Nano

Nano Energy 110 (2023) 108364
Contents lists available at ScienceDirect
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

generally form ionic bonds with host materials, anion non-metallic
Electrochemical energy storage technologies, particularly recharge charge carriers can interact with positively charged structural atoms
able batteries, show significant potential for the application in grid-scale in the electrode to form hybrid covalent-ionic bonds, which serve as an
energy storage, transportation, and portable electronics, owing to their additional redox center for charge transfer, resulting in superior elec
reliability, ease of deployment, and technological maturity [1,2]. trochemical performance [20]. Anionic charge carriers are usually
Among these battery systems, lithium-ion batteries (LIBs), which have earth-abundant elements, which makes them cheaper than metallic
high gravimetric energy density and good cycle life, have been very charge carriers, thus bringing new opportunities to further reduce the
successful over the past 30 years [3,4]. However, with energy density cost of energy storage [21,22]. Among these anions, Cl− is particularly
advancements in LIBs approaching their limits and the ongoing deple attractive owing to its obvious merits, including: (1) high theoretical
tion of limited global lithium resources, the demands for higher energy volumetric and gravimetric energy density of up to 2500 Wh L-1 or 1100
density and lower cost have driven the investigation of so-called Wh kg-1, which exceeds that of traditional LIBs and comparable to that
“beyond Li-ion” technologies [5,6]. Although new rechargeable batte of Li-S batteries (see Supplementary Table S1 for details); (2) high
ries with low-cost metal ions as charge carriers, including alkali metal electronegativity, which provides a wide electrochemical stability win
ions (Na+, K+) [7,8] and multivalent metal ions (Mg2+, Zn2+, Ca2+, dow; (3) low manufacturing costs due to the abundant
Al3+) [9–13] have been proposed as promising alternatives to LIBs for chloride-containing materials (see Supplementary Table S2 for details);
large-scale applications, tremendous research efforts are still needed to and (4) dendrite-free formation at metallic anodes upon cycling.
address their limited energy densities and lifetime costs to meet the Therefore, the large-scale energy storage applications can be realized
current market demand. due to the above-mentioned features of Cl− .
In recent years, rechargeable anion-based batteries using anions (e. A timeline summarizing the major milestones of rechargeable
g., F− , Cl− , PF−6 , ClO-4, HSO-4, and NO-3) as charge carriers have aroused chloride-based batteries is presented in Fig. 1. Based on the operating
* Corresponding authors.
E-mail addresses: [email protected] (P. Deng), [email protected] (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 2. Chloride-based rocking-chair batteries
types: chloride-based RCBs, chloride-based DIBs, and other chloride-
based batteries. Pioneering work by Fichtner et al. reported a non- Well-known LIBs are typical rocking-chair batteries that involve
aqueous chloride-based RCBs in 2013 using lithium metal as the shuttling of Li+ cations between the cathode and anode during the
anode and metal chlorides (BiCl3, CoCl2, and VCl2) as the cathode [15]. charge/discharge process. Replacing Li+ cations with Cl− anions, that is,
Subsequently, the first aqueous and all-solid-state chloride-based RCBs designing a chloride-based rocking-chair battery, is an attractive
were successively reported in 2017 and 2018, and aqueous NaCl solu approach to reduce production costs for scaled-up applications. How
tion and poly(ethylene oxide)-tributylmethylammonium chlor ever, there are inevitable challenges before their full potential can be
ide-succinonitrile (PEO-TBMACl-SN) were employed as electrolytes, realized, such as exploring appropriate electrode materials that can
respectively, widening the application scenario of chloride-based bat accommodate Cl− anions. In this section, we review research progress on
teries [23,24]. The concept of DIBs has been applied to chloride-based the important components of chloride-based RCBs, including cathode
systems since 2015, and Dai et al. reported a new type of rechargeable materials, anodes, and electrolytes. Table 1 and Fig. S1 summarizes and
Al-graphite battery [25]. The reaction mechanism involves the compares the electrochemical performances of the reported chloride-
intercalation/de-intercalation of chloroaluminate anions (AlCl-4) in the based rocking-chair batteries.
graphite cathode and the electrochemical deposition/dissolution of Al at
the anode. Thereafter, DIBs based on Cl-containing dual-halogen and 2.1. Cathode materials
single Cl ions as charge carriers were first realized in 2019 and 2020,
respectively [26,27]. Ji et al. introduced another novel concept, of One of the major challenges for the development of chloride-based
reverse DIBs in 2019 [28]. Although both anions and cations participate RCBs is the cathode material. To date, only limited materials have
in the electrochemical process, they are each stored at the anode and been exploited as feasible Cl ion host materials, including metal chlo
cathode sides, respectively. More recently, other emerging rides, metal oxychlorides, layered double hydroxides (LDH), and
chloride-based systems have been developed, such as alkali-metal/Cl2 organic polymers. Metal chlorides and oxychlorides as traditional elec
batteries (2021) [29] and chlorine flow batteries (2022) [30], which trode materials generally suffer from large volume change caused by the
have significantly enriched the scope of rechargeable chloride-based conversion reaction. Therefore, intercalation-type electrodes (e.g.,
batteries. LDHs, polymers) as Cl ion hosts with good stability has spurred
In this review, we provide an overview of state-of-the-art de increased interests in recent years. The structural features and electro
velopments in rechargeable chloride-based batteries, including chloride- chemical properties of these materials will be discussed as follows.
based RCBs and DIBs systems, as well as other emerging Cl-based bat
teries. The major achievements of the individual technologies are briefly 2.1.1. Metal chlorides and oxychlorides
summarized in each section, with consideration from the fundamental The first demonstration of rechargeable chloride-based RCBs was
mechanism to electrode materials. Finally, based on our understanding, achieved in 2013 by Fichtner et al. using metal chlorides (CoCl2, VCl3,
the current challenges and potential future directions of this burgeoning and BiCl3) and Li metal as the cathode and anode, respectively [15]. The
battery technology are presented. We anticipate that this review offers ionic liquid, consisting of 1-methyl-3-octylimidazolium chloride
key insights into the future development of rechargeable chloride-based ([OMIM][Cl]) and 1-butyl-3-methylimidazolium tetrafluoroborate
batteries. ([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.
