Nano Energy 110 (2023) 108364

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Nano Energy
journal homepage: www.elsevier.com/locate/nanoen

Review

Recent advances and future perspectives of rechargeable

chloride-based batteries
Jinlin Yang , Yuhao Liu , Yu Zhang , Guan Wang , Xiaodong Shi , Hui Zhang , Jing Li ,
Peilin Deng *, Xinlong Tian *
State Key Laboratory of Marine Resource Utilization in South China Sea, Hainan Provincial Key Lab of Fine Chemistry, School of Chemical Engineering and Technology,
Hainan University, Haikou 570228, China

A R T I C L E I N F O A B S T R A C T

Keywords: The growing demand for low-cost, sustainable, and energy-dense energy storage devices has spurred intensive
Chloride-based batteries investigations into post-lithium battery systems. Rechargeable chloride-based batteries with chloride anions as
Rechargeable batteries charge carriers are promising candidates for electrochemical energy storage systems owing to their high theo­
Electrochemistry
retical volumetric energy density and the natural abundance of chloride-containing materials. This review
Electrodes
Electrolytes
provides an integrated understanding of the evolution of various chloride-based battery systems, including
rocking-chair batteries (RCBs), dual-ion batteries (DIBs), and other emerging chloride-based batteries. The
operating principles, battery performance metrics, and electrochemical features of the chloride anion storage
materials are discussed in detail. Finally, the perspectives for possible future efforts in this field are analyzed to
promote progress in the development of state-of-the-art chloride-based batteries with the expectation of
providing guidelines for large-scale applications in the future.

1. Introduction widespread interest [14–19]. Unlike metallic charge carriers, which

Electrochemical energy storage technologies, particularly recharge­
able batteries, show significant potential for the application in grid-scale
energy storage, transportation, and portable electronics, owing to their
reliability, ease of deployment, and technological maturity [1,2].
Among these battery systems, lithium-ion batteries (LIBs), which have
high gravimetric energy density and good cycle life, have been very
successful over the past 30 years [3,4]. However, with energy density
advancements in LIBs approaching their limits and the ongoing deple­
tion of limited global lithium resources, the demands for higher energy
density and lower cost have driven the investigation of so-called
“beyond Li-ion” technologies [5,6]. Although new rechargeable batte­
ries with low-cost metal ions as charge carriers, including alkali metal
ions (Na+, K+) [7,8] and multivalent metal ions (Mg2+, Zn2+, Ca2+,
Al3+) [9–13] have been proposed as promising alternatives to LIBs for
large-scale applications, tremendous research efforts are still needed to
address their limited energy densities and lifetime costs to meet the
current market demand.
In recent years, rechargeable anion-based batteries using anions (e.
g., F− , Cl− , PF−6 , ClO-4, HSO-4, and NO-3) as charge carriers have aroused
generally form ionic bonds with host materials, anion non-metallic
charge carriers can interact with positively charged structural atoms
in the electrode to form hybrid covalent-ionic bonds, which serve as an
additional redox center for charge transfer, resulting in superior elec­
trochemical performance [20]. Anionic charge carriers are usually
earth-abundant elements, which makes them cheaper than metallic
charge carriers, thus bringing new opportunities to further reduce the
cost of energy storage [21,22]. Among these anions, Cl− is particularly
attractive owing to its obvious merits, including: (1) high theoretical
volumetric and gravimetric energy density of up to 2500 Wh L-1 or 1100
Wh kg-1, which exceeds that of traditional LIBs and comparable to that
of Li-S batteries (see Supplementary Table S1 for details); (2) high
electronegativity, which provides a wide electrochemical stability win­
dow; (3) low manufacturing costs due to the abundant
chloride-containing materials (see Supplementary Table S2 for details);
and (4) dendrite-free formation at metallic anodes upon cycling.
Therefore, the large-scale energy storage applications can be realized
due to the above-mentioned features of Cl− .
A timeline summarizing the major milestones of rechargeable
chloride-based batteries is presented in Fig. 1. Based on the operating

* Corresponding authors.
E-mail addresses: dengpeilin@hainaiu.edu.cn (P. Deng), tianxl@hainanu.edu.cn (X. Tian).

https://doi.org/10.1016/j.nanoen.2023.108364
Received 31 December 2022; Received in revised form 21 February 2023; Accepted 17 March 2023
Available online 21 March 2023
2211-2855/© 2023 Elsevier Ltd. All rights reserved.
J. Yang et al. Nano Energy 110 (2023) 108364

mechanism, chloride-based batteries can be divided into three main
types: chloride-based RCBs, chloride-based DIBs, and other chloride-
based batteries. Pioneering work by Fichtner et al. reported a non-
aqueous chloride-based RCBs in 2013 using lithium metal as the
anode and metal chlorides (BiCl3, CoCl2, and VCl2) as the cathode [15].
Subsequently, the first aqueous and all-solid-state chloride-based RCBs
were successively reported in 2017 and 2018, and aqueous NaCl solu­
tion and poly(ethylene oxide)-tributylmethylammonium chlor­
ide-succinonitrile (PEO-TBMACl-SN) were employed as electrolytes,
respectively, widening the application scenario of chloride-based bat­
teries [23,24]. The concept of DIBs has been applied to chloride-based
systems since 2015, and Dai et al. reported a new type of rechargeable
Al-graphite battery [25]. The reaction mechanism involves the
intercalation/de-intercalation of chloroaluminate anions (AlCl-4) in the
graphite cathode and the electrochemical deposition/dissolution of Al at
the anode. Thereafter, DIBs based on Cl-containing dual-halogen and
single Cl ions as charge carriers were first realized in 2019 and 2020,
respectively [26,27]. Ji et al. introduced another novel concept, of
reverse DIBs in 2019 [28]. Although both anions and cations participate
in the electrochemical process, they are each stored at the anode and
cathode sides, respectively. More recently, other emerging
chloride-based systems have been developed, such as alkali-metal/Cl2
batteries (2021) [29] and chlorine flow batteries (2022) [30], which
have significantly enriched the scope of rechargeable chloride-based
batteries.
In this review, we provide an overview of state-of-the-art de­
velopments in rechargeable chloride-based batteries, including chloride-
based RCBs and DIBs systems, as well as other emerging Cl-based bat­
teries. The major achievements of the individual technologies are briefly
summarized in each section, with consideration from the fundamental
mechanism to electrode materials. Finally, based on our understanding,
the current challenges and potential future directions of this burgeoning
battery technology are presented. We anticipate that this review offers
key insights into the future development of rechargeable chloride-based
batteries.
2. Chloride-based rocking-chair batteries
Well-known LIBs are typical rocking-chair batteries that involve
shuttling of Li+ cations between the cathode and anode during the
charge/discharge process. Replacing Li+ cations with Cl− anions, that is,
designing a chloride-based rocking-chair battery, is an attractive
approach to reduce production costs for scaled-up applications. How­
ever, there are inevitable challenges before their full potential can be
realized, such as exploring appropriate electrode materials that can
accommodate Cl− anions. In this section, we review research progress on
the important components of chloride-based RCBs, including cathode
materials, anodes, and electrolytes. Table 1 and Fig. S1 summarizes and
compares the electrochemical performances of the reported chloride-
based rocking-chair batteries.
2.1. Cathode materials
One of the major challenges for the development of chloride-based
RCBs is the cathode material. To date, only limited materials have
been exploited as feasible Cl ion host materials, including metal chlo­
rides, metal oxychlorides, layered double hydroxides (LDH), and
organic polymers. Metal chlorides and oxychlorides as traditional elec­
trode materials generally suffer from large volume change caused by the
conversion reaction. Therefore, intercalation-type electrodes (e.g.,
LDHs, polymers) as Cl ion hosts with good stability has spurred
increased interests in recent years. The structural features and electro­
chemical properties of these materials will be discussed as follows.
2.1.1. Metal chlorides and oxychlorides
The first demonstration of rechargeable chloride-based RCBs was
achieved in 2013 by Fichtner et al. using metal chlorides (CoCl2, VCl3,
and BiCl3) and Li metal as the cathode and anode, respectively [15]. The
ionic liquid, consisting of 1-methyl-3-octylimidazolium chloride
([OMIM][Cl]) and 1-butyl-3-methylimidazolium tetrafluoroborate
([BMIM][BF4]), is used as the electrolyte exhibited high chloride ion
conductivity (9.1 × 10-4 S cm-1) at 298 K. Although decent specific

Fig. 1. A brief development history of rechargeable chloride-based batteries. (a) Reproduced with permission from [15]. Copyright 2013, Wiley VCH. (b) Repro­
duced with permission from [25]. Copyright 2015, Nature Publishing Group. (c) Reproduced with permission from [23]. Copyright 2017, Elsevier. (d) Reproduced
with permission from [24]. Copyright 2019, Wiley VCH. (e) Reproduced with permission from [26]. Copyright 2019, Nature Publishing Group. (f) Reproduced with
permission from [28]. Copyright 2020, American Chemical Society. (g) Reproduced with permission from [27]. Copyright 2020, Wiley VCH. (h) Reproduced with
permission from [29]. Copyright 2021, Nature Publishing Group. (i) Reproduced with permission from [30]. Copyright 2022, Nature Publishing Group.

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J. Yang et al. Nano Energy 110 (2023) 108364

Table 1
Summary of the electrochemical performance of the reported chloride-based rocking-chair batteries.
Cathode Anode Electrolyte Voltage Specific capacity Cycle Ref.
window (V) (mAh g-1) number

BiCl3 Li [OMIM][Cl]-[BMIM][BF4] 1.6–3.5 176.6 3 [15]

VCl3 Li [OMIM][Cl]-[BMIM][BF4] 1.5–3.5 111.8 / [15]
CoCl2 Li [OMIM][Cl]-[BMIM][BF4] 1.6–3.5 80 / [15]
CuCl Li 0.5 M TBMACl in PP14TFSI 1.5–4.0 278 100 [31]
CuCl Mg PDDAC-PEG 0.5–2.2 27 3 [32]
BiCl3 Li 0.5 M PP14Cl in PP14TFSI 1.6–4.0 298 60 [33]
BiCl3 Pb Pb0.98K0.02Cl1.98 0.2–0.8 187 30 [34]
BiOCl Li 0.5 M N116(14)Cl in N1114TFSI 1.6–3.0 60 6 [35]
BiOCl Mg 0.5 M PP14Cl in PP14TFSI 0.7–2.1 102 / [36]
FeOCl Mg 0.5 M PP14Cl in PP14TFSI 0.7–2.5 130 30 [36]
FeOCl Li 0.5 M PP14Cl in PP14TFSI 1.6–3.5 158 30 [35]
FeOCl Li PEO-TBMACl-SN 1.6–4.2 130 20 [24]
FeOCl Li PMMA-PP14Cl-PP14TFSI 1.6–3.5 122 7 [37]
FeOCl/CMK-3 Li 0.5 M PP14Cl in PP14TFSI 1.6–3.5 202 30 [38]
FeOCl/graphene Li 0.5 M PP14Cl in PP14TFSI 1.6–3.5 184 6 [39]
FeOCl/PANI Li 0.5 M PP14Cl in PP14TFSI 1.6–3.5 145 50 [40]
FeOCl/PPy Li 0.5 M PP14Cl in PP14TFSI 1.6–3.5 187 30 [41]
VOCl Li 0.5 M PP14Cl in PC 1.0–2.8 189 100 [42]
VOCl Mg 0.5 M PP14Cl in PC 0.6–2.2 101 53 [43]
Sb4O5Cl2 Li 0.5 M PP14Cl in PC 1.0–3.0 150 80 [44]
WOCl4 Li 3 M Pyr14Cl in PC:EC 0.5–3.9 120 50 [45]
CoFe-Cl LDH Li 0.5 M BPyCl in PP14TFSI and PC 1.2–3.0 239.3 100 [46]
Ni2V0.9Al0.1-Cl LDH Li 0.5 M BPyCl in PP14TFSI and PC 1.2–3.0 312.2 1000 [47]
CoNi-Cl LDH Li 0.5 M BpyCl in PC 1.2–3.0 186 50 [48]
NiFe-Cl LDH Li 0.5 M BPy14Cl in PC 1.2–3.0 350.6 800 [49]
NiMn-Cl LDH Li 0.5 M BPy14Cl in PC 1.1–3.0 284.7 150 [50]
PPyCl/CNTs Li 0.5 M PP14Cl in PP14TFSI 1.0–4.0 118 40 [51]
PANI/CNTs Li 0.5 M PP14Cl in PP14TFSI 1.2–4.0 80 50 [52]
PXVCl2 Li 0.5 M TBMACl in PC 1.5–3.2 175 60 [53]
PANI Zn TBACl in PVDF-HF 0.2–1.3 160 / [54]
Ag BiOCl 1 M NaCl 0–1.5 153 45 [23]
Ag BiOCl 1 M NaCl+1 M NH4Cl 0–1.0 123.7 200 [55]
Ag Sb4O5Cl2 1 M NaCl 0–1.5 34.6 50 [56]
AgCl Bi 1 M NaCl 0–1.2 87.9 1000 [57]
AgCl Sb 1 M NaCl 0–1.5 67.5 200 [58]
Graphene Zn 25 M (CH3)4NCl 0.8–3.1 136 2000 [59]
Graphite Zn 5 M (CH3)4NCl+5 M LiF 0.5–3.0 210 10000 [60]

capacities of 80, 111.8, and 176.6 mAh g-1 were observed for CoCl2, was ascribed to the large volumetric change and severe dissolution of
VCl3, and BiCl3, respectively, in the first cycle, the capacities deterio­ the cathode material during cycling. Recently, a new cathode material of
rated rapidly during subsequent cycles. The poor cycling performance CuCl has also been explored for chloride-based RCBs [31]. Because a

