode-free sodium
battery based on sodiated iron hexacyanoferrate (Prussian Blue)
as the cathode active material paired with a carbon-coated alu-
minum foil.[103] Using 1 m NaPF6 in diglyme as the electrolyte,
they showed a first cycle loss of ≈40%, but subsequently retained
90% of their second cycle capacity at 150 cycles (NIRR = 99.6%),
albeit with a low sodium plating capacity of 0.17 mAh cm−2 and
an applied current of 0.22 mA cm−2.
Cohn et al. have also demonstrated anode-free sodium bat-
teries pairing a sodiated Na3V2(PO4)3 cathode with an alu-
minum current collector coated with various thin nucleation
layers.[104] Among the different nongraphitic carbons and
sodium-alloying metals evaluated as nucleation layers, carbon
black and bismuth showed the highest Coulombic efficiencies
for sodium plating and stripping. With a 1 m NaPF6 in diglyme
electrolyte and carbon black as the nucleation layer, the authors
demonstrated a remarkable capacity retention of 82.5% after
100 cycles (NIRR = 99.8%) at a reasonable 0.5 mA cm−2 current
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Figure 6. A visual summary of the investigations conducted thus far into
anode-free sodium-ion cells with the associated NIRR.
rate and a 1.26 mAh cm−2 sodium plating capacity. Importantly,
the work employed no presodiation treatments on the current
collectors and exhibited low first cycle losses. This work dem-
onstrates that the combination of a favorable nucleation layer
with a favorable electrolyte such as 1 m NaPF6 in diglyme can
enable excellent cyclability in anode-free systems. It is expected
that further improvements in cyclability can be delivered with
modified electrolytes (e.g., additives) and systematic application
of more optimized formation procedures and cycling protocols
(e.g., pressure). A visual summary of all the work conducted
into anode-free sodium batteries is presented in Figure 6.
7. Anode-Free Solid-State Batteries
One of the fundamental limitations of lithium-metal batteries
employing liquid electrolytes, including the anode-free full
cells discussed throughout this paper, is the potential for den-
dritic lithium growth leading to internal shorting of the cell and
catastrophic cell failure. This has generated widespread interest
in all-solid-state lithium-metal batteries as a means of circum-
venting the safety concerns associated with a flammable organic
liquid electrolyte.[105,106] By inhibiting the growth of lithium den-
drites, solid-state electrolytes (SSEs) eliminate the risk of internal
shorting of the cell and consequent thermal runaway.[107,108] The
transference number of SSEs is close to 1, which also helps
impede the formation of lithium dendrites.[109,110] Solid-state
electrolytes can also enable higher energy density due to the
elimination of the polymer separator and the need for less elec-
trolyte loadings compared to liquid electrolytes.[26] An anode-free
full cell employing SSEs would enable a dramatic enhancement
in achievable energy density. The decomposition of liquid elec-
trolytes leads to substantial gas evolution, which has a severely
detrimental impact on electrochemical performance.[64,111] In
contrast, SSEs show limited gas evolution.[112] SSEs are espe-
cially promising for systems that undergo considerable active-
material crossover, such as NMC, spinel, and sulfur cathodes, as
they prevent the formation and passage of such species.
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Despite these advantages, the development of all-solid-state
lithium-metal batteries faces a number of challenges. Tra-
ditional oxide-based solid-state electrolytes suffer from rela-
tively poor ionic conductivity at room temperature. Even opti-
mized SSE materials such as LIPON, perovskite-type LLTO,
NASICON-type LAGP and LATP, and garnet-type LLZO display
ionic conductivities that fall short of their liquid electrolyte
counterparts.[113–115] This inhibits cell operation at acceptable
current densities with high cathode loadings. Hence, consider-
able efforts have been devoted toward improving the ionic con-
ductivity of SSEs. Over the last decade, sulfide-based solid elec-
trolytes have been developed which show ionic conductivities
approaching liquid electrolytes at room temperature.[73,74,116,117]
Solid electrolytes with a sulfide anionic framework show
lower Li+-ion diffusion barriers compared to solid electrolytes
with an oxide anionic framework due to the larger size and
higher polarizability of the sulfide anion. Another advantage
of sulfide-based SSEs is that the grain boundary resistance can
be reduced by a simple cold-pressing technique. In contrast,
oxide-based SSEs such as garnet-type LLZO require a high-
temperature sintering process for reduction of grain boundary
resistance.[117] Nevertheless, sulfide-based solid electrolytes
suffer from a number of disadvantages. Their high moisture
sensitivity leads to the formation of toxic H2S gas, and hence
material preparation and cell assembly have to be done in an
inert atmosphere. Sulfide-based SSEs also display limited elec-
trochemical stability windows. They tend to reduce upon con-
tact with metallic lithium to form a resistive decomposition
layer at the lithium interface.[118] Argyrodite-type solid electro-
lytes, in which one of the sulfide anions is replaced by a halide
(Cl, Br, I), demonstrate significantly better compatibility with
lithium metal.[119,120] A significant challenge with all-solid-state
lithium-metal batteries is achieving a conformal low-impedance
interfacial contact between the solid electrolyte and lithium
metal. Furthermore, maintaining such an intimate contact over
extended cycling with the large volume changes that accom-
pany plating and stripping of lithium is even more difficult.