2
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.
3
higher oxidation state of CuCl2 can be formed during the charging like layers and weakly bound charge-balancing interlayer anions [61,
process by the oxidation of CuCl, the CuCl/Li battery delivered an initial 62]. Because of the large interlayer gallery and high exchangeability of
capacity of 278 mAh g-1 at 5 mA g-1 and retained 70 mAh g-1 even after interlayer anions, LDHs can provide open 2D channels for anion trans
100 cycles. port. In 2019, Han et al. [46] designed a CoFe-LDH with Cl− in the
Compared to metal chlorides, higher chemical stability can be interlayer and first explored its potential application in chloride-ion
generally realized in metal oxychlorides (e.g., VOCl, BiOCl, FeOCl, and batteries (Fig. 3a). Theoretical calculations suggest that CoFe-Cl LDH
WOCl4) due to the strong bonding of metal cations with the Lewis basic has a favorable chloride ion diffusion path with a diffusion energy
O2- anions, which can alleviate the dissolution of the cathode material. barrier of only 0.12–0.25 eV (Fig. 3b), which is attributed to its large
Fichtner et al. were the first to demonstrate the reversible storage of interlayer spacing and open 2D channels. Consequently, the CoFe-Cl
chloride ions in BiOCl and FeOCl [35]. The initial discharge capacities LDH||Li metal cells delivered a large specific capacity of 239 mAh g-1,
achieved for BiOCl and FeOCl cathode were 60 and 158 mAh g-1, exceeding most of the previously reported metal chlorides and oxy
respectively, approaching 60 % of the theoretical capacity (Fig. 2a–b). chlorides (Fig. 3c). Unfortunately, the capacity declined rapidly during
The chloride ion storage in BiOCl/FeOCl proceeds mainly via a revers the subsequent 100 cycles. The author suggests that this may be due to
ible conversion reaction. During the discharge process, the dein local structural distortions or partial dissolution of Co from the LDH
tercalation of Cl− from the metal oxychloride cathode occurs platelets. To address this issue, trimetallic Ni2V0.9Al0.1-Cl LDH with
simultaneously with the rapid transformation to amorphous metal ox enhanced structural stability was synthesized via the hydrothermal
ides, that is, Bi2O3 and FeO. The cathode restores chloride ions to form method [47]. The crystal structure of the Ni2V0.9Al0.1 layer consists of
metal oxychlorides during the subsequent charging process. Another NiO6 and VO6 octahedra connected by shared edges, in which V ions in
metal oxychloride explored for chloride-based RCBs is VOCl. Fichtner et the octahedral centers are partly substituted by Al ions (Fig. 3d). The
al [42]. prepared a solution of 0.5 M 1-butyl-1-methylpiperidinium introduction of inactive Al ions effectively inhibits the structural
chloride (PP14Cl) in propylene carbonate (PC) as a new electrolyte, distortion, thus improving the structural stability and promoting reac
which possessed a high ionic conductivity of 4.4 × 10-3 S cm-1 and wide tion kinetics. Under the potential window of 1.2–3.0 V, a remarkable
electrochemical stability window of up to 3.2 V versus Li. Comprehen specific capacity of 312.2 mAh g-1 was achieved in Ni2V0.9Al0.1-Cl LDH
sive characterizations confirmed that VOCl experiences interlayer electrode, more importantly, maintaining an ultralong lifetime of over
expansion during the initial discharge due to the irreversibly interca 1000 cycles (Fig. 3e). Moreover, the diffusion coefficient of Cl− esti
lated PP+ 14 ions. Chloride ions can be intercalated and deintercalated mated by the galvanostatic intermittent titration technique (GITT)
more easily because intercalated PP+ 14 acts as a pillar and maintains wide indicated that the Al-doped Ni2V0.9Al0.1-Cl LDH had a considerably
interlayer channels. In comparison to BiOCl and FeOCl, VOCl can ach higher value than the Al-free Ni2V-Cl LDH electrode.
ieve a higher capacity of 189 mAh g-1 with superior reversibility Inspired by previous work, Han et al. prepared other types of LDH
(Fig. 2c). Recently, Fichtner et al [45]. reported a new metal oxy with various chemical compositions, such as CoNi-X (X = F, Cl, Br) [48],
chloride, WOCl4 as the cathode material for chloride-based RCBs. The NiFe-Cl [49], and NiMn-Cl LDH [50]. They found that reversible shuttles
characterization results confirmed that WOCl4 underwent a conversion of halide ions (F− , Cl− , and Br− ) can be realized in CoNi LDH, demon
reaction upon discharging, with the formation of WO3 and WClx (x = 4, strating their potential for application to halogen-ion batteries (Fig. 3f).
5, 6) as discharge products. Thus, fast capacity fading was observed As a proof-of-concept, the first rechargeable bromide-ion batteries was
during 50 cycles owing to the large volume changes resulting from the prepared based on a CoNi-Br LDH cathode and metallic lithium anode,
conversion reaction. which presented a large specific capacity of 339 mAh g-1 and over 50
To further improve the electrochemical performance of metal oxy cycles. Similarly, the CoNi-F||Li and CoNi-Cl||Li cells show maximum
chlorides, researchers have made great efforts, including nanoconfine specific capacity of 113 and 186 mAh g-1, respectively. Ex situ analysis
ment, conductive polymer coating, and compositing with a carbon by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and
matrix. For instance, Shen et al [38]. synthesized a FeOCl/CMK-3 energy-dispersive X-ray spectroscopy (EDS) revealed the reversible
composite as cathode for chloride-based RCBs via a nanoconfined intercalation/deintercalation of halogen ions into/from CoNi-X LDH,
strategy (Fig. 2d). Benefiting from the confined effect of CMK-3 to accompanied by a valence change of Co3+/Co2+ and Ni3+/Ni2+.