Fig. 2. Galvanostatic curves of the (a) BiOCl/Li, (b) FeOCl/Li, and (c) VOCl/Li systems. Reproduced with permission from [35,42]. Copyright 2013, 2016, Wiley
VCH. (d) Schematic illustration of the preparation process of FeOCl/CMK-3. (e) Comparison of the cycling performance of FeOCl/CMK-3, FeOCl/carbon black, and
FeOCl cathodes. Reproduced with permission from [38]. Copyright 2019, American Chemical Society.

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J. Yang et al.
higher oxidation state of CuCl2 can be formed during the charging
process by the oxidation of CuCl, the CuCl/Li battery delivered an initial
capacity of 278 mAh g-1 at 5 mA g-1 and retained 70 mAh g-1 even after
100 cycles.
Compared to metal chlorides, higher chemical stability can be
generally realized in metal oxychlorides (e.g., VOCl, BiOCl, FeOCl, and
WOCl4) due to the strong bonding of metal cations with the Lewis basic
O2- anions, which can alleviate the dissolution of the cathode material.
Fichtner et al. were the first to demonstrate the reversible storage of
chloride ions in BiOCl and FeOCl [35]. The initial discharge capacities
achieved for BiOCl and FeOCl cathode were 60 and 158 mAh g-1,
respectively, approaching 60 % of the theoretical capacity (Fig. 2a–b).
The chloride ion storage in BiOCl/FeOCl proceeds mainly via a revers­
ible conversion reaction. During the discharge process, the dein­
tercalation of Cl− from the metal oxychloride cathode occurs
simultaneously with the rapid transformation to amorphous metal ox­
ides, that is, Bi2O3 and FeO. The cathode restores chloride ions to form
metal oxychlorides during the subsequent charging process. Another
metal oxychloride explored for chloride-based RCBs is VOCl. Fichtner et
al [42]. prepared a solution of 0.5 M 1-butyl-1-methylpiperidinium
chloride (PP14Cl) in propylene carbonate (PC) as a new electrolyte,
which possessed a high ionic conductivity of 4.4 × 10-3 S cm-1 and wide
electrochemical stability window of up to 3.2 V versus Li. Comprehen­
sive characterizations confirmed that VOCl experiences interlayer
expansion during the initial discharge due to the irreversibly interca­
lated PP+ 14 ions. Chloride ions can be intercalated and deintercalated
more easily because intercalated PP+ 14 acts as a pillar and maintains wide
interlayer channels. In comparison to BiOCl and FeOCl, VOCl can ach­
ieve a higher capacity of 189 mAh g-1 with superior reversibility
(Fig. 2c). Recently, Fichtner et al [45]. reported a new metal oxy­
chloride, WOCl4 as the cathode material for chloride-based RCBs. The
characterization results confirmed that WOCl4 underwent a conversion
reaction upon discharging, with the formation of WO3 and WClx (x = 4,
5, 6) as discharge products. Thus, fast capacity fading was observed
during 50 cycles owing to the large volume changes resulting from the
conversion reaction.
To further improve the electrochemical performance of metal oxy­
chlorides, researchers have made great efforts, including nanoconfine­
ment, conductive polymer coating, and compositing with a carbon
matrix. For instance, Shen et al [38]. synthesized a FeOCl/CMK-3
composite as cathode for chloride-based RCBs via a nanoconfined
strategy (Fig. 2d). Benefiting from the confined effect of CMK-3 to
provide enhanced electrical conductivity and structural integrity, the
FeOCl/CMK-3 cathode displayed significantly improved cycling stability
compared to pure FeOCl and a simple composite with carbon black
(Fig. 2e). Other carbon-based composite methods, including mechanical
milling with carbon nanotubes and designing graphene aerogel struc­
tures, have also been used for metal oxychlorides (FeOCl and Sb4O5Cl2),
but the performance improvement has not been satisfactory [39,44].
Recently, conductive polymers have been investigated as coating layers
for metal oxychlorides [41]. The introduction of polypyrrole (PPy)
increased the electrical contact, chloride ion diffusion, and structural
stability of the FeOCl electrodes, which ultimately contributed to the
better cycling stability of FeOCl@PPy (82.9 %) over that of pristine
FeOCl (13.2 %) after 30 cycles.
In summary, metal chlorides and oxychlorides cathodes face signif­
icant challenges associated with large volumetric change and severe
dissolution in the electrolytes, leading to rapid capacity fade and limited
operational lifetime. To address these issues, both the nanostructured
electrode design and the stabilization of the electrode/electrolyte
interface through surface coating and/or electrolyte optimization
should be implemented.
2.1.2. Layered double hydroxides
As a class of typical layered materials, layered double hydroxides
(LDHs) are composed of alternately stacked, positively charged brucite-
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Nano Energy 110 (2023) 108364
like layers and weakly bound charge-balancing interlayer anions [61,
62]. Because of the large interlayer gallery and high exchangeability of
interlayer anions, LDHs can provide open 2D channels for anion trans­
port. In 2019, Han et al. [46] designed a CoFe-LDH with Cl− in the
interlayer and first explored its potential application in chloride-ion
batteries (Fig. 3a). Theoretical calculations suggest that CoFe-Cl LDH
has a favorable chloride ion diffusion path with a diffusion energy
barrier of only 0.12–0.25 eV (Fig. 3b), which is attributed to its large
interlayer spacing and open 2D channels. Consequently, the CoFe-Cl
LDH||Li metal cells delivered a large specific capacity of 239 mAh g-1,
exceeding most of the previously reported metal chlorides and oxy­
chlorides (Fig. 3c). Unfortunately, the capacity declined rapidly during
the subsequent 100 cycles. The author suggests that this may be due to
local structural distortions or partial dissolution of Co from the LDH
platelets. To address this issue, trimetallic Ni2V0.9Al0.1-Cl LDH with
enhanced structural stability was synthesized via the hydrothermal
method [47]. The crystal structure of the Ni2V0.9Al0.1 layer consists of
NiO6 and VO6 octahedra connected by shared edges, in which V ions in
the octahedral centers are partly substituted by Al ions (Fig. 3d). The
introduction of inactive Al ions effectively inhibits the structural
distortion, thus improving the structural stability and promoting reac­
tion kinetics. Under the potential window of 1.2–3.0 V, a remarkable
specific capacity of 312.2 mAh g-1 was achieved in Ni2V0.9Al0.1-Cl LDH
electrode, more importantly, maintaining an ultralong lifetime of over
1000 cycles (Fig. 3e). Moreover, the diffusion coefficient of Cl− esti­
mated by the galvanostatic intermittent titration technique (GITT)
indicated that the Al-doped Ni2V0.9Al0.1-Cl LDH had a considerably
higher value than the Al-free Ni2V-Cl LDH electrode.
Inspired by previous work, Han et al. prepared other types of LDH
with various chemical compositions, such as CoNi-X (X = F, Cl, Br) [48],
NiFe-Cl [49], and NiMn-Cl LDH [50]. They found that reversible shuttles
of halide ions (F− , Cl− , and Br− ) can be realized in CoNi LDH, demon­
strating their potential for application to halogen-ion batteries (Fig. 3f).
As a proof-of-concept, the first rechargeable bromide-ion batteries was
prepared based on a CoNi-Br LDH cathode and metallic lithium anode,
which presented a large specific capacity of 339 mAh g-1 and over 50
cycles. Similarly, the CoNi-F||Li and CoNi-Cl||Li cells show maximum
specific capacity of 113 and 186 mAh g-1, respectively. Ex situ analysis
by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and
energy-dispersive X-ray spectroscopy (EDS) revealed the reversible
intercalation/deintercalation of halogen ions into/from CoNi-X LDH,
accompanied by a valence change of Co3+/Co2+ and Ni3+/Ni2+.
Although LDH have great potential for application in chloride ion bat­
teries, the intrinsic limitation derived from the poor electrical conduc­
tivity and unavoidable self-aggregation hampers their electrochemical
activity. Such problems can be mitigated by constructing an integrated
hierarchical architecture. Luo et al [50]. successfully realized a hierar­
chical NiMn-Cl LDH/carbon nanotube (CNT) network via an in situ
co-precipitation method (Fig. 3 g). Representative scanning electron
microscope (SEM) images revealed uniform growth of NiMn-LDH
nanosheets on the CNT skeleton, featuring an obvious porous structure
(Fig. 3h). The enhanced electrical conductivity combined with a large
specific surface area facilitated fast ion/electron transport in NiMn-Cl
LDH/CNT, thereby exhibiting a better rate performance than that of
pure NiMn-Cl LDH.
Compared with metal chlorides and oxychlorides, LDHs as cathodes
for chloride-based RCBs presents a significant enhancement in reversible
capacity and cycling stability because of their inherent stable 2D
transport channels. To further improve the performance of LDHs ma­
terials, future research should focus on enhancing its electrical con­
ductivity, such as design of novel composites with conductive materials,
and introduction of defects or heteroatom. Besides, more in-depth study
of the underlying intercalation mechanisms is necessary.
2.1.3. Organic materials
Organic materials are potentially excellent cathode candidates for
J. Yang et al. Nano Energy 110 (2023) 108364

Fig. 3. (a) Crystal structures of CoFe-Cl LDH. (b) The calculated energy barrier for Cl− ion diffusion in CoFe-Cl LDH. (c) Galvanostatic charge-discharge curves of the
CoFe-Cl LDH cathode at 100 mA g-1. Reproduced with permission from [46]. Copyright 2019, Wiley VCH. (d) Crystal structures of Ni2V0.9Al0.1-Cl LDH. (e) Long-term
cycling performance of the Ni2V0.9Al0.1-Cl LDH cathode at 200 mA g-1. Reproduced with permission from [47]. Copyright 2019, Wiley VCH. (f) Schematic diagram of
the halide ions shuttle mechanism. Reproduced with permission from [48]. Copyright 2020, Elsevier. (g) Schematic illustration of the hierarchical structure and (h)
representative SEM images of NiMn-Cl LDH/CNT. Reproduced with permission from [50]. Copyright 2020, American Chemical Society.