Modifying the lithium–electrolyte interface with an artificial
SEI layer is a possible solution. These buffer layers could be
composed of an organic polymer coating, a secondary inorganic
solid electrolyte, or even lithiophilic materials that alloy with
lithium, such as Si, Ge, and Au.[107] The use of polymer–ceramic
composite solid electrolytes, which demonstrate significantly
better wettability with metallic lithium, may also be considered.
Recently, Lee et al. demonstrated a solid-state battery in the
anode-free full cell with a LiNi0.90Co0.05Mn0.05O2 (NMC) cathode
and an argyrodite-type Li6PS5Cl sulfide solid electrolyte.[121]
The solid electrolyte layer was uniformly applied onto the
cathode by employing pressure using a warm isostatic press.
The NMC cathode was coated with a thin layer of Li2O–ZrO2
coating to maintain interfacial stability with the solid electro-
lyte. On the anode side, a 5 µm thick nanocomposite layer
composed of lithiophilic Ag nanoparticles and carbon black
was used as the buffer layer between the solid electrolyte and
the stainless-steel current collector. The nanocomposite buffer
layer enabled uniform, dense and dendrite-free lithium depo-
sition on the current collector substrate and acted as a stable
interface between the solid electrolyte and lithium metal. The
authors demonstrated truly remarkable performance with their
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solid-state anode-free batteries in large-area pouch cell format.
With a cathode capacity of 6.8 mAh cm−2 and an applied cur-
rent density of 0.5C (=3.4 mA cm−2), 89% of the initial discharge
capacity was retained after 1000 cycles. This corresponds to a
lithium inventory retention rate of 99.988%, which approaches
the Coulombic efficiency of commercial Li-ion batteries with
graphite anodes. The pouch cell was pressurized to 490 MPa
during cell fabrication with a warm isostatic pressure system.
During cell operation, the temperature was maintained at 60°C
and a uniaxial stack pressure of 2– 4 MPa was applied. The
application of pressure and temperature controls is necessary
for maintaining an intimate low-impedance contact between the
solid electrolyte and the deposited lithium metal and ensuring
facile ionic diffusion through the interfacial layers.
The performance shown in this paper far exceeds any reported
work on anode-free full cells and sets a new benchmark for what
is achievable with this configuration. It also reveals some of the
design considerations that are necessary for achieving revers-
ible lithium deposition in solid-state anode-free batteries. The
solid electrolyte chosen should possess high ionic conductivity at
room temperature and demonstrate excellent compatibility with
metallic lithium. Engineering a suitable buffer layer between the
solid electrolyte and the anode current collector is critical, as it
plays a vital role in ensuring dense and uniform lithium plating
while maintaining stable interfacial contact between the solid
electrolyte and deposited lithium during cell operation. Finally,
the application of pressure during cell assembly and operation
is necessary for achieving optimal electrochemical performance.
8. Conclusions and Outlook
The anode-free full cell configuration is an important mile-
stone in the development of lithium-metal batteries. For any
given lithium-containing cathode system, the anode-free full cell
delivers the highest possible energy density due to the complete
elimination of all anode active material and utilization of the
maximum possible voltage output from the cathode. Given the
high specific volume of lithium (1.87 cm3 g−1), the gains in volu-
metric energy density can be particularly significant. From a prac-
tical perspective, the elimination of free lithium metal and facile
cell assembly in the discharged state is a significant advantage.