provide enhanced electrical conductivity and structural integrity, the Although LDH have great potential for application in chloride ion bat
FeOCl/CMK-3 cathode displayed significantly improved cycling stability teries, the intrinsic limitation derived from the poor electrical conduc
compared to pure FeOCl and a simple composite with carbon black tivity and unavoidable self-aggregation hampers their electrochemical
(Fig. 2e). Other carbon-based composite methods, including mechanical activity. Such problems can be mitigated by constructing an integrated
milling with carbon nanotubes and designing graphene aerogel struc hierarchical architecture. Luo et al [50]. successfully realized a hierar
tures, have also been used for metal oxychlorides (FeOCl and Sb4O5Cl2), chical NiMn-Cl LDH/carbon nanotube (CNT) network via an in situ
but the performance improvement has not been satisfactory [39,44]. co-precipitation method (Fig. 3 g). Representative scanning electron
Recently, conductive polymers have been investigated as coating layers microscope (SEM) images revealed uniform growth of NiMn-LDH
for metal oxychlorides [41]. The introduction of polypyrrole (PPy) nanosheets on the CNT skeleton, featuring an obvious porous structure
increased the electrical contact, chloride ion diffusion, and structural (Fig. 3h). The enhanced electrical conductivity combined with a large
stability of the FeOCl electrodes, which ultimately contributed to the specific surface area facilitated fast ion/electron transport in NiMn-Cl
better cycling stability of FeOCl@PPy (82.9 %) over that of pristine LDH/CNT, thereby exhibiting a better rate performance than that of
FeOCl (13.2 %) after 30 cycles. pure NiMn-Cl LDH.
In summary, metal chlorides and oxychlorides cathodes face signif Compared with metal chlorides and oxychlorides, LDHs as cathodes
icant challenges associated with large volumetric change and severe for chloride-based RCBs presents a significant enhancement in reversible
dissolution in the electrolytes, leading to rapid capacity fade and limited capacity and cycling stability because of their inherent stable 2D
operational lifetime. To address these issues, both the nanostructured transport channels. To further improve the performance of LDHs ma
electrode design and the stabilization of the electrode/electrolyte terials, future research should focus on enhancing its electrical con
interface through surface coating and/or electrolyte optimization ductivity, such as design of novel composites with conductive materials,
should be implemented. and introduction of defects or heteroatom. Besides, more in-depth study
of the underlying intercalation mechanisms is necessary.
2.1.2. Layered double hydroxides
As a class of typical layered materials, layered double hydroxides 2.1.3. Organic materials
(LDHs) are composed of alternately stacked, positively charged brucite- Organic materials are potentially excellent cathode candidates for
4
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 FeOCl using an in situ intercalation/polymerization strategy [40]. The
mental friendliness, and more importantly, limited solubility in elec embedded large-sized PANI significantly enlarged the interlayer dis
trolytes, mitigating the dissolution issue faced by other materials [63]. tance of FeOCl from 0.79 to 1.4 nm while forming a cleaved lamellar
Some typical conductive polymers have been developed as electrode morphology (Fig. 4d–e), thus promoting chloride ion transport and
materials for Li-, Na-, K-, Mg-, Zn-, and Al-ion batteries, for example, restricting the volume expansion upon cycling. As a consequence, the
polypyrrole (PPy) and polyaniline (PANI) [64–66]. In 2017, the FeOCl/PANI cathode demonstrated a reversible capacity of 120 mAh g-1
chloride-ion-doped polypyrrole (PPyCl) material used as the cathode for at 10 mA g-1 after 50 cycles, which is twice as high as that of pristine
chloride-based RCBs was firstly reported by Zhao et al. [51]. Taking FeOCl (Fig. 4f–g).
carbon nanotubes (CNTs) as the skeleton, PPyCl was uniformly coated Previously reported polymers, including PPy and PANI, use nitrogen
on the surface of the CNTs to form PPyCl@CNTs by in situ chemical as the redox center and exhibit high chemical stability. However, the
oxidative polymerization. SEM and transmission electron microscopy reversible capacity is still quite low owing to insufficient nitrogen active
(TEM) revealed that the PPyCl@CNTs had a nanotube morphology with sites. Polymerized polyxylylviologen chloride (PXVCl2) with fully active
a distinct hierarchical structure (Fig. 4a). When paired with a metallic nitrogen sites was first developed as electrode material for chloride
lithium anode, the PPyCl/Li system delivered a specific capacity of 118 batteries [53]. By introducing graphene into the PXVCl2 matrix, the
mAh g-1 and almost remain unchanged after 40 cycles (Fig. 4b). The PXVCl2/graphene composite electrodes exhibited a reversible capacity
as-assembled soft-packing battery could light up a light-emitting diode of 175 mAh g-1, which is higher than other previously reported
(LED) for more than five minutes, demonstrating their potential for conductive polymer electrodes.
practical applications. XPS spectra confirmed that the N+ species (C− N+ Overall, organic polymers are promising cathode materials for
and C– – N+) in PPyCl underwent oxidation and reduction reactions chloride-based RCBs due to their structural tunability and stability.
caused by chloride ion intercalation/deintercalation during cycling However, low theoretical capacity will likely limit their practical ap
(Fig. 4c). plications. A combination of organic cathodes with inorganic cathodes,
In addition, conductive polymers can be used as intercalated species to achieve a balance between capacity and cycling stability, could be a
for inorganic layered materials to improve their conductivity and elec potential research direction for the future development of chloride-
trochemical performance. For instance, PANI can be incorporated into based RCBs.