chloride-based batteries because of their structural diversity, environ­
mental friendliness, and more importantly, limited solubility in elec­
trolytes, mitigating the dissolution issue faced by other materials [63].
Some typical conductive polymers have been developed as electrode
materials for Li-, Na-, K-, Mg-, Zn-, and Al-ion batteries, for example,
polypyrrole (PPy) and polyaniline (PANI) [64–66]. In 2017, the
chloride-ion-doped polypyrrole (PPyCl) material used as the cathode for
chloride-based RCBs was firstly reported by Zhao et al. [51]. Taking
carbon nanotubes (CNTs) as the skeleton, PPyCl was uniformly coated
on the surface of the CNTs to form PPyCl@CNTs by in situ chemical
oxidative polymerization. SEM and transmission electron microscopy
(TEM) revealed that the PPyCl@CNTs had a nanotube morphology with
a distinct hierarchical structure (Fig. 4a). When paired with a metallic
lithium anode, the PPyCl/Li system delivered a specific capacity of 118
mAh g-1 and almost remain unchanged after 40 cycles (Fig. 4b). The
as-assembled soft-packing battery could light up a light-emitting diode
(LED) for more than five minutes, demonstrating their potential for
practical applications. XPS spectra confirmed that the N+ species (C− N+
and C– – N+) in PPyCl underwent oxidation and reduction reactions
caused by chloride ion intercalation/deintercalation during cycling
(Fig. 4c).
In addition, conductive polymers can be used as intercalated species
for inorganic layered materials to improve their conductivity and elec­
trochemical performance. For instance, PANI can be incorporated into
FeOCl using an in situ intercalation/polymerization strategy [40]. The
embedded large-sized PANI significantly enlarged the interlayer dis­
tance of FeOCl from 0.79 to 1.4 nm while forming a cleaved lamellar
morphology (Fig. 4d–e), thus promoting chloride ion transport and
restricting the volume expansion upon cycling. As a consequence, the
FeOCl/PANI cathode demonstrated a reversible capacity of 120 mAh g-1
at 10 mA g-1 after 50 cycles, which is twice as high as that of pristine
FeOCl (Fig. 4f–g).
Previously reported polymers, including PPy and PANI, use nitrogen
as the redox center and exhibit high chemical stability. However, the
reversible capacity is still quite low owing to insufficient nitrogen active
sites. Polymerized polyxylylviologen chloride (PXVCl2) with fully active
nitrogen sites was first developed as electrode material for chloride
batteries [53]. By introducing graphene into the PXVCl2 matrix, the
PXVCl2/graphene composite electrodes exhibited a reversible capacity
of 175 mAh g-1, which is higher than other previously reported
conductive polymer electrodes.
Overall, organic polymers are promising cathode materials for
chloride-based RCBs due to their structural tunability and stability.
However, low theoretical capacity will likely limit their practical ap­
plications. A combination of organic cathodes with inorganic cathodes,
to achieve a balance between capacity and cycling stability, could be a
potential research direction for the future development of chloride-
based RCBs.

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J. Yang et al.
Fig. 4. (a) SEM and TEM images of the PPyCl@CNTs nanocomposite. (b) Cycling performance of the PPyCl@CNTs/Li systems. The inset shows soft-packing chloride-
based RCBs powering the LED light. (c) Schematic illustration of the chloride ion intercalation/deintercalation mechanism in PPyCl. Reproduced with permission
from [51]. Copyright 2017, American Chemical Society. (d) SEM images and (e) crystal structures of polyaniline-intercalated FeOCl. Galvanostatic curves of (f) FeOCl
and (g) polyaniline-intercalated FeOCl cathodes. Reproduced with permission from [40]. Copyright 2019, Wiley VCH.
2.2. Anode
Most of the currently reported non-aqueous chloride batteries
employ lithium metal as the anode because of its high reduction po­
tential and easy reaction with chloride ions during cycling. Replacing
lithium with other earth-abundant metals, such as Na, K, Zn, Mg, and Al,
as anodes will significantly reduces the production cost of batteries.
Among them, multivalent metals are particularly interesting because
they can provide multielectron redox reactions, which potentially result
in higher specific capacities and energy densities. Zhao et al. first
demonstrated a chloride-ion battery using Mg metal as the anode [36].
Considering that the decomposition of the electrolyte on the pure Mg
anode surface may inhibit Cl− ion transfer and block reversible Mg
plating/stripping, they prepared an Mg/C composite as anode by two
methods: ball milling of mixed Mg and carbon black powders and
thermally decomposing a MgH2/C composite. When FeOCl (or BiOCl) is
used as the cathode, the full FeOCl/Mg (or BiOCl/Mg) batteries deliv­
ered maximum specific capacities of 130 (or 102) mAh g-1. Unfortu­
nately, because the large volume change of Mg disrupts the electrical
contact with carbon black, these battery systems suffer from rapid ca­
pacity decay upon cycling. Gao et al. [43] prepared an anode comprised
of a MgCl2/Mg/C composite using a similar ball-milling method.
Although the capacity retention is obviously improved compared to that
of the Mg/C composite, the capacity of the MgCl2/Mg/C composite is
still unsatisfactory for practical applications. Another bivalent metal,
zinc, has also been reported as an anode in chloride-ion batteries.
Gschwind et al. [54] constructed a room-temperature solid-state
chloride-ion battery composed of CuCl2/C or PNAI as the cathode ma­
terial, Zn as the anode, and chloride-conducting polymer electrolytes.
However, the results are preliminary, and only the first discharge curves
are shown. The development of other non-lithium metals as anodes for
chloride-ion batteries remains a significant challenge.
2.3. Electrolytes
2.3.1. Liquid electrolytes
Liquid electrolytes can be divided into two categories: non-aqueous
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Nano Energy 110 (2023) 108364
and aqueous. Non-aqueous, organic solvent-based liquid electrolytes
are the main choice for chloride-based batteries, particularly room-
temperature ionic liquids (ILs), which are currently the most
commonly used electrolytes because of their low or no vapor pressure
and wide electrochemical windows. An earlier study by Zhao et al. [15]
reported a binary ionic liquid consisting of 1-butyl-3-methylimidazo­
lium tetrafluoroborate ([BMIM][BF4]) and 1-methyl-3-octylimidazo­
lium chloride ([OMIM][Cl]) in a ratio of 3:1 as the electrolyte. This
electrolyte exhibits a high ionic conductivity of 9.1 × 10-4 S cm-1 at
298 K. Following this study, they developed two electrolytes, 0.5 M
benzyldimethyltetradecylammonium chloride (N116(14)Cl) in bis(tri­
fluoromethylsulfonyl)imide (N1114TFSI) and 0.5 M 1-butyl-1-methylpi­
peridinium chloride (PP14Cl) in 1-butyl-1-methylpiperidinium bis
(trifluoromethylsulfonyl)imide (PP14TFSI) [35], where the ionic con­
ductivity was measured to be 7.3 × 10-4 and 6.1 × 10-4 S cm-1, respec­
tively, at 298 K. More importantly, the immersion test conducted by the
researchers proves that the cathode material can remain stable in the
electrolyte for more than two months, indicating that the ionic liquid
electrolytes do not react with the cathode. To further enhance the ionic
conductivity of non-aqueous electrolytes, some research groups have
attempted to incorporate low-viscosity carbonate solvents (e.g., pro­
pylene carbonate (PC)) into ionic liquids or to directly replace ionic
liquids with carbonate solvents [42–44,48–50]. These strategies have
proven effective in improving the ion storage performance and stability
of cathode materials. Although significant progress has been made in
non-aqueous electrolytes, many questions remain unresolved, such as
those related to ionic conductivity, viscosity, and compatibility.
Compared to flammable, non-aqueous electrolytes, rechargeable
chloride-based batteries employing aqueous electrolytes are intrinsi­
cally safe, environmentally benign, and cost-effective. However,
aqueous chloride-based RCBs have not been reported until recently, due
to the lack of stable electrode materials to achieve reversible Cl− storage.
The first aqueous rechargeable chloride-based RCBs was demonstrated
in 2017 using a silver metal cathode, a BiOCl anode, and an electrolyte
based on a 1 M NaCl aqueous solution [23]. As shown in Fig. 5a, upon
charging, the Cl− ions are extracted from the BiOCl anode, transported
through the aqueous NaCl electrolyte, and eventually reacted with the
J. Yang et al. Nano Energy 110 (2023) 108364

Fig. 5. (a) Schematic showing the working principles of BiOCl/Ag battery during the charge process. (b) Cyclic voltammograms and (c) cycling performance of the
BiOCl/Ag battery system in 1 M NaCl aqueous electrolyte. Reproduced with permission from [23]. Copyright 2017, Elsevier. (d) Comparison of the cycling per­
formance of BiOCl/Ag battery system with different electrolytes. Reproduced with permission from [55]. Copyright 2022, Elsevier. (e) Electrochemical stability
window of (CH3)4NCl electrolytes with various concentrations. Reproduced with permission from [59]. Copyright 2021, Elsevier. (f) Optical photos and (g) linear
sweep voltammetry scan of the PEO1-TBMACl1-SN3 solid polymer electrolyte film. (h) Galvanostatic charge-discharge curves of the FeOCl/Li batteries in
PEO1-TBMACl1-SN3 solid polymer electrolyte. Reproduced with permission from [24]. Copyright 2019, Wiley VCH. (i) Schematic synthesis route of cubic CsSnCl3. (j)
Theoretical calculations of Cl− migration barriers in the cubic and monoclinic CsSnCl3. Reproduced with permission from [75]. Copyright 2020, American Chem­
ical Society.

Ag cathode to form AgCl. The opposite reaction occurred upon dis­
charging. The cyclic voltammetric (CV) curves of BiOCl/Ag battery
shows a pair of redox peaks appeared at 0.84/0.41 V after the second
cycle (Fig. 5b), attributed to the reversible Cl− insertion/extraction be­
tween the cathode and anode. This new battery system delivered a
reversible specific capacity of 92.1 mAh g-1 with a Coulombic efficiency
(CE) of ~100 % at 400 mA g-1 (Fig. 5c), which is comparable to other
aqueous Li- or Na-ion batteries. Similar to BiOCl, Sb4O5Cl2 has also been
applied in aqueous chloride-based RCBs with a 1 M NaCl solution as the
electrolyte, but its specific discharge capacity is merely 34.6 mAh g-1
[56]. Recently, Lu et al. proposed an interesting electrolyte regulation
strategy for improving the reaction kinetics of both electrodes in
chloride-based RCBs by introducing ammonia chloride (NH4Cl) into the
aqueous NaCl electrolyte as an additive [55]. Due to the dissociation of
ammonium ions (NH+ 4 ) in the aqueous electrolyte, producing ammonia
(NH3) and protons (H+), AgCl reacted with NH3 to form an Ag(NH3)+ 2
intermediate phase, facilitating the AgCl/Ag conversion reaction at the
cathode. The H+ ions produced from the dissociation of NH+ 4 can func­
tion as oxygen acceptors to promote the valence state transfer of
Bi3+/Bi0 at the anode side. Clearly, with a small amount of NH4Cl in the
NaCl electrolyte, the cycling stability of the BiOCl/Ag battery was
improved compared with that of the pure NaCl electrolyte (Fig. 5d).
Although rechargeable aqueous chloride-based RCBs have been
achieved using a NaCl solution as the electrolyte, their energy density is