As we have discussed, anode-free cells can enable the diag-
nostic evaluation of capacity-loss mechanisms in their truest
sense, as lithium inventory in the cell can be directly monitored
over the course of cycling due to the lack of excess lithium. In
this review, we have introduced the metric of lithium inven-
tory retention rate, or LIRR, to best quantify this loss across
the broad range of work currently published in the literature.
Tables 1 and 2 summarize some of the important work reviewed
in this paper on lithium-based and sodium-based anode-free
full cells, respectively, and compare the inventory retention
rates based on the reported electrochemical performance.
For meaningful progress, it is important to determine cer-
tain cell design, testing, and performance parameters that are
uniformly applied to studies in this field. In particular, the theo-
retical capacity of the cell, the first cycle lithium stripping (or
discharge) capacity, the capacity retention at a specific number
of cycles (say 100), or the number of cycles taken to reach a
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Table 1. A summary of the published work on lithium-based anode-free full cells discussed in this article.

Ref. Year Anode Cathode Electrolyte Initial areal capacity Current rate LIRR [%]
[mAh cm−2] [mA cm−2]
[22] 2016 Cu LFP 4 m LiFSI in DME 1.7 0.2 98.98
[52] 2017 Cu LFP 5% VC + 1 m LiPF6 in EC/EMC (3:7, v/v) 2 0.1 (charge), 95.07
0.5 (discharge)
[60] 2017 Sn–Cu NCA 1 m LiPF6 in FEC:EMC (1:4, wt/wt) 1 0.5 97.62
[24] 2018 Cu Li2S 2 m LiCF3SO3 + 0.1 m LiNO3 in DOL/DME (1:1, v/v) 2.33 0.47 99.35
[53] 2018 Cu@ PEO LFP 1 m LiTFSI + 2% LiNO3 in DOL:DME (1:1, v/v) 0.71 0.14 99.11
[47] 2018 Cu NMC 811 1 m LiPF6 in FEC:FEMC:HFE (2:6:2, by weight) 2.75 0.5 96.60
[54] 2019 Cu@ MLG LFP 1 m LiTFSI + 2% LiNO3 in DOL:DME (1:1, v/v) 1.56 0.2 99.50
[46] 2019 Cu NMC 622 2.3 m LiTFSI and 4.6 m LiFSI in DME 1.44 0.144 (charge), 98.90
0.48 (discharge)
[44] 2019 Cu NMC 111 1 m LiPF6 in EC:DEC:FEC (1:1:2, v/v) 2 0.2 98.18
[68] 2019 Cu NMC 532 1 m LiPF6 in FEC:TFEC (1:2, v/v) 3 0.6 (charge), 99.08
1.5 (discharge)
[42] 2019 Cu LFP 2 m LiFSI + 1 m LiTFSI in DOL/DME (1:1, v/v) 1.6 0.2 98.62
[50] 2019 Cu NMC 111 2 wt% KPF6 + 2 vol% TMSP + 1 m LiPF6 in 1.7 0.2 96.40
EC:DEC (1:1, v/v)
[23] 2019 Cu NMC 111 1 m LiDFOB + 0.2 m LiBF4 in FEC/DEC (1:2, v/v) 2.4 0.48 (charge), 99.75
1.2 (discharge)
[51] 2019 Cu LFP 0.2 m LiNO3 + 1 m LiDFOB in TEP:EC:DMC 1 0.1 (charge), 97.90
(8.4:8.4:83.2, v/v) 0.4 (discharge)
[49] 2019 Cu NMC 111 0.5 m KNO3 + 1 m LiPF6 in EC:DEC (1:1, v/v) 1.7 0.2 98.18
[67] 2019 Cu LFP 3 m LiFSI in DOL:DME (1:1, v/v) 1.7 0.1 and 0.5 (formation), 99.11
1 (cycling)
[55] 2019 Cu@ LLCZN/PVDF NMC 111 1 m LiPF6 in EC:DEC (1:1, v/v) 2.13 0.2 98.24
[69] 2019 Cu NMC 532 1.8 m LiDFOB + 0.4 m LiBF4 in FEC:DEC (1:2, v/v). 2.5 0.5 (charge), 99.89
1.25 (discharge)
[45] 2019 Cu LFP 1.86 m LiTFSI in EC 3.5 1 97.70
[56] 2020 Cu@ GO NMC 111 1 m LiPF6 + 5% FEC in EC:DEC (1:1, v/v) 2 0.2 98.37
[121] 2020 SS@ Ag-C NMC 900505 Solid Li6PS5Cl 6.8 0.68 and 1.36 (formation), 99.99
3.4 (cycling)
[85] 2020 Ni Li2S + 0.1 Te 1 m LiTFSI + 0.1 m LiNO3 in DOL/DME (1:1, v/v) 2.5 1 99.72

given capacity retention (say 50%), and the applied current
densities should be clearly reported. The parameters described
earlier should be used to calculate the value of the LIRR that
can be used for comparison across different works. Any initial
formation steps that are employed should be clearly described.