5
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 and aqueous. Non-aqueous, organic solvent-based liquid electrolytes

are the main choice for chloride-based batteries, particularly room-
Most of the currently reported non-aqueous chloride batteries temperature ionic liquids (ILs), which are currently the most
employ lithium metal as the anode because of its high reduction po commonly used electrolytes because of their low or no vapor pressure
tential and easy reaction with chloride ions during cycling. Replacing and wide electrochemical windows. An earlier study by Zhao et al. [15]
lithium with other earth-abundant metals, such as Na, K, Zn, Mg, and Al, reported a binary ionic liquid consisting of 1-butyl-3-methylimidazo
as anodes will significantly reduces the production cost of batteries. lium tetrafluoroborate ([BMIM][BF4]) and 1-methyl-3-octylimidazo
Among them, multivalent metals are particularly interesting because lium chloride ([OMIM][Cl]) in a ratio of 3:1 as the electrolyte. This
they can provide multielectron redox reactions, which potentially result electrolyte exhibits a high ionic conductivity of 9.1 × 10-4 S cm-1 at
in higher specific capacities and energy densities. Zhao et al. first 298 K. Following this study, they developed two electrolytes, 0.5 M
demonstrated a chloride-ion battery using Mg metal as the anode [36]. benzyldimethyltetradecylammonium chloride (N116(14)Cl) in bis(tri
Considering that the decomposition of the electrolyte on the pure Mg fluoromethylsulfonyl)imide (N1114TFSI) and 0.5 M 1-butyl-1-methylpi
anode surface may inhibit Cl− ion transfer and block reversible Mg peridinium chloride (PP14Cl) in 1-butyl-1-methylpiperidinium bis
plating/stripping, they prepared an Mg/C composite as anode by two (trifluoromethylsulfonyl)imide (PP14TFSI) [35], where the ionic con
methods: ball milling of mixed Mg and carbon black powders and ductivity was measured to be 7.3 × 10-4 and 6.1 × 10-4 S cm-1, respec
thermally decomposing a MgH2/C composite. When FeOCl (or BiOCl) is tively, at 298 K. More importantly, the immersion test conducted by the
used as the cathode, the full FeOCl/Mg (or BiOCl/Mg) batteries deliv researchers proves that the cathode material can remain stable in the
ered maximum specific capacities of 130 (or 102) mAh g-1. Unfortu electrolyte for more than two months, indicating that the ionic liquid
nately, because the large volume change of Mg disrupts the electrical electrolytes do not react with the cathode. To further enhance the ionic
contact with carbon black, these battery systems suffer from rapid ca conductivity of non-aqueous electrolytes, some research groups have
pacity decay upon cycling. Gao et al. [43] prepared an anode comprised attempted to incorporate low-viscosity carbonate solvents (e.g., pro
of a MgCl2/Mg/C composite using a similar ball-milling method. pylene carbonate (PC)) into ionic liquids or to directly replace ionic
Although the capacity retention is obviously improved compared to that liquids with carbonate solvents [42–44,48–50]. These strategies have
of the Mg/C composite, the capacity of the MgCl2/Mg/C composite is proven effective in improving the ion storage performance and stability
still unsatisfactory for practical applications. Another bivalent metal, of cathode materials. Although significant progress has been made in
zinc, has also been reported as an anode in chloride-ion batteries. non-aqueous electrolytes, many questions remain unresolved, such as
Gschwind et al. [54] constructed a room-temperature solid-state those related to ionic conductivity, viscosity, and compatibility.
chloride-ion battery composed of CuCl2/C or PNAI as the cathode ma Compared to flammable, non-aqueous electrolytes, rechargeable
terial, Zn as the anode, and chloride-conducting polymer electrolytes. chloride-based batteries employing aqueous electrolytes are intrinsi
However, the results are preliminary, and only the first discharge curves cally safe, environmentally benign, and cost-effective. However,
are shown. The development of other non-lithium metals as anodes for aqueous chloride-based RCBs have not been reported until recently, due
chloride-ion batteries remains a significant challenge. to the lack of stable electrode materials to achieve reversible Cl− storage.
The first aqueous rechargeable chloride-based RCBs was demonstrated
2.3. Electrolytes 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
2.3.1. Liquid electrolytes charging, the Cl− ions are extracted from the BiOCl anode, transported
Liquid electrolytes can be divided into two categories: non-aqueous through the aqueous NaCl electrolyte, and eventually reacted with the
6
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 chloride-based RCBs by introducing ammonia chloride (NH4Cl) into the
charging. The cyclic voltammetric (CV) curves of BiOCl/Ag battery aqueous NaCl electrolyte as an additive [55]. Due to the dissociation of
shows a pair of redox peaks appeared at 0.84/0.41 V after the second ammonium ions (NH+ 4 ) in the aqueous electrolyte, producing ammonia
cycle (Fig. 5b), attributed to the reversible Cl− insertion/extraction be (NH3) and protons (H+), AgCl reacted with NH3 to form an Ag(NH3)+ 2
tween the cathode and anode. This new battery system delivered a intermediate phase, facilitating the AgCl/Ag conversion reaction at the
reversible specific capacity of 92.1 mAh g-1 with a Coulombic efficiency cathode. The H+ ions produced from the dissociation of NH+ 4 can func
(CE) of ~100 % at 400 mA g-1 (Fig. 5c), which is comparable to other tion as oxygen acceptors to promote the valence state transfer of
aqueous Li- or Na-ion batteries. Similar to BiOCl, Sb4O5Cl2 has also been Bi3+/Bi0 at the anode side. Clearly, with a small amount of NH4Cl in the
applied in aqueous chloride-based RCBs with a 1 M NaCl solution as the NaCl electrolyte, the cycling stability of the BiOCl/Ag battery was
electrolyte, but its specific discharge capacity is merely 34.6 mAh g-1 improved compared with that of the pure NaCl electrolyte (Fig. 5d).