7
J. Yang et al.
still relatively low due to a narrow voltage window. High-concentration
‘‘water-in-salt” type electrolyte has been successfully used in the fabri­
cation of high-energy aqueous Li/Na/Zn/Al batteries [67–70].
Hydrogen evolution can be effectively inhibited in such electrolytes
because of the absence of free water molecules, thus resulting in a wider
potential window. The concept of ‘‘water-in-salt’’ electrolyte was first
employed in chloride-based RCBs by Li et al. [59]. Tetramethylammo­
nium chloride (CH3)4NCl was selected as the electrolyte salt due to its
high solubility at room temperature and good stability against hydro­
lysis. When the concentration of (CH3)4NCl electrolyte increased from 1
to 25 mol kg− 1 (m), a wider electrochemical stability window of 3.10 V
was realized (Fig. 5e). Spectral analysis and the theoretical model reveal
that the destruction of hydrogen bonds between water molecules is
aggravated due to the increase in electrolyte concentration. As a result,
the reactivity of free water molecules is significantly reduced and, thus,
widening the electrochemical stability window. In a saturated
(CH3)4NCl electrolyte, the assembled chloride batteries using the gra­
phene cathode and a Zn metal anode could achieve a high reversible
capacity of 136 mAh g-1 and a specific energy of 252 Wh kg-1. Addi­
tionally, an impressive cycle life (>2000 cycles) was obtained, repre­
senting the most stable cycling performance for aqueous chloride-based
RCBs.
2.3.2. Solid-state electrolytes
Although liquid electrolytes offer the benefits of high conductivity
and excellent wetting of the electrode surfaces, there are still challenges
related to their use in chloride-based RCBs due to unavoidable electrode
dissolution and probable side reactions with the electrode. In addition,
increasing the concentration of Cl− ions in the electrolyte increases the
likelihood of chlorine gas production. These issues can be effectively
addressed by using solid-state electrolytes (SSEs). Current SSEs are
classified into two major categories: organic polymers and inorganic
solid electrolytes. Compared to inorganic SSEs, organic polymer elec­
trolytes exhibit better flexibility, lower interfacial contact resistance
with electrodes, and easy processing [71]. The common polymer matrix
for SSEs including polyethylene oxide (PEO), polyvinyl alcohol (PVA),
polyvinylchloride (PVC), polymethyl methacrylate (PMMA), and poly­
vinylidene fluoride (PVDF), etc. The feasibility of the chloride-based
RCBs using polymer as the electrolytes was firstly demonstrated by
Gschwind et al. [54]. Three polymers, gelatin, polyvinylchloride (PVC),
and polyvinyldifluoride-hexafluoropolymer (PVDF-HF), were mixed
with chloride-containing salts to form chloride-conducting membranes.
The assembled PANI||Zn and CuCl2/C||Zn batteries achieved initial
capacities of 160 and 130 mAh g-1, respectively, in PVDF-HF based
membrane electrolytes. However, the reversibility of these systems re­
mains uncertain. Other chloride-ion-conducting polymer membranes
have also been reported in recent years, including polyethylene oxide
(PEO)-tributylmethylammonium chloride (TBMACl)-succinonitrile (SN)
[24], polymethyl methacrylate (PMMA)-1-butyl-1-methylpiperidinium
chloride (PP14Cl)-1-butyl-1-methylpiperidinium bis(trifluoromethyl
sulfonyl)imide (PP14TFSI) [37], polydiallyl dimethylammonium chlo­
ride (PDDAC)-polyethylene glycol (PEG) [32], and tetramethylammo­
nium chloride ((CH3)4NCl)-polyvinyl alcohol (PVA) [60], all of which
exhibit good chloride ion conductivity and flexibility. For example, Zhao
et al. [24] constructed a PEO-TBMACl-SN solid polymer electrolyte
composed of PEO as the polymer matrix, TBMACl as the chloride salt,
and SN as the solid plasticizer. This polymer membrane possessed high
mechanical flexibility against bending (Fig. 5f), as well as a high ionic
conductivity above 10-5 S cm-1. In addition, the wide voltage window (>
4.24 V vs. Li/Li+) ensured deep charging and discharging of the elec­
trodes, thereby leading to a large reversible capacity of 110 mAh g-1 for
FeOCl/Li batteries (Fig. 5g–h).
Inorganic SSEs generally exhibit a relatively wide electrochemical
stability window, which allows batteries to operate over a wide poten­
tial. Nevertheless, their intrinsic roughness and rigidity inevitably result
in poor interfacial contact with the electrode. The issues of chemical
8
Nano Energy 110 (2023) 108364
stability and thermal stability also must be resolved before inorganic
SSEs can be used in chloride-based RCBs. Early explorations have shown
that some inorganic chlorides such as BaCl2, SrCl2, LaCl3, and LaOCl can
act as chloride ion conductors [72–74], but high operating temperatures
(> 200 ℃) limit their practical use. Recently, Okada et al. [34] first
reported KCl-doped PbCl2, that is, Pb1-xKxCl2-x (x = 0.01, 0.02, 0.03), as
a solid electrolyte, achieving a high ionic conductivity of ~10-4 S cm-1 at
room temperature. Because no cathode dissolution occurred in the solid
electrolytes, the assembled BiCl3/Pb cell delivered a maximum specific
capacity of 187 mAh g-1 at a rate of 0.042 C and retained 85 % of its
original capacity after 30 cycles. Unfortunately, the energy density of
the battery may be limited by its narrow electrochemical stability win­
dow (0.2–0.8 V). Further development of solid electrolytes with wider
electrochemical windows is necessary. To this end, a room-temperature
stable inorganic halide perovskite of CsSnCl3 as solid electrolyte with a
wider electrochemical window (~ 6.1 V) was successfully prepared via
mechanical milling and subsequent heat treatment (Fig. 5i) [75].
Benefiting from the rich nanograins and tin vacancy, the cubic CsSnCl3
electrolyte remained highly stable with no phase transformation to the
monoclinic phase for more than three months. DFT calculations revealed
that the Cl− ion migration energy in cubic CsSnCl3 is 0.20 eV (Fig. 5j),
which is considerably lower than that of monoclinic CsSnCl3 (0.44 eV).
Therefore, the ionic conductivity of cubic CsSnCl3 (3.6 × 10-4 S cm-1)
was significantly improved compared to that of monoclinic CsSnCl3
(10-10–10-9 S cm-1) based on electrochemical impedance spectroscopy
(EIS) measurements.
3. Chloride-based dual-ion batteries
In conventional “rocking-chair” cells, such as alkali-metal lithium or
sodium ion batteries, the cationic charge carriers (i.e., Li+, or Na+)
migrate between the cathode and anode during the charge/discharge
process. In DIBs, both anions and cations are participated in the elec­
trochemical reactions. Anion intercalation can occur on the cathode side
under a high operating potential, which is beneficial for the battery to
achieve a higher energy density [76]. A variety of anions have been
reported for reversible storage in DIBs [77,78], such as hexa­
fluorophosphate (PF-6), tetrafluoroborate (BF-4), perchlorate (ClO-4), bis
(fluorosulfonyl) imide (FSI-), trifluoromethanesulfonic (CF3SO-3), bis
(trifluoromethanesulfonyl) imide (TFSI-), and difluoro (oxalate) borate
(DFOB-). Recently, DIBs based on different chloride-based anion car­
riers, including single-chloride ions, dual-halogens, and superhalides,
have also been reported [79]. In this section, we discuss recent progress
in electrode materials and their working mechanisms for DIBs based on
chloride-based anion storage.
3.1. Single chloride-ion storage
To date, most DIBs have operated in nonaqueous electrolytes. Ji et al.
[27] reported a novel aqueous DIBs, that employed Mn3O4 as cathode
materials, Zn metal as the anode, in addition to 20 M ZnCl2 plus 5 M
NH4Cl as the electrolyte. The cell chemistry involves the
intercalation/de-intercalation of Cl− into/from the Mn3O4 and the
plating/stripping of Zn2+ on the Zn metal. The typical galvanostatic
profile of Mn3O4 demonstrates a low initial discharge capacity of 48
mAh g-1 (Fig. 6a), which was attributed to the irreversible reductive
insertion of Zn2+ into Mn3O4 to form Zn0.2Mn3O4. Because Zn2+ and Cl−
are counter ions, the pre-intercalated Zn2+ further facilitates the
reversible storage of Cl− . This phenomenon can be defined as the
counter-ion insertion mechanism. New compounds of AyMOxBz can be
obtained as chloride-hosting electrodes by this generic methodology, for
example, Zn0.2Mn3O4Cl1.7 featured in this study (Fig. 6b). Therefore, a
Cl− storage capacity reaching up to 200 mAh g-1 in subsequent cycles.
The electrochemical quartz crystal microbalance (EQCM) results
coupled with cyclic voltammetry revealed a slight mass change rate of
~35 g/mole e- during electrochemical cycling, confirming that chloride
J. Yang et al. Nano Energy 110 (2023) 108364

Fig. 6. (a) Galvanostatic profiles of Mn3O4 cathode in the first three cycles. (b) Schematic depicting the counter-ion insertion mechanism. (c) CV curves of Mn3O4 and
corresponding EQCM results. Reproduced with permission from [27]. Copyright 2020, Wiley VCH. (d) Schematic image of the chemical structures of m-PTPA. (e)
Chloride ion combination energy profiles of m-PTPA. (f) Galvanostatic charge-discharge curves of aqueous DIBs based on PTPA and m-PTPA cathodes. Reproduced
with permission from [80]. Copyright 2021, Wiley VCH. (g) Schematic of the conversion-intercalation mechanism occurring in the (LiBr)0.5(LiCl)0.5–graphite
cathode. (h) Cyclic voltammogram curves and (i) Galvanostatic curves of the (LiBr)0.5(LiCl)0.5–graphite cathode. Reproduced with permission from [26]. Copyright
2019, Nature Publishing Group. (j) Typical discharge profiles of the zinc-based DIBs involving single-halogen (purple) or dual-halogen redox reactions (red). (k)
Cyclic voltammograms of the zinc-based DIBs in the electrolyte of ZnCl2⋅2H2O and ZnCl2⋅(0.03KBr)⋅2H2O. Reproduced with permission from [81]. Copyright 2020,
Wiley VCH.

ions are the primary charge carriers (Fig. 6c).
Except for inorganic oxides, other anion hosting materials such as
organic materials have also been studied in the chloride-based DIBs
system. Liu et al. [80] investigated the feasibility of using a poriferous
polytriphenylamine conjugated microporous polymer (m-PTPA) as
cathode for aqueous DIBs with attractive energy density (236 Wh kg-1)
and peak power density (6.8 kW kg-1). Density functional theory (DFT)
calculations combined with Fourier transform-infrared spectroscopy
(FT-IR) proved that the N atoms in the amine/imine group were
redox-active sites for chemical interaction with Cl− anions (Fig. 6d).
Thanks to their unique porous structure enables the exposure of active
nitrogen sites, m-PTPA possessed a higher Cl− storage number compared
to nonporous conjugated polytriphenylamine (PTPA). Thus, the result­
ing DIBs showed a significant increase in specific capacity from 99.8 to
210.7 mAh g-1, corresponding to 39.4 % and 83.2 % accessibility effi­
cacy of active sites for PTPA and m-PTPA cathode, respectively
(Fig. 6e–f).
3.2. Dual-halogen storage
In addition to single Cl ions, some dual-halogen species, such as Br-Cl
and I-Cl, have also been investigated in DIBs. This novel dual-halogen