Reasonable plating/stripping capacities (>2 mAh cm−2) and
current densities (>1 mA cm−2) should also be employed. The
performance of equivalent half cells may be reported in order to
ensure that the anode-free full cells are operating in a lithium-
limited regime during cycling. Where possible, the cathodes
should be cycled to 100% depth of discharge. Any lithiation
capacities associated with the current collector substrate should
also be clearly reported. It should be attempted to report the
electrolyte amount employed in the cell, in units of mg mAh−1.
Finally, reasonable control cells should be devised to demon-
strate the performance improvements.

Table 2. A summary of the published work on sodium-based anode-free full cells discussed in this article.

Refs. Year Anode Cathode Electrolyte Initial areal capacity [mAh cm−2] Current rate [mA cm−2] NIRR [%]
[25] 2017 Al@C Na1.5FeS2 1 m NaPF6 in diglyme 1.7 0.125 N/A
[102] 2018 Cu Na2Fe2(CN)6 1 m NaBF4 in tetraglyme electrolyte 1.14 0.18 (charge), 0.9 (discharge) 99.73
[101] 2018 Cu@Au Na1.3FeS2 1 m NaCF3SO3 in diglyme 0.5 0.2 (charge), 2 (discharge) 98.81
[104] 2018 Al@C Na3V2(PO4)3 1 m NaPF6 in diglyme 1.26 0.5 99.81
[103] 2019 Al@C Na2Fe2(CN)6 1 m NaPF6 in diglyme 0.17 0.22 99.60

Adv. Energy Mater. 2020, 2000804 2000804 (15 of 18) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Given the tremendous progress and insights showcased
throughout the scientific work published in this nascent
area thus far, there is an encouraging path forward for
future developments. Further optimization of the liquid
electrolyte, anode-side current collector, and formation and
cycling parameters will continue leading the charge for
further progress in increasing LIRR to the levels needed
to ensure commercial deployment (a LIRR approaching
99.99%). For the development of optimized electrolyte for-
mulations, a clear understanding of the SEI layer formed
on the lithium surface and the role played by individual SEI
components is necessary. The formation of high ionic con-
ductivity interphasial species such as Li3PS4 and high sur-
face energy interphasial species such as LiF is particularly
effective at improving lithium cycling efficiency. Hence,
the use of fluorinated electrolytes and mixed polysulfide
additives may be considered. Localized high-concentration
electrolytes, which combine the low viscosity and high wet-
tability of regular electrolytes with the lithium stabilization
of concentrated electrolytes, may be promising. Modifying
the anode-side current collector with lithiophilic materials
is another useful strategy for improving the reversibility
of lithium deposition. Finally, the application of pressure
is necessary to achieve high lithium inventory retention
rates and needs to be explored further. However, substan-
tial improvements will likely not occur in isolation, and the
onus will be on the entire community to integrate devel-
opments across a broad range of strategies to ensure the
greatest retention of lithium inventory. Furthermore, these
developments will need to be proven with practically rele-
vant cell parameters, including large-area pouch cells and
lean electrolyte conditions to ensure the scalability of the
technology. The possibility of such a drastic increase in vol-
umetric and gravimetric energy densities could enable the
largest step-change in energy storage technology seen since
the introduction of the lithium-ion battery, and we look for-
ward to seeing developments in this area moving forward.
Acknowledgements
This work was supported by the Assistant Secretary for Energy
Efficiency and Renewable Energy, Office of Vehicle Technologies of the
U.S. Department of Energy through the Advanced Battery Materials
Research (BMR) Program (Battery500 Consortium) award number
DE-EE0007762.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
anode-free cells, full cells, lithium batteries, lithium deposition, lithium-
metal anodes
Received: March 2, 2020
Revised: April 17, 2020
Published online:
Adv. Energy Mater. 2020, 2000804 2000804 (16 of 18)
www.advenergymat.de
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