[56]. Recently, Lu et al. proposed an interesting electrolyte regulation Although rechargeable aqueous chloride-based RCBs have been
strategy for improving the reaction kinetics of both electrodes in achieved using a NaCl solution as the electrolyte, their energy density is
7
still relatively low due to a narrow voltage window. High-concentration stability and thermal stability also must be resolved before inorganic
‘‘water-in-salt” type electrolyte has been successfully used in the fabri SSEs can be used in chloride-based RCBs. Early explorations have shown
cation of high-energy aqueous Li/Na/Zn/Al batteries [67–70]. that some inorganic chlorides such as BaCl2, SrCl2, LaCl3, and LaOCl can
Hydrogen evolution can be effectively inhibited in such electrolytes act as chloride ion conductors [72–74], but high operating temperatures
because of the absence of free water molecules, thus resulting in a wider (> 200 ℃) limit their practical use. Recently, Okada et al. [34] first
potential window. The concept of ‘‘water-in-salt’’ electrolyte was first reported KCl-doped PbCl2, that is, Pb1-xKxCl2-x (x = 0.01, 0.02, 0.03), as
employed in chloride-based RCBs by Li et al. [59]. Tetramethylammo a solid electrolyte, achieving a high ionic conductivity of ~10-4 S cm-1 at
nium chloride (CH3)4NCl was selected as the electrolyte salt due to its room temperature. Because no cathode dissolution occurred in the solid
high solubility at room temperature and good stability against hydro electrolytes, the assembled BiCl3/Pb cell delivered a maximum specific
lysis. When the concentration of (CH3)4NCl electrolyte increased from 1 capacity of 187 mAh g-1 at a rate of 0.042 C and retained 85 % of its
to 25 mol kg− 1 (m), a wider electrochemical stability window of 3.10 V original capacity after 30 cycles. Unfortunately, the energy density of
was realized (Fig. 5e). Spectral analysis and the theoretical model reveal the battery may be limited by its narrow electrochemical stability win
that the destruction of hydrogen bonds between water molecules is dow (0.2–0.8 V). Further development of solid electrolytes with wider
aggravated due to the increase in electrolyte concentration. As a result, electrochemical windows is necessary. To this end, a room-temperature
the reactivity of free water molecules is significantly reduced and, thus, stable inorganic halide perovskite of CsSnCl3 as solid electrolyte with a
widening the electrochemical stability window. In a saturated wider electrochemical window (~ 6.1 V) was successfully prepared via
(CH3)4NCl electrolyte, the assembled chloride batteries using the gra mechanical milling and subsequent heat treatment (Fig. 5i) [75].
phene cathode and a Zn metal anode could achieve a high reversible Benefiting from the rich nanograins and tin vacancy, the cubic CsSnCl3
capacity of 136 mAh g-1 and a specific energy of 252 Wh kg-1. Addi electrolyte remained highly stable with no phase transformation to the
tionally, an impressive cycle life (>2000 cycles) was obtained, repre monoclinic phase for more than three months. DFT calculations revealed
senting the most stable cycling performance for aqueous chloride-based that the Cl− ion migration energy in cubic CsSnCl3 is 0.20 eV (Fig. 5j),
RCBs. 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)
2.3.2. Solid-state electrolytes was significantly improved compared to that of monoclinic CsSnCl3
Although liquid electrolytes offer the benefits of high conductivity (10-10–10-9 S cm-1) based on electrochemical impedance spectroscopy
and excellent wetting of the electrode surfaces, there are still challenges (EIS) measurements.
related to their use in chloride-based RCBs due to unavoidable electrode
dissolution and probable side reactions with the electrode. In addition, 3. Chloride-based dual-ion batteries
increasing the concentration of Cl− ions in the electrolyte increases the
likelihood of chlorine gas production. These issues can be effectively In conventional “rocking-chair” cells, such as alkali-metal lithium or
addressed by using solid-state electrolytes (SSEs). Current SSEs are sodium ion batteries, the cationic charge carriers (i.e., Li+, or Na+)
classified into two major categories: organic polymers and inorganic migrate between the cathode and anode during the charge/discharge
solid electrolytes. Compared to inorganic SSEs, organic polymer elec process. In DIBs, both anions and cations are participated in the elec
trolytes exhibit better flexibility, lower interfacial contact resistance trochemical reactions. Anion intercalation can occur on the cathode side
with electrodes, and easy processing [71]. The common polymer matrix under a high operating potential, which is beneficial for the battery to
for SSEs including polyethylene oxide (PEO), polyvinyl alcohol (PVA), achieve a higher energy density [76]. A variety of anions have been
polyvinylchloride (PVC), polymethyl methacrylate (PMMA), and poly reported for reversible storage in DIBs [77,78], such as hexa
vinylidene fluoride (PVDF), etc. The feasibility of the chloride-based fluorophosphate (PF-6), tetrafluoroborate (BF-4), perchlorate (ClO-4), bis
RCBs using polymer as the electrolytes was firstly demonstrated by (fluorosulfonyl) imide (FSI-), trifluoromethanesulfonic (CF3SO-3), bis
Gschwind et al. [54]. Three polymers, gelatin, polyvinylchloride (PVC), (trifluoromethanesulfonyl) imide (TFSI-), and difluoro (oxalate) borate
and polyvinyldifluoride-hexafluoropolymer (PVDF-HF), were mixed (DFOB-). Recently, DIBs based on different chloride-based anion car
with chloride-containing salts to form chloride-conducting membranes. riers, including single-chloride ions, dual-halogens, and superhalides,
The assembled PANI||Zn and CuCl2/C||Zn batteries achieved initial have also been reported [79]. In this section, we discuss recent progress
capacities of 160 and 130 mAh g-1, respectively, in PVDF-HF based in electrode materials and their working mechanisms for DIBs based on
membrane electrolytes. However, the reversibility of these systems re chloride-based anion storage.
mains uncertain. Other chloride-ion-conducting polymer membranes
have also been reported in recent years, including polyethylene oxide 3.1. Single chloride-ion storage
(PEO)-tributylmethylammonium chloride (TBMACl)-succinonitrile (SN)
[24], polymethyl methacrylate (PMMA)-1-butyl-1-methylpiperidinium To date, most DIBs have operated in nonaqueous electrolytes. Ji et al.