9
J. Yang et al.
storage chemistry results in a higher operating voltage and reversible
capacity, thereby significantly improving the cell energy density.
Recently, Yang et al. proposed a unique halogen conversion-
intercalation chemistry that integrates the merits of conversion re­
actions (high energy) and intercalation reactions (high reversibility)
[26]. A highly concentrated water-in-bisalt (WiBS) electrolyte expands
the electrochemical window to ~4.9 V versus Li/Li+, realizing the high
reversibility of halide oxidation/reduction at high potentials. For the
graphite cathode, the reversible electrochemical behavior was based on
a two-step redox reaction involving both Br− and Cl− . As shown in
Fig. 6g, upon charging from 4.0 to 4.2 V, Br− was first oxidized to atomic
bromine (Br0) with oxidation state of near zero, and subsequently
inserted into graphite, forming the Cn[Br] compound. Upon further
charging to 4.5 V, the Cl− also underwent oxidation to a near-zero state
(Cl0) and then combined with Cn[Br], resulting in the formation of
intercalation compound Cn[BrCl]. The opposite reaction occurred dur­
ing the discharge process, in which Cl0 and Br0 were successively
extracted from the graphite host and reduced to halides. The corre­
sponding CV curve exhibits two pairs of redox peaks at 4.0–4.2 V and
4.2–4.5 V, demonstrating a two-step conversion-intercalation reaction
mechanism associated with Br− and Cl− (Fig. 6 h). Similar electro­
chemical behavior was observed in the galvanostatic curves, with two
pairs of well-defined sloping plateaus (Fig. 6i). The graphite cathode
delivered a high reversible capacity of 243 mAh g-1 with nearly 100 %
CE, confirming the high reversibility of the graphite for dual-halogen
storage.
The Br-Cl dual-halogen storage chemistry has also been extended to
aqueous zinc-based battery systems [81]. Conventional zinc-ion and
dual-ion batteries usually suffer from drawbacks of low working voltage
and limited capacity, respectively. By employing dual-halogen redox
couples (Br0/Br− and Cl0/Cl− ) at the graphite cathode with a molten
hydrate electrolyte, the designed zinc dual-halogen battery exhibited a
significantly increased discharge capacity (257 mAh g-1) and operation
potential (1.71 V) compared with single-halogen batteries based solely
on Br0/Br− (78 mAh g-1/1.60 V, Fig. 6j). The authors found that it was
difficult to insert chloride ions into graphite directly, whereas bromine
ions could function as chemical mediators to bring chloride into the
graphite interlayer. As depicted in Fig. 6k, the graphite cathode
exhibited completely different electrochemical behaviors in ZnCl2
electrolytes with and without additional KBr salt. Two pairs of redox
peaks were identified in cyclic voltammograms of the ZnCl2⋅(0.03KBr)⋅
2 H2O electrolyte, which were ascribed to the reversible formation of
graphite-halogen compounds (C[BrmCln]). In contrast, no obvious redox
peaks were observed in the ZnCl2⋅2H2O electrolyte, suggesting the
important role of bromine in the electrochemical reactions. Inspired by
this research, Guo et al. found that iodine played a similar mediator role
to bromide, enabling the storage of chlorine in the carbon cathode by
forming interhalogen [ICl2]− species [82]. Because the chlorine or ox­
ygen evolution reaction could be effectively suppressed in a new
aqueous deep eutectic solvent (DES) gel electrolyte composed of 30 m
ZnCl2, 120 m choline chloride (ChCl), and 5 m KI, DIBs based on the
graphenic carbon cathode delivered a record-high reversible capacity of
up to 1100 mAh g-1. Such a conversion-intercalation mechanism rep­
resents a new approach for designing high-energy rechargeable
batteries.
3.3. Superhalides storage
Superhalides, such as PF−6 , BF−4 , and TFSI− have received the most
attention for DIBs in the past ten years [77]. Recently, Cl-containing
metal-based superhalides, including Al-Cl, Zn-Cl, and Mg-Cl super­
halides, have been investigated as anionic charge carriers for DIBs [25,
83,84]. A typical example is Al-Cl superhalides, that is, chloroaluminate.
Dai’s group proposed the first Al/graphite battery employing metallic Al
anode and pyrolytic graphite (PG) or graphitic foam as the cathode [25].
The operating mechanism is based on the insertion/extraction of
10
Nano Energy 110 (2023) 108364
chloroaluminate anions (AlCl−4 ) in the graphite cathode and the strip­
ping/plating of aluminum at the anode (Fig. 7a). During the discharging
process, Al dissolves from the metal anode to form AlCl−4 and Al2Cl−7
species, and then, an intercalation reaction of AlCl−4 occurs in the
graphite. The constructed Al/PG cells exhibited a specific capacity of
approximately 65 mAh g-1 under a current rate of 66 mA g-1 (Fig. 7b).
Two distinctive plateaus regions of 2.25–2.0 V and 1.9–1.5 V were
found in the discharge process, corresponding to the anion intercalation
stage of graphite. Considering that the open frame structure may facil­
itate the intercalation of AlCl−4 anions, the author prepared a
three-dimensional graphitic foam as a cathode by chemical vapour
deposition. Compared to PG, the constructed Al/graphitic foam cells
could be achieve faster charging rate of up to 75 C, and no evidence of
capacity fading was found after 7500 cycles (Fig. 7c–d). Chlor­
oaluminate anion intercalation was confirmed by XPS, in situ Raman
spectroscopy, and Auger electron spectroscopy (AES). Since this work,
various carbon-based materials, including natural graphite, graphene,
and MOF-derived carbon, have been widely used as alternative cathodes
for aluminum batteries based on AlCl−4 storage mechanisms [85–87].
Unlike Al-based DIBs, which use an ionic liquid as the electrolyte,
other reported DIBs based on superhalides as charge carriers employ
aqueous electrolytes. Ji et al. developed a highly concentrated water-in-
salt electrolyte based on inexpensive ZnCl2 [83]. When the concentra­
tion of ZnCl2 was increased from 5 to 30 m, the parasitic hydrogen
evolution reaction (HER) and oxygen evolution reaction (OER) were
effectively suppressed, and a new ionic species of [ZnClx]2− x appeared.
Pairing the nitrogen-doped graphene cathode with a Zn metal anode,
author demonstrated a new aqueous Zn-based DIBs with [ZnClx]2− x as
charge carriers. The 3D porous structure of the carbon cathode and high
concentration electrolytes enabled reversibly storage of [ZnClx]2− x
through electrical double layer adsorption and ion insertion at a high
working potential (1.95 V versus Zn) (Fig. 8a–b). In addition, the battery
retained a reversible capacity of ~80 mAh g-1 after 800 cycles,
demonstrating an excellent cycling stability (Fig. 8c). Using [ZnCl4]2- as
anionic charge carriers, the same group reported another storage system
defined as reverse dual-ion batteries (RDIBs) [28], which share similar
operating mechanisms with DIBs, whereas storage ions on opposite
electrodes. During the discharging process, [ZnCl4]2- and Zn2+ were
inserted into the ferrocene anode and the Prussian blue cathode,
respectively (Fig. 8d). Conversely, [ZnCl4]2- anions and Zn2+ cations
were simultaneously extracted from the electrodes upon charging.
Interestingly, when the concentration of ZnCl2 was increased to 30 m,
the cation insertion potential at the cathode increased, while the anion
insertion potential at the anode decreased, thereby widening the po­
tential gap between the two electrodes (Fig. 8e). Unfortunately, RDIBs
only deliver a low specific capacity of ~30 mAh g-1 based on the total
active mass of both the cathode and anode, and further investigation is
required to optimize the performance of this novel system.
Mg-Cl superhalides can be reversibly intercalated into graphite,
which was first confirmed by Kim et al. [84]. The results of stimulated
Raman spectroscopy indicated that Mg2+ cations are preferentially co­
ordinated by Cl− to form Mg-Cl superhalides, that is, [MgCl4]2− and
[MgCl3(OH2)]− , in an aqueous DES electrolyte composed of 9 m MgCl2
and 30 m choline chloride (ChCl). Although a high initial capacity of
150 mAh g-1 was achieved in these electrolytes, the graphite electrode
exhibited rapid capacity fading after 25 cycles. The authors ascribed this
Mg-Cl superhalide storage process to graphite being partially turbos­
tratic rather than a homogeneous intercalation reaction, which was
confirmed by ex situ XRD, Raman spectroscopy, and high-resolution
transmission electron microscopy (HRTEM). Inspired by previous
work, a lighter and smaller superhalide of [LiCl2]− was verified in a DES
electrolyte composed of 20 m LiCl and 20 m ChCl [88]. Because the
strong coordination of water molecules with the strong Lewis acid of Li+
in aqueous electrolytes, trace water molecules will inevitably coin­
tercalate with [LiCl2]− upon discharging, which results in a significantly
improved cycling stability, but with a decreased anion intercalation
J. Yang et al.
Fig. 7. (a) Schematic illustrations of the working principle for Al/graphite cell. Galvanostatic curves of Al-ion battery using (b) pyrolytic graphite and (c) graphitic
foam cathode. (d) Cycling performance of the Al/graphitic foam pouch cell at 4000 mA g-1. Reproduced with permission from [25]. Copyright 2015, Nature Pub­
lishing Group.
potential. Ex situ characterization revealed that the insertion of hy­
drated [LiCl2]− rendered graphite partially turbostratic, similar to the
Mg-Cl superhalides. By developing new formulations of “water-in-salt”
or DES electrolytes, more superhalides are expected to be investigated as
charge carriers for DIBs.
4. Other chloride-based rechargeable batteries
4.1. Desalination battery
Desalination is one of the most promising and effective approaches
for addressing the challenge of global freshwater shortage [89].
Tremendous efforts have been devoted to developing efficient desali­
nation technologies in the past decade, for example, thermal desalina­
tion, reverse osmosis desalination, forward osmosis desalination, and
capacitive desalination (CDI) [90–92]. Among which, thermal and
reverse osmosis desalination are the most mature technologies at pre­
sent, accounting for more than 90 % of the global desalination capacity;
however, both techniques require considerable energy consumption.
Although CDI has recently attracted increasing attention owing to its
low energy consumption and mild operating conditions, its low desali­
nation efficiency still hinders its practical implementation [93]. To
address these issues, the development of new desalination technologies
is required.
In 2012, a “desalination battery” combining the advantages of low
energy consumption and high desalination capacity was first proposed
by Mantia et al. [94]. They employed Na2Mn5O10 and Ag electrodes to
capture Na+ and Cl− , respectively, exhibiting a low energy consumption
of 0.29 Wh L-1 for the removal of 25 % NaCl. Generally, desalination
11
Nano Energy 110 (2023) 108364
batteries are in a dual-ion configuration composed of Na+ and Cl−
capture electrodes. Fig. 9a–b illustrates the ideal operating principle of
the desalination battery. When the potential of the Cl− capture electrode
was higher than that of the Na+ capture electrode, salt removal
accompanied by electrical energy storage occurred upon charging.
These processes are reversed upon discharging, the electrode re­
generates and accompanied by a release of energy. Therefore, the
development of Na+ and Cl− storage materials is crucial for
high-performance desalination batteries. Conventional sodium interca­
lation materials have been investigated for use in desalination batteries,
including NaTi2(PO4)3 [95–97], Na3V2(PO4)3 [98,99], Na0.44MnO2
[100,101], Na1.1V3O7.9 [102], and Cu3[Fe(CN)6]2 [103]. These mate­
rials showed high Na+ storage capacity in sodium-ion batteries.
Compared with Na+ storage materials, there are extremely limited
candidates for capturing Cl− , including two conversion-type materials:
Ag and Bi. Because these two metals and their chlorinated forms are
stable under saline aqueous conditions, sustainable desalination/sali­
nation through conversion reactions of Ag/AgCl or Bi/BiOCl in seawater
is feasible. Ag electrodes were the first used Cl− capture materials in
desalination batteries. Following the successful work of Mantia, Chen
et al. [101] experimentally demonstrated that the reversible reaction of
Ag + Cl− ↔ AgCl + e− occurs during the desalination/salination process.
As shown in Fig. 9c–d, the silver diffraction peaks from the XRD pattern
drastically increased and decreased due to the reversible extrac­
tion/recovery of Cl, which agrees with the EDS results. Owing to the
excellent reversibility of the AgCl and Na0.44MnO2 electrodes, this
desalination system delivered a high salt absorption/desorption capac­
ity of 57.4 mg g-1 for 100 cycles, which is considerably higher than that
of the traditional CDI deionization system. Subsequent work has
J. Yang et al. Nano Energy 110 (2023) 108364

Fig. 8. (a) Schematic illustrations of the working principles of N-doped few-layered graphene in Zinc DIBs. (b) Galvanostatic charge/discharge curves and (c) cycling
performance of Zinc DIBs at 100 mA g-1. Reproduced with permission from [83]. Copyright 2020, Wiley VCH. (d) Schematic illustration of the operation scheme of
the RDIBs. (e) Comparison of CV curves of individual electrodes in ZnCl2 electrolytes with different concentrations. Reproduced with permission from [28]. Copyright
2019, American Chemical Society.

attempted to solve the low electronic conductivity of Ag electrodes by
composite with carbon materials. For example, by designing a free­
standing AgCl/reduced graphene oxide (rGO) aerogel to add more
electron transport channels and enhance the electrical conductivity
[99], the desalination capacity of Na3V2(PO4)3/rGO–AgCl/rGO was
significantly increased to 107.5 mg g-1. Although Ag has many advan­
tages as a Cl− capture material, its high cost and large volume expansion
limit its practical applications. Compared with Ag, Bi is less expensive,
demonstrating the advantages of constructing large-scale desalination
cells. Using Bi as Cl− capture electrode for desalination cells was first
realized by Yang and Choi’s group in 2017 [95,100]. The Pourbaix di­
agram shows that Bi exists in the form of insoluble BiOCl over a wide pH
range of 0–10.5, which makes Bi an ideal Cl− ion capture material. In
aqueous media, Bi undergoes the following conversion reaction with Cl−
to form BiOCl:Bi + Cl− + H2O ↔ BiOCl + 2H+ + 3e− , which corresponds
to a theoretical capacity of ~279.7 mg g-1. Based on this principle, Chen
et al [100]. proposed a novel deionization system called the flow
dual-ion electrochemical deionization. When coupled with Na0.44MnO2,
the BiOCl-based deionization system delivered a stable and reversible
desalination capacity of 68.5 mg g-1 at a current density of 100 mA g-1
(Fig. 9e-f), which is nearly three times higher than that of the hybrid
capacitive deionization. The electric charge efficiencies for salt
desorption and absorption were 0.977 and 0.958, respectively. Despite
the reported excellent performance, Bi/BiOCl electrodes for seawater
desalination still have some drawbacks. First, the Cl− and Na+ ions
captured are an unbalanced reaction that involves three-electron and
one-electron transfer processes, respectively. In addition, the reaction
kinetics of Bi→BiOCl in neutral solutions are faster than those of BiO­
Cl→Bi. Further intensive studies of Bi/BiOCl as an electrode material for
desalination batteries should focus on increasing its utilization and
improving electrode stability.
In summary, as a promising desalination technology, desalination
batteries have received wide attention owing to their low energy con­
sumption and high salt removal capacity. Nevertheless, this technology
remains in its infancy and is likely to be driven by exploring the novel
electrode materials with higher desalination capacities and excellent
stabilities. Due to limited space, a more comprehensive introduction to
desalinated batteries will not be covered here but can be found in other
outstanding reviews [90,91].

12
J. Yang et al. Nano Energy 110 (2023) 108364

Fig. 9. (a-b) Schematic illustrations of

the operating principles of Bi/
NaTi2(PO4)3 desalination cell. Repro­
duced with permission from [95].
Copyright 2017, American Chemical
Society. (c) XRD patterns and (d) EDS
analysis of initial AgCl electrode, Cl
extraction and Cl recovery. Reproduced
with permission from [101]. Copyright
2017, Royal Society of Chemistry.
Electrochemical salt removal/release
capacity and corresponding electric
charge efficiency during (e) cycling
process and (f) rate capability test.
Reproduced with permission from
[100]. Copyright 2017, Royal Society of
Chemistry.

4.2. Alkali-metal/Cl2 battery
The demand for higher energy densities has been driving the
development of battery technology in recent decades. As early as the
1970 s, the primary lithium-thionyl chloride (Li-SOCl2) battery was
invented and widely applied [104–106]. This battery is characterized by
a high discharge capacity of ~2300 mAh g-1 and a high energy density of
up to 710 Wh kg-1. However, as these batteries are primary systems,
recharging after the first discharge is infeasible. Until recently, Dai’s
group first developed a rechargeable alkali-metal-Cl2 battery derived
from their primary types [29]. This battery employed amorphous carbon
nanospheres (aCNS) as the cathode, Na metal or Li metal as the anode,
and AlCl3 salt dissolved in SOCl2 with fluoride-based additives as the
electrolyte (Fig. 10a). In this system, the operating mechanism was
based on the redox reactions of Cl2/Cl− in the aCNS cathode and Na/Na+
(or Li/Li+) on the metal anode. During the discharge process, NaCl (or
LiCl) was deposited on the aCNS cathode, and the SOCl2 reduction re­
action occurred to form SO2 and S. The opposite reaction took place
during the charging process. The deposited NaCl was converted to Na
and Cl2, accompanied by oxidation of SOCl2 to form SCl2, S2Cl2, and
SO2Cl2. As a result, unprecedented high initial capacities of 2810 and
3309 mAh g-1 were achieved for the Na/Cl2 and Li/Cl2 batteries,
respectively (Fig. 10b). When cycling at 100 mA g-1, the Na/Cl2 battery
delivered a specific cathode capacity of 1800 mAh g-1 for over 15 cycles

13
J. Yang et al. Nano Energy 110 (2023) 108364

Fig. 10. (a) Schematic illustrations of the Na/Cl2 battery. (b) The initial discharge profiles of the Na/Cl2 battery. (c) Cycling performance of Na/Cl2 battery at a
current density of 100 mA g-1. (d) Na/Cl2 battery powering the LED light. Reproduced with permission from [29]. Copyright 2021, Nature Publishing Group. (e)
Configurations of the Cl2-CCl4 system. (f) Comparison of the galvanostatic charge-discharge curve of Cl2-CCl4 and Cl2 without CCl4. (g) The voltage efficiencies of the
full CFB at different current densities. Reproduced with permission from [30]. Copyright 2022, Nature Publishing Group.

with a CE of 90 % (Fig. 10c). To practically demonstrate the power
supply capability of the Na/Cl2 battery, a light-emitting diode (LED) was
illuminated under a discharge current of 1563.35 mA g-1 (Fig. 10d).
Following this study, the same group developed new graphite positive
electrodes for use in Li/Cl2 batteries [107]. Activated by CO2 in a
high-temperature environment, pristine graphite generated more de­
fects, accompanied by an increase of pore volume and specific surface
area. Consequently, the Li/Cl2 battery delivered a discharge capacity of
~1910 mAh g-1 at 50 mA g-1 and remained at 1200 mAh g-1 for more
than 35 cycles. Raman spectroscopy in combination with XRD revealed
the structural evolution of graphite caused by inter­
calation/deintercalation and exfoliation, which creates a capacious,
porelike space for LiCl/Cl2 trapping and reversible redox reactions.
These works illustrates the attractive application prospects of
liquid/gas-based materials toward the future rechargeable high-energy
batteries.
4.3. Chlorine flow battery
Redox flow batteries (RFB) are critical for large-scale stationary en­
ergy storage because of their scalability and flexibility in decoupling
power and energy [108,109]. Currently, RFB can be generally classified
into several types: vanadium-, zinc-, iron-based, etc. However, the
development of these systems has been limited by their high chemical
costs and low energy densities. Very recently, Wang’s group reported a
new RFB system employing the highly reversible Cl2/Cl− redox reactions
[30]. Cl2/Cl− redox chemistry offers three distinct advantages: (i)
Cl2/Cl− redox couple can provide a high theoretical capacity of 755 mAh
g-1, which is considerably higher than the VO+ 2 /VO
2+
commonly used in
RFB (226 mAh g-1); (ii) the fast single-electron transfer reaction of
Cl2/Cl− makes RFB suitable for high-power applications; and (iii) the
potentially low cost of NaCl as an electrolyte significantly reduces the
production cost of RFB. To investigate the Cl2/Cl− redox reaction in the
NaCl electrolyte, the authors constructed a concentric cell that
employed RuO2-TiO2 coated porous carbon (RuO2-TiO2@C), activated
carbon, and Ag/AgCl as the working, counter, and reference electrodes,
respectively (Fig. 10e). Upon charging, Cl− is oxidized in the working
electrode to form Cl2 and subsequently is stored in carbon tetrachloride
(CCl4), for which RuO2-TiO2 serve as a catalyst to promote the Cl−
oxidation kinetics. Upon discharging, the Cl2 in CCl4 was reduced to Cl−
in the RuO2-TiO2@C electrode and returned to the NaCl electrolyte.
Owing to the high solubility of Cl2 in CCl4, the cell capacity loss was
significantly reduced from 92 % to 3 % (Fig. 10f). By replacing the
activated carbon counter electrode with NaTi2(PO4)3, a full CFB was
achieved. Benefiting from the membrane-free design and fast reaction
kinetics, the cell voltage efficiency was calculated as 93.6 % at
10 mA cm-2 and ~ 77 % at 100 mA cm-2 (Fig. 10g). Thus, the CFB ex­
hibits a high energy density of 125.7 Wh L-1 with an energy efficiency of
>91 % at 10 mA cm-2, which exceeds those of all reported flow batteries
in the past decade. In addition, the battery could provide the peak power