chloride (PP14Cl)-1-butyl-1-methylpiperidinium bis(trifluoromethyl [27] reported a novel aqueous DIBs, that employed Mn3O4 as cathode
sulfonyl)imide (PP14TFSI) [37], polydiallyl dimethylammonium chlo materials, Zn metal as the anode, in addition to 20 M ZnCl2 plus 5 M
ride (PDDAC)-polyethylene glycol (PEG) [32], and tetramethylammo NH4Cl as the electrolyte. The cell chemistry involves the
nium chloride ((CH3)4NCl)-polyvinyl alcohol (PVA) [60], all of which intercalation/de-intercalation of Cl− into/from the Mn3O4 and the
exhibit good chloride ion conductivity and flexibility. For example, Zhao plating/stripping of Zn2+ on the Zn metal. The typical galvanostatic
et al. [24] constructed a PEO-TBMACl-SN solid polymer electrolyte profile of Mn3O4 demonstrates a low initial discharge capacity of 48
composed of PEO as the polymer matrix, TBMACl as the chloride salt, mAh g-1 (Fig. 6a), which was attributed to the irreversible reductive
and SN as the solid plasticizer. This polymer membrane possessed high insertion of Zn2+ into Mn3O4 to form Zn0.2Mn3O4. Because Zn2+ and Cl−
mechanical flexibility against bending (Fig. 5f), as well as a high ionic are counter ions, the pre-intercalated Zn2+ further facilitates the
conductivity above 10-5 S cm-1. In addition, the wide voltage window (> reversible storage of Cl− . This phenomenon can be defined as the
4.24 V vs. Li/Li+) ensured deep charging and discharging of the elec counter-ion insertion mechanism. New compounds of AyMOxBz can be
trodes, thereby leading to a large reversible capacity of 110 mAh g-1 for obtained as chloride-hosting electrodes by this generic methodology, for
FeOCl/Li batteries (Fig. 5g–h). example, Zn0.2Mn3O4Cl1.7 featured in this study (Fig. 6b). Therefore, a
Inorganic SSEs generally exhibit a relatively wide electrochemical Cl− storage capacity reaching up to 200 mAh g-1 in subsequent cycles.
stability window, which allows batteries to operate over a wide poten The electrochemical quartz crystal microbalance (EQCM) results
tial. Nevertheless, their intrinsic roughness and rigidity inevitably result coupled with cyclic voltammetry revealed a slight mass change rate of
in poor interfacial contact with the electrode. The issues of chemical ~35 g/mole e- during electrochemical cycling, confirming that chloride
8
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). nitrogen sites, m-PTPA possessed a higher Cl− storage number compared
Except for inorganic oxides, other anion hosting materials such as to nonporous conjugated polytriphenylamine (PTPA). Thus, the result
organic materials have also been studied in the chloride-based DIBs ing DIBs showed a significant increase in specific capacity from 99.8 to
system. Liu et al. [80] investigated the feasibility of using a poriferous 210.7 mAh g-1, corresponding to 39.4 % and 83.2 % accessibility effi
polytriphenylamine conjugated microporous polymer (m-PTPA) as cacy of active sites for PTPA and m-PTPA cathode, respectively
cathode for aqueous DIBs with attractive energy density (236 Wh kg-1) (Fig. 6e–f).
and peak power density (6.8 kW kg-1). Density functional theory (DFT)
calculations combined with Fourier transform-infrared spectroscopy
3.2. Dual-halogen storage
(FT-IR) proved that the N atoms in the amine/imine group were
redox-active sites for chemical interaction with Cl− anions (Fig. 6d).
In addition to single Cl ions, some dual-halogen species, such as Br-Cl
Thanks to their unique porous structure enables the exposure of active
and I-Cl, have also been investigated in DIBs. This novel dual-halogen
9
storage chemistry results in a higher operating voltage and reversible chloroaluminate anions (AlCl−4 ) in the graphite cathode and the strip
capacity, thereby significantly improving the cell energy density. ping/plating of aluminum at the anode (Fig. 7a). During the discharging
Recently, Yang et al. proposed a unique halogen conversion- process, Al dissolves from the metal anode to form AlCl−4 and Al2Cl−7
intercalation chemistry that integrates the merits of conversion re species, and then, an intercalation reaction of AlCl−4 occurs in the
actions (high energy) and intercalation reactions (high reversibility) graphite. The constructed Al/PG cells exhibited a specific capacity of
[26]. A highly concentrated water-in-bisalt (WiBS) electrolyte expands approximately 65 mAh g-1 under a current rate of 66 mA g-1 (Fig. 7b).
the electrochemical window to ~4.9 V versus Li/Li+, realizing the high Two distinctive plateaus regions of 2.25–2.0 V and 1.9–1.5 V were
reversibility of halide oxidation/reduction at high potentials. For the found in the discharge process, corresponding to the anion intercalation
graphite cathode, the reversible electrochemical behavior was based on stage of graphite. Considering that the open frame structure may facil
a two-step redox reaction involving both Br− and Cl− . As shown in itate the intercalation of AlCl−4 anions, the author prepared a
Fig. 6g, upon charging from 4.0 to 4.2 V, Br− was first oxidized to atomic three-dimensional graphitic foam as a cathode by chemical vapour
bromine (Br0) with oxidation state of near zero, and subsequently deposition. Compared to PG, the constructed Al/graphitic foam cells
inserted into graphite, forming the Cn[Br] compound. Upon further could be achieve faster charging rate of up to 75 C, and no evidence of
charging to 4.5 V, the Cl− also underwent oxidation to a near-zero state capacity fading was found after 7500 cycles (Fig. 7c–d). Chlor
(Cl0) and then combined with Cn[Br], resulting in the formation of oaluminate anion intercalation was confirmed by XPS, in situ Raman
intercalation compound Cn[BrCl]. The opposite reaction occurred dur spectroscopy, and Auger electron spectroscopy (AES). Since this work,
ing the discharge process, in which Cl0 and Br0 were successively various carbon-based materials, including natural graphite, graphene,
extracted from the graphite host and reduced to halides. The corre and MOF-derived carbon, have been widely used as alternative cathodes
sponding CV curve exhibits two pairs of redox peaks at 4.0–4.2 V and for aluminum batteries based on AlCl−4 storage mechanisms [85–87].