14
J. Yang et al.
density of 325 mW cm-2 at a current density of 350 mA cm-2. Although
this technology has been considered for future grid-scale energy storage,
the risk of Cl2 leakage is a major concern.
5. Conclusions and perspectives
Rechargeable chloride-based batteries stand out from a variety of
“post Li-ion” battery technologies for the advantages of resource
affordability and high energy density. Their unique battery chemistry
also provides new insights into the exploration of electrode materials
and storage mechanisms. In this review, we summarized the latest
research in rechargeable chloride-based batteries, including chloride-
based RCBs and DIBs systems, as well as other emerging Cl-based bat­
teries. The charge storage mechanism, electrode and electrolyte design
strategies for each technology are fully discussed. Although significant
progress has been made in improving the performance of rechargeable
chloride-based batteries, extensive efforts are still required in the
following aspects:
(1) Chloride-based RCBs share similar working mechanisms with
LIBs, and exploring appropriate electrode materials and optimizing the
electrolyte system are the key to improving electrochemical perfor­
mance. The dissolution of cathode materials in electrolytes and large
volume changes caused by phase transformation are critical issues that
result in poor cycle stability. These issues can be addressed via structural
engineering and/or the development of solid/gel polymer electrolytes.
Structural engineering is mainly focused on surface coating and
compositing with carbon-based materials or conducting polymers,
which have proven effective in enhancing structural integrity. Using
solid/gel polymer electrolytes instead of liquid electrolytes can avoid
material dissolution and provide higher safety; however, the matters of
low ionic conductivity and poor electrode compatibility should be
addressed before further research is conducted.
(2) Chloride-based DIBs exhibit a different operating mechanism
compared to RCBs, which offer higher operating potentials and energy
densities. Previous research has firmly established and demonstrated the
availability and feasibility of Cl-containing species, including single-
chloride ions, dual-halogens, and superhalides, as charge carriers to
construct chloride-based DIBs. For metal-based superhalides, there is a
plethora of new research opportunities. By using new formulations of
“water-in-salt” or deep eutectic solvent electrolytes, many more super­
halide charge carriers, except Al-Cl, Zn-Cl, Mg-Cl, and Li-Cl, is expected
and can be identified for anion storage. Additionally, the reverse DIBs
system is still in its infancy and only a limited number of electrode
materials have been reported. Current reverse DIBs still have the issues
of low output voltage and energy densities; further intensive efforts
should be devoted to searching for electrode couples while developing
compatible electrolytes.
(3) As a novel battery system, the storage mechanism of rechargeable
chloride-based batteries differs from that of conventional metal-ion
batteries, involving different electrode reactions, side reactions, and
interface chemistries. Thus, a clear and in-depth understanding of these
mechanisms, informed by complementary advanced characterization
techniques and theoretical calculations, is required to rationally
improve upon chloride-based batteries at the material level. Currently,
most of the reported characterization methods for chloride-based bat­
teries are ex situ techniques, and more advanced operando analytical
techniques such as in situ XRD, in situ TEM, and in situ Raman spec­
troscopy are needed to probe the ionic diffusion, interfacial phenomena,
and structural stability of electrodes in rechargeable chloride-based
batteries.
(4) Alkali-metal/Cl2 and chlorine flow batteries are promising high-
energy storage systems. However, the high levels of toxicity and
corrosion caused by Cl2/Cl− should be carefully considered throughout
the battery study process, from protocol design to battery packaging,
and in the analysis of the battery test results.
As an ideal low-cost energy storage system, rechargeable chloride-
15
Nano Energy 110 (2023) 108364
based battery technologies are still in the preliminary stage. There are
still several bottlenecks and substantial investigation room for the future
development. We hope that this review offers some insights into future
research on high-performance rechargeable chloride-based batteries
and other anion storage batteries.
CRediT authorship contribution statement
Jinlin Yang: Investigation, Conceptualization, Writing – original
draft, Writing – review & editing. Yu Zhang, Guan Wang: Investigation,
Visualization. Yuhao Liu, Xiaodong Shi, Hui Zhang: Conceptualiza­
tion, Writing – review & editing, Funding Support. Jing Li, Peilin Deng,
Xinlong Tian: Writing – review & editing, Funding Support.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
This work was supported by the Hainan Provincial Natural Science
Foundation of China (222MS006, 222MS009), National Natural Science
Foundation of China (22109034, 22109035, 52164028, 62105083,
52274297), the Foundation of State Key Laboratory of Marine Resource
Utilization in South China Sea (Hainan University, Grant No.
MRUKF2021029), and the Start-up Research Foundation of Hainan
University (KYQD(ZR)-20008, 20082, 20083, 20084, 21065, 21124,
21125), and the specific research fund of The Innovation Platform for
Academicians of Hainan Province.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.nanoen.2023.108364.
References
[1] B. Dunn, H. Kamath, J.-M. Tarascon, Science 334 (2011) 928–935.
[2] A. Kwade, W. Haselrieder, R. Leithoff, A. Modlinger, F. Dietrich, K. Droeder, Nat.
Energy 3 (2018) 290–300.
[3] Z. Zhu, T. Jiang, M. Ali, Y. Meng, Y. Jin, Y. Cui, W. Chen, Chem. Rev. 122 (2022)
16610–16751.
[4] M. Winter, B. Barnett, K. Xu, Chem. Rev. 118 (2018) 11433–11456.
[5] Y. Tian, G. Zeng, A. Rutt, T. Shi, H. Kim, J. Wang, J. Koettgen, Y. Sun, B. Ouyang,
T. Chen, Z. Lun, Z. Rong, K. Persson, G. Ceder, Chem. Rev. 121 (2021)
1623–1669.
[6] J.W. Choi, D. Aurbach, Nat. Rev. Mater. 1 (2016) 16013.
[7] C. Delmas, Adv. Energy Mater. 8 (2018), 1703137.
[8] R. Rajagopalan, Y. Tang, X. Ji, C. Jia, H. Wang, Adv. Funct. Mater. 30 (2020),
1909486.
[9] J. Muldoon, C.B. Bucur, T. Gregory, Chem. Rev. 114 (2014) 11683–11720.
[10] N. Zhang, X. Chen, M. Yu, Z. Niu, F. Cheng, J. Chen, Chem. Soc. Rev. 49 (2020)
4203–4219.
[11] M.E. Arroyo-de Dompablo, A. Ponrouch, P. Johansson, M.R. Palacín, Chem. Rev.
120 (2020) 6331–6357.
[12] K.L. Ng, B. Amrithraj, G. Azimi, Joule 6 (2022) 134–170.
[13] P. Canepa, G.S. Gautam, D.C. Hannah, R. Malik, M. Liu, K.G. Gallagher, K.
A. Persson, G. Ceder, Chem. Rev. 117 (2017) 4287–4341.
[14] M.A. Reddy, M. Fichtner, J. Mater. Chem. 21 (2011) 17059–17063.
[15] X. Zhao, S. Ren, M. Bruns, M. Fichtner, J. Power Sources 245 (2014) 706–711.
[16] J.A. Seel, J.R. Dahn, J. Electrochem. Soc. 147 (2000) 892–898.
[17] S. Panero, E. Spila, B. Scrosati, J. Electrochem. Soc. 143 (1996) L29–L30.
[18] V.W. Rudorff, U. Hofman, U. Graphitsalze, Z. Anorg. Allg. Chem. 238 (1938)
1–50.
[19] H. Jiang, Z. Wei, L. Ma, Y. Yuan, J.J. Hong, X. Wu, D.P. Leonard, J. Holoubek, J.
J. Razink, W.F. Stickle, F. Du, T. Wu, J. Lu, X. Ji, Angew. Chem. Int. Ed. 58 (2019)
5286–5291.
J. Yang et al.
[20] G. Liang, F. Mo, X. Ji, C. Zhi, Nat. Rev. Mater. 6 (2021) 109–123.
[21] Q. Dou, N. Wu, H. Yuan, K.H. Shin, Y. Tang, D. Mitlin, H.S. Park, Chem. Soc. Rev.
50 (2021) 6734–6789.
[22] J. Xu, Y. Liu, C. Xu, J. Li, Z. Yang, H. Yan, H. Yu, L. Yan, L. Zhang, J. Shu, Coord.
Chem. Rev 424 (2020).
[23] F. Chen, Z.Y. Leong, H.Y. Yang, Energy Storage Mater. 7 (2017) 189–194.
[24] C. Chen, T. Yu, M. Yang, X. Zhao, X. Shen, Adv. Sci. 6 (2019), 1802130.
[25] M.-C. Lin, M. Gong, B. Lu, Y. Wu, D.-Y. Wang, M. Guan, M. Angell, C. Chen,
J. Yang, B.-J. Hwang, H. Dai, Nature 520 (2015) 324–328.
[26] C. Yang, J. Chen, X. Ji, T.P. Pollard, X. Lu, C.J. Sun, S. Hou, Q. Liu, C. Liu, T. Qing,
Y. Wang, O. Borodin, Y. Ren, K. Xu, C. Wang, Nature 569 (2019) 245–250.
[27] H. Jiang, X. Ji, Carbon Energy 2 (2020) 437–442.
[28] X. Wu, Y. Xu, C. Zhang, D.P. Leonard, A. Markir, J. Lu, X. Ji, J. Am. Chem. Soc.
141 (2019) 6338–6344.
[29] G. Zhu, X. Tian, H.C. Tai, Y.Y. Li, J. Li, H. Sun, P. Liang, M. Angell, C.L. Huang, C.
S. Ku, W.H. Hung, S.K. Jiang, Y. Meng, H. Chen, M.C. Lin, B.J. Hwang, H. Dai,
Nature 596 (2021) 525–530.
[30] S. Hou, L. Chen, X. Fan, X. Fan, X. Ji, B. Wang, C. Cui, J. Chen, C. Yang, W. Wang,
C. Li, C. Wang, Nat. Commun. 13 (2022) 1281.
[31] J. Liu, J. Zhang, X. Chen, Y. Sun, P. Gao, ChemElectroChem 9 (2022),
e202200332.
[32] Q. Wang, J. Liu, J. Zhang, X.-M. Lou, Q. Tan, P. Gao, Mater. Lett. 329 (2022),
133150.
[33] C. Zhang, S. Sun, M. Wu, X. Zhao, Chin. Chem. Lett. 33 (2022) 2200–2204.
[34] R. Sakamoto, N. Shirai, A. Inoishi, S. Okada, ChemElectroChem 8 (2021)
4441–4444.
[35] X. Zhao, Z. Zhao-Karger, D. Wang, M. Fichtner, Angew. Chem. Int. Ed. 52 (2013)
13621–13624.
[36] X. Zhao, Q. Li, Z. Zhao-Karger, P. Gao, K. Fink, X. Shen, M. Fichtner, ACS Appl.
Mater. Interfaces 6 (2014) 10997–11000.
[37] L. Wu, Z. Chen, X. Ma, Int. J. Electrochem. Sci. 14 (2019) 2414–2421.
[38] T. Yu, Q. Li, X. Zhao, H. Xia, L. Ma, J. Wang, Y.S. Meng, X. Shen, ACS Energy Lett.
2 (2017) 2341–2348.
[39] X. Zhao, Q. Li, T. Yu, M. Yang, K. Fink, X. Shen, Sci. Rep. 6 (2016) 19448.
[40] T. Yu, R. Yang, X. Zhao, X. Shen, ChemElectroChem 6 (2019) 1761–1767.
[41] R. Yang, T. Yu, X. Zhao, J. Alloy. Compd. 788 (2019) 407–412.
[42] P. Gao, M.A. Reddy, X. Mu, T. Diemant, L. Zhang, Z. Zhao-Karger, V.
S. Chakravadhanula, O. Clemens, R.J. Behm, M. Fichtner, Angew. Chem. Int. Ed.
55 (2016) 4285–4290.
[43] P. Gao, X. Zhao, Z. Zhao-Karger, T. Diemant, R.J. Behm, M. Fichtner, ACS Appl.
Mater. Interfaces 6 (2014) 22430–22435.
[44] K. Lakshmi, K. Janas, M. Shaijumon, J. Power Sources 433 (2019), 126685.
[45] G. Karkera, M. Soans, B. Dasari, E. Umeshbabu, M.A. Cambaz, Z. Meng,
T. Diemant, M. Fichtner, Energy Technol. 10 (2022), 2200193.
[46] Q. Yin, D. Rao, G. Zhang, Y. Zhao, J. Han, K. Lin, L. Zheng, J. Zhang, J. Zhou,
M. Wei, Adv. Funct. Mater. 29 (2019), 1900983.
[47] Q. Yin, J. Luo, J. Zhang, S. Zhang, J. Han, Y. Lin, J. Zhou, L. Zheng, M. Wei, Adv.
Funct. Mater. 30 (2020), 1907448.
[48] Q. Yin, J. Zhang, J. Luo, J. Han, M. Shao, M. Wei, Chem. Eng. J. 389 (2020),
124376.
[49] Q. Yin, J. Luo, J. Zhang, L. Zheng, G. Cui, J. Han, D. O’Hare, J. Mater. Chem. A 8
(2020) 12548–12555.