4.2–4.5 V, demonstrating a two-step conversion-intercalation reaction Unlike Al-based DIBs, which use an ionic liquid as the electrolyte,
mechanism associated with Br− and Cl− (Fig. 6 h). Similar electro other reported DIBs based on superhalides as charge carriers employ
chemical behavior was observed in the galvanostatic curves, with two aqueous electrolytes. Ji et al. developed a highly concentrated water-in-
pairs of well-defined sloping plateaus (Fig. 6i). The graphite cathode salt electrolyte based on inexpensive ZnCl2 [83]. When the concentra
delivered a high reversible capacity of 243 mAh g-1 with nearly 100 % tion of ZnCl2 was increased from 5 to 30 m, the parasitic hydrogen
CE, confirming the high reversibility of the graphite for dual-halogen evolution reaction (HER) and oxygen evolution reaction (OER) were
storage. effectively suppressed, and a new ionic species of [ZnClx]2− x appeared.
The Br-Cl dual-halogen storage chemistry has also been extended to Pairing the nitrogen-doped graphene cathode with a Zn metal anode,
aqueous zinc-based battery systems [81]. Conventional zinc-ion and author demonstrated a new aqueous Zn-based DIBs with [ZnClx]2− x as
dual-ion batteries usually suffer from drawbacks of low working voltage charge carriers. The 3D porous structure of the carbon cathode and high
and limited capacity, respectively. By employing dual-halogen redox concentration electrolytes enabled reversibly storage of [ZnClx]2− x
couples (Br0/Br− and Cl0/Cl− ) at the graphite cathode with a molten through electrical double layer adsorption and ion insertion at a high
hydrate electrolyte, the designed zinc dual-halogen battery exhibited a working potential (1.95 V versus Zn) (Fig. 8a–b). In addition, the battery
significantly increased discharge capacity (257 mAh g-1) and operation retained a reversible capacity of ~80 mAh g-1 after 800 cycles,
potential (1.71 V) compared with single-halogen batteries based solely demonstrating an excellent cycling stability (Fig. 8c). Using [ZnCl4]2- as
on Br0/Br− (78 mAh g-1/1.60 V, Fig. 6j). The authors found that it was anionic charge carriers, the same group reported another storage system
difficult to insert chloride ions into graphite directly, whereas bromine defined as reverse dual-ion batteries (RDIBs) [28], which share similar
ions could function as chemical mediators to bring chloride into the operating mechanisms with DIBs, whereas storage ions on opposite
graphite interlayer. As depicted in Fig. 6k, the graphite cathode electrodes. During the discharging process, [ZnCl4]2- and Zn2+ were
exhibited completely different electrochemical behaviors in ZnCl2 inserted into the ferrocene anode and the Prussian blue cathode,
electrolytes with and without additional KBr salt. Two pairs of redox respectively (Fig. 8d). Conversely, [ZnCl4]2- anions and Zn2+ cations
peaks were identified in cyclic voltammograms of the ZnCl2⋅(0.03KBr)⋅ were simultaneously extracted from the electrodes upon charging.
2 H2O electrolyte, which were ascribed to the reversible formation of Interestingly, when the concentration of ZnCl2 was increased to 30 m,
graphite-halogen compounds (C[BrmCln]). In contrast, no obvious redox the cation insertion potential at the cathode increased, while the anion
peaks were observed in the ZnCl2⋅2H2O electrolyte, suggesting the insertion potential at the anode decreased, thereby widening the po
important role of bromine in the electrochemical reactions. Inspired by tential gap between the two electrodes (Fig. 8e). Unfortunately, RDIBs
this research, Guo et al. found that iodine played a similar mediator role only deliver a low specific capacity of ~30 mAh g-1 based on the total
to bromide, enabling the storage of chlorine in the carbon cathode by active mass of both the cathode and anode, and further investigation is
forming interhalogen [ICl2]− species [82]. Because the chlorine or ox required to optimize the performance of this novel system.
ygen evolution reaction could be effectively suppressed in a new Mg-Cl superhalides can be reversibly intercalated into graphite,
aqueous deep eutectic solvent (DES) gel electrolyte composed of 30 m which was first confirmed by Kim et al. [84]. The results of stimulated
ZnCl2, 120 m choline chloride (ChCl), and 5 m KI, DIBs based on the Raman spectroscopy indicated that Mg2+ cations are preferentially co
graphenic carbon cathode delivered a record-high reversible capacity of ordinated by Cl− to form Mg-Cl superhalides, that is, [MgCl4]2− and
up to 1100 mAh g-1. Such a conversion-intercalation mechanism rep [MgCl3(OH2)]− , in an aqueous DES electrolyte composed of 9 m MgCl2
resents a new approach for designing high-energy rechargeable and 30 m choline chloride (ChCl). Although a high initial capacity of
batteries. 150 mAh g-1 was achieved in these electrolytes, the graphite electrode
exhibited rapid capacity fading after 25 cycles. The authors ascribed this
3.3. Superhalides storage Mg-Cl superhalide storage process to graphite being partially turbos
tratic rather than a homogeneous intercalation reaction, which was
Superhalides, such as PF−6 , BF−4 , and TFSI− have received the most confirmed by ex situ XRD, Raman spectroscopy, and high-resolution
attention for DIBs in the past ten years [77]. Recently, Cl-containing transmission electron microscopy (HRTEM). Inspired by previous
metal-based superhalides, including Al-Cl, Zn-Cl, and Mg-Cl super work, a lighter and smaller superhalide of [LiCl2]− was verified in a DES
halides, have been investigated as anionic charge carriers for DIBs [25, electrolyte composed of 20 m LiCl and 20 m ChCl [88]. Because the
83,84]. A typical example is Al-Cl superhalides, that is, chloroaluminate. strong coordination of water molecules with the strong Lewis acid of Li+
Dai’s group proposed the first Al/graphite battery employing metallic Al in aqueous electrolytes, trace water molecules will inevitably coin
anode and pyrolytic graphite (PG) or graphitic foam as the cathode [25]. tercalate with [LiCl2]− upon discharging, which results in a significantly
The operating mechanism is based on the insertion/extraction of improved cycling stability, but with a decreased anion intercalation
10
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 batteries are in a dual-ion configuration composed of Na+ and Cl−
drated [LiCl2]− rendered graphite partially turbostratic, similar to the capture electrodes. Fig. 9a–b illustrates the ideal operating principle of
Mg-Cl superhalides. By developing new formulations of “water-in-salt” the desalination battery. When the potential of the Cl− capture electrode
or DES electrolytes, more superhalides are expected to be investigated as was higher than that of the Na+ capture electrode, salt removal
charge carriers for DIBs. accompanied by electrical energy storage occurred upon charging.