[50] J. Luo, Q. Yin, J. Zhang, S. Zhang, L. Zheng, J. Han, ACS Appl. Energy Mater. 3
(2020) 4559–4568.
[51] X. Zhao, Z. Zhao, M. Yang, H. Xia, T. Yu, X. Shen, ACS Appl. Mater. Interfaces 9
(2017) 2535–2540.
[52] Z. Zhao, T. Yu, Y. Miao, X. Zhao, Electrochim. Acta 270 (2018) 30–36.
[53] T. Xia, T. Zhu, Y. Miao, X. Zhao, A.C.S. Appl, Energy Mater. 5 (2022) 6980–6985.
[54] F. Gschwind, D. Steinle, D. Sandbeck, C. Schmidt, E. von Hauff, ChemistryOpen 5
(2016) 525–530.
[55] J. Sun, Q. Sun, H. Ye, Y. Wang, J.A.S. Oh, D. Ji, Q. Zeng, K. Zeng, L. Lu, Mater.
Today Energy 26 (2022), 101020.
[56] X. Hu, F. Chen, S. Wang, Q. Ru, B. Chu, C. Wei, Y. Shi, Z. Ye, Y. Chu, X. Hou,
L. Sun, ACS Appl. Mater. Interfaces 11 (2019) 9144–9148.
[57] Z. Zhang, K. Shen, Y. Zhou, X. Hou, Q. Ru, Q. He, C.-y Su, L. Sun, S.H. Aung,
F. Chen, Ionics 26 (2020) 2395–2403.
[58] Q. Zhang, R. Karthick, X. Zhao, L. Zhang, Y. Shi, L. Sun, C.Y. Su, F. Chen,
Nanoscale 12 (2020) 12268–12274.
[59] T. Li, M. Li, H. Li, H. Zhao, iScience 24 (2021), 101976.
[60] H. Li, M. Li, H. Zhao, T. Li, Z. Fang, J. Power, Sources 512 (2021), 230507.
[61] J. Yu, Q. Wang, D. O’Hare, L. Sun, Chem. Soc. Rev. 46 (2017) 5950–5974.
[62] X. Long, Z. Wang, S. Xiao, Y. An, S. Yang, Mater. Today 19 (2016) 213–226.
[63] S. Muench, A. Wild, C. Friebe, B. Ha¨upler, T. Janoschka, U.S. Schubert, Chem.
Rev. 116 (2016) 9438–9484.
[64] Y. Lu, Q. Zhang, L. Li, Z. Niu, J. Chen, Chem 4 (2018) 2786–2813.
[65] Y. Liang, Y. Yao, Joule 2 (2018) 1690–1706.
[66] P. Poizot, J. Gaubicher, S. Renault, L. Dubois, Y. Liang, Y. Yao, Chem. Rev. 120
(2020) 6490–6557.
[67] L. Suo, O. Borodin, T. Gao, M. Olguin, J. Ho, X. Fan, C. Luo, C. Wang, K. Xu,
Science 350 (2015) 938–943.
[68] L. Suo, O. Borodin, Y. Wang, X. Rong, W. Sun, X. Fan, S. Xu, M.A. Schroeder, A.
V. Cresce, F. Wang, C. Yang, Y.-S. Hu, K. Xu, C. Wang, Adv. Energy Mater. 7
(2017), 1701189.
[69] F. Wang, O. Borodin, T. Gao, X. Fan, W. Sun, F. Han, A. Faraone, J.A. Dura, K. Xu,
C. Wang, Nat. Mater. 17 (2018) 543–549.
16
Nano Energy 110 (2023) 108364
[70] W. Pan, Y. Zhao, J. Mao, Y. Wang, X. Zhao, K.W. Leong, S. Luo, X. Liu, H. Wang,
J. Xuan, S. Yang, Y. Chen, D.Y.C. Leung, Adv. Energy Mater. 11 (2021), 2101514.
[71] L. Fan, S. Wei, S. Li, Q. Li, Y. Lu, Adv. Energy Mater. 8 (2018), 1702657.
[72] C.M. Mari, R.M. Cappello, C. Galbiati, Solid State Ion. 111 (1998) 93–97.
[73] C.C. Liang, J.R. Rea, A.V. Joshi, D.L. Foster, J. Solid State Chem. 22 (1977)
171–177.
[74] H. Matsumoto, T. Miyake, H. Iwahara, Mater. Res. Bull. 36 (2001) 1177–1184.
[75] T. Xia, Y. Li, L. Huang, W. Ji, M. Yang, X. Zhao, ACS Appl. Mater. Interfaces 12
(2020) 18634–18641.
[76] T. Placke, A. Heckmann, R. Schmuch, P. Meister, K. Beltrop, M. Winter, Joule 2
(2018) 2528–2550.
[77] X. Zhou, Q. Liu, C. Jiang, B. Ji, X. Ji, Y. Tang, H.-M. Cheng, Angew. Chem. Int. Ed.
59 (2020) 3802–3832.
[78] X. Ou, D. Gong, C. Han, Z. Liu, Y. Tang, Adv. Energy Mater. 11 (2021), 2102498.
[79] Q. Liu, Y. Wang, X. Yang, D. Zhou, X. Wang, P. Jaumaux, F. Kang, B. Li, X. Ji,
G. Wang, Chem 7 (2021) 1993–2021.
[80] H. Zhang, L. Zhong, J. Xie, F. Yang, X. Liu, X. Lu, Adv. Mater. 33 (2021),
2101857.
[81] H. Liu, C.Y. Chen, H. Yang, Y. Wang, L. Zou, Y.S. Wei, J. Jiang, J. Guo, W. Shi,
Q. Xu, P. Cheng, Adv. Mater. 32 (2020), e2004553.
[82] Q. Guo, K.-I. Kim, S. Li, A.M. Scida, P. Yu, S.K. Sandstrom, L. Zhang, S. Sun,
H. Jiang, Q. Ni, D. Yu, M.M. Lerner, H. Xia, X. Ji, ACS Energy Lett. 6 (2021)
459–467.
[83] Q. Guo, K.-i Kim, H. Jiang, L. Zhang, C. Zhang, D. Yu, Q. Ni, X. Chang, T. Chen,
H. Xia, X. Ji, Adv. Funct. Mater. 30 (2020), 2002825.
[84] K.-I. Kim, Q. Guo, L. Tang, L. Zhu, C. Pan, C.-H. Chang, J. Razink, M.M. Lerner,
C. Fang, X. Ji, Angew. Chem. Int. Ed. 59 (2020) 19924–19928.
[85] D.-Y. Wang, C.-Y. Wei, M.-C. Lin, C.-J. Pan, H.-L. Chou, H.-A. Chen, M. Gong,
Y. Wu, C. Yuan, M. Angell, Y.-J. Hsieh, Y.-H. Chen, C.-Y. Wen, C.-W. Chen, B.-
J. Hwang, C.-C. Chen, H. Dai, Nat. Commun. 8 (2017) 14283.
[86] Y. Wu, M. Gong, M.-C. Lin, C. Yuan, M. Angell, L. Huang, D.-Y. Wang, X. Zhang,
J. Yang, B.-J. Hwang, H. Dai, Adv. Mater. 28 (2016) 9218–9222.
[87] C. Li, S. Dong, R. Tang, X. Ge, Z. Zhang, C. Wang, Y. Lu, L. Yin, Energy Environ.
Sci. 11 (2018) 3201–3211.
[88] K.-i Kim, L. Tang, P. Mirabedini, A. Yokoi, J.M. Muratli, Q. Guo, M.M. Lerner,
K. Gotoh, P.A. Greaney, C. Fang, X. Ji, Adv. Funct. Mater. 32 (2022), 2112709.
[89] J. Eke, A. Yusuf, A. Giwa, A. Sodiq, Desalination 495 (2020), 114633.
[90] F.E. Ahmed, A. Khalil, N. Hilal, Desalination 517 (2021), 115183.
[91] D. Xu, W. Wang, M. Zhu, C. Li, ACS Appl. Mater. Interfaces 12 (2020)
57671–57685.
[92] I. Ullah, M.G. Rasul, Energies 12 (2019) 119.
[93] Y. Liu, K. Wang, X. Xu, K. Eid, A.M. Abdullah, L. Pan, Y. Yamauchi, ACS Nano 15
(2021) 13924–13942.
[94] M. Pasta, C.D. Wessells, Y. Cui, L.F. Mantia, Nano Lett. 12 (2012) 839–843.
[95] D.-H. Nam, K.-S. Choi, J. Am. Chem. Soc. 139 (2017) 11055–11063.
[96] W. Wei, X. Feng, R. Wang, R. Zheng, D. Yang, H. Chen, Nano Lett. 21 (2021)
4830–4837.
[97] Y. Huang, F. Chen, L. Guo, J. Zhang, T. Chen, H.Y. Yang, Desalination 451 (2019)
241–247.
[98] W. Zhao, L. Guo, M. Ding, Y. Huang, H.Y. Yang, ACS Appl. Mater. Interfaces 10
(2018) 40540–40548.
[99] W. Zhao, M. Ding, L. Guo, H.Y. Yang, Small 15 (2019), 1805505.
[100] F. Chen, Y. Huang, L. Guo, L. Sun, Y. Wang, H.Y. Yang, Energy Environ. Sci. 10
(2017) 2081–2089.
[101] F. Chen, Y. Huang, L. Guo, M. Ding, H.Y. Yang, Nanoscale 9 (2017) 10101–10108.
[102] Z. Yue, Y. Ma, J. Zhang, H. Li, J. Mater. Chem. A 7 (2019) 16892–16901.
[103] D.-H. Nam, M.A. Lumley, K.-S. Choi, Chem. Mater. 31 (2019) 1460–1468.
[104] H.V. Venkatasetty, D.J. Saathoff, J. Electrochem. Soc. 128 (1981) 773–777.
[105] W.K. Istone, R.J. Brodd, J. Electrochem. Soc. 131 (1984) 2467–2470.
[106] R. Gangadharan, P.N.N. Namboodiri, K.V. Prasad, R. Viswanathan, J. Power
Sources 4 (1979) 1–9.
[107] G. Zhu, P. Liang, C.L. Huang, C.C. Huang, Y.Y. Li, S.C. Wu, J. Li, F. Wang, X. Tian,
W.H. Huang, S.K. Jiang, W.H. Hung, H. Chen, M.C. Lin, B.J. Hwang, H. Dai,
J. Am. Chem. Soc. 144 (2022) 22505.
[108] G.L. Soloveichik, Chem. Rev. 115 (2015) 11533–11558.
[109] Z. Li, Y.-C. Lu, Adv. Mater. 32 (2020), 2002132.
Jinlin Yang received his Ph.D. degree in materials science
from Soochow University in 2022. He is currently an associate
research fellow in State Key Laboratory of Marine Resource
Utilization in South China Sea at Hainan University. His
research focuses on rational synthesis of two-dimensional ma­
terials for next-generation energy storage devices.
J. Yang et al.
Yuhao Liu obtained his Bachelor’s degree from Ludong Uni­
versity of Physics and Optical Engineering in 2012/06. From
2012/09–2017/06, he studied at the College of Physics at
Huazhong University of Science and Technology, and he
received his Ph.D. degree in 2017/6. From 2017/06–2020/06,
he worked as the postdoctoral fellow in Wuhan National Lab­
oratory for Optoelectronics (WNLO) at Huazhong University of
Science and Technology. Currently, he holds the associate
professor position in School of Science in Hainan University.
His research interest is the fabrication and utilization of metal
chalcogenide photocatalysts for the application of photo­
catalytic hydrogen evolution.
Yu Zhang obtained her Bachelor’s degree from Hunan Uni­
versity of Arts and Science in 2022. She is currently a M.S.
candidate in the Chemical Engineering and Technology at
Hainan University. Her research interests focuses on the design
of functional nanomaterials for electrochemical energy storage
devices.
Guan Wang received his B.S. degree in Huanghuai University.
He is now pursing his M.S. degree under the supervision of
Prof. Xinlong Tian in School of Chemical Engineering and
Technology at Hainan University. His main interest is the
design and preparation of nanomaterials for electrocatalysis.
Xiaodong Shi received his PhD degree from Central South
University, and joined the China State Key Laboratory of Ma­
rine Resource Utilization in South China Sea, Hainan Univer­
sity, as an associate research fellow in 2022. His current
research focuses on the synthesis and application of nano­
materials for energy storage devices, such as seawater batte­
ries, sodium/potassium-ion batteries and aqueous zinc-ion
batteries.
17
Nano Energy 110 (2023) 108364
Hui Zhang is a professor in Hainan University in China. Prior
to her current appointment, Prof. Zhang worked as a post­
doctoral fellow in Okinawa Institute of Science and Technology
Graduate University in Japan and King Abdullah University of
Science and Technology in Saudi Arabia, respectively. She
received her B.E. and Ph.D. from Sichuan University and
Peking University, respectively. Her research interest is
development of advanced materials for high-energy-density
storage systems, including lithium batteries, aqueous batte­
ries and metal-air batteries.
Jing Li obtained her Bachelor’s degree from Henan University
of Science and Technology in 2009/06. From 2010/09–2013/
06, she studied at the School of Chemistry and Chemical En­
gineering at Guizhou University and obtained her master’s
degree. She received her Ph.D. degree from South China Uni­
versity of Technology in 2019/09. Currently, she holds the
lecturer position in School of Chemical Engineering and
Technology in Hainan University. Her research interest is the
research and application of transition metal-based catalysts for
electrolysis of water/seawater.
Peilin Deng received his Ph.D. degree in engineering from
Huazhong University of Science and Technology in 2020. He is
now an associate researcher in the School of Chemical Engi­
neering and Technology at Hainan University. He mainly fo­
cuses on the research and development of key technologies for
low carbon conversion and utilization, and works on interna­
tional frontier research directions such as electrochemical
reduction of carbon dioxide and efficient conversion of
combustible ice, oriented to new materials with high activity,
long life and low cost.
Xinlong Tian is currently a full professor in State Key Labo­
ratory of Marine Resource Utilization in South China Sea at
Hainan University, China. He received his Ph.D. degree from
South China University of Technology in 2016. Afterwards, he
worked as a postdoctoral researcher in Huazhong University of
Science and Technology from 2016 to 2019. Now he is the
Principal Investigator of the Marine Clean Energy Innovation
Group, and his research interests are in the areas of nano­
structured functional materials and their applications in Elec­
trochemistry, Electrocatalysis, Sustainable energy and Fuel
cells.