These processes are reversed upon discharging, the electrode re
4. Other chloride-based rechargeable batteries generates and accompanied by a release of energy. Therefore, the
development of Na+ and Cl− storage materials is crucial for
4.1. Desalination battery high-performance desalination batteries. Conventional sodium interca
lation materials have been investigated for use in desalination batteries,
Desalination is one of the most promising and effective approaches including NaTi2(PO4)3 [95–97], Na3V2(PO4)3 [98,99], Na0.44MnO2
for addressing the challenge of global freshwater shortage [89]. [100,101], Na1.1V3O7.9 [102], and Cu3[Fe(CN)6]2 [103]. These mate
Tremendous efforts have been devoted to developing efficient desali rials showed high Na+ storage capacity in sodium-ion batteries.
nation technologies in the past decade, for example, thermal desalina Compared with Na+ storage materials, there are extremely limited
tion, reverse osmosis desalination, forward osmosis desalination, and candidates for capturing Cl− , including two conversion-type materials:
capacitive desalination (CDI) [90–92]. Among which, thermal and Ag and Bi. Because these two metals and their chlorinated forms are
reverse osmosis desalination are the most mature technologies at pre stable under saline aqueous conditions, sustainable desalination/sali
sent, accounting for more than 90 % of the global desalination capacity; nation through conversion reactions of Ag/AgCl or Bi/BiOCl in seawater
however, both techniques require considerable energy consumption. is feasible. Ag electrodes were the first used Cl− capture materials in
Although CDI has recently attracted increasing attention owing to its desalination batteries. Following the successful work of Mantia, Chen
low energy consumption and mild operating conditions, its low desali et al. [101] experimentally demonstrated that the reversible reaction of
nation efficiency still hinders its practical implementation [93]. To Ag + Cl− ↔ AgCl + e− occurs during the desalination/salination process.
address these issues, the development of new desalination technologies As shown in Fig. 9c–d, the silver diffraction peaks from the XRD pattern
is required. drastically increased and decreased due to the reversible extrac
In 2012, a “desalination battery” combining the advantages of low tion/recovery of Cl, which agrees with the EDS results. Owing to the
energy consumption and high desalination capacity was first proposed excellent reversibility of the AgCl and Na0.44MnO2 electrodes, this
by Mantia et al. [94]. They employed Na2Mn5O10 and Ag electrodes to desalination system delivered a high salt absorption/desorption capac
capture Na+ and Cl− , respectively, exhibiting a low energy consumption ity of 57.4 mg g-1 for 100 cycles, which is considerably higher than that
of 0.29 Wh L-1 for the removal of 25 % NaCl. Generally, desalination of the traditional CDI deionization system. Subsequent work has
11
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 (Fig. 9e-f), which is nearly three times higher than that of the hybrid
composite with carbon materials. For example, by designing a free capacitive deionization. The electric charge efficiencies for salt
standing AgCl/reduced graphene oxide (rGO) aerogel to add more desorption and absorption were 0.977 and 0.958, respectively. Despite
electron transport channels and enhance the electrical conductivity the reported excellent performance, Bi/BiOCl electrodes for seawater
[99], the desalination capacity of Na3V2(PO4)3/rGO–AgCl/rGO was desalination still have some drawbacks. First, the Cl− and Na+ ions
significantly increased to 107.5 mg g-1. Although Ag has many advan captured are an unbalanced reaction that involves three-electron and
tages as a Cl− capture material, its high cost and large volume expansion one-electron transfer processes, respectively. In addition, the reaction
limit its practical applications. Compared with Ag, Bi is less expensive, kinetics of Bi→BiOCl in neutral solutions are faster than those of BiO
demonstrating the advantages of constructing large-scale desalination Cl→Bi. Further intensive studies of Bi/BiOCl as an electrode material for
cells. Using Bi as Cl− capture electrode for desalination cells was first desalination batteries should focus on increasing its utilization and
realized by Yang and Choi’s group in 2017 [95,100]. The Pourbaix di improving electrode stability.
agram shows that Bi exists in the form of insoluble BiOCl over a wide pH In summary, as a promising desalination technology, desalination
range of 0–10.5, which makes Bi an ideal Cl− ion capture material. In batteries have received wide attention owing to their low energy con
aqueous media, Bi undergoes the following conversion reaction with Cl− sumption and high salt removal capacity. Nevertheless, this technology
to form BiOCl:Bi + Cl− + H2O ↔ BiOCl + 2H+ + 3e− , which corresponds remains in its infancy and is likely to be driven by exploring the novel
to a theoretical capacity of ~279.7 mg g-1. Based on this principle, Chen electrode materials with higher desalination capacities and excellent
et al [100]. proposed a novel deionization system called the flow stabilities. Due to limited space, a more comprehensive introduction to
dual-ion electrochemical deionization. When coupled with Na0.44MnO2, desalinated batteries will not be covered here but can be found in other
the BiOCl-based deionization system delivered a stable and reversible outstanding reviews [90,91].
desalination capacity of 68.5 mg g-1 at a current density of 100 mA g-1
12
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 and AlCl3 salt dissolved in SOCl2 with fluoride-based additives as the
electrolyte (Fig. 10a). In this system, the operating mechanism was
The demand for higher energy densities has been driving the based on the redox reactions of Cl2/Cl− in the aCNS cathode and Na/Na+
development of battery technology in recent decades. As early as the (or Li/Li+) on the metal anode. During the discharge process, NaCl (or
1970 s, the primary lithium-thionyl chloride (Li-SOCl2) battery was LiCl) was deposited on the aCNS cathode, and the SOCl2 reduction re
invented and widely applied [104–106]. This battery is characterized by action occurred to form SO2 and S. The opposite reaction took place
a high discharge capacity of ~2300 mAh g-1 and a high energy density of during the charging process. The deposited NaCl was converted to Na
up to 710 Wh kg-1. However, as these batteries are primary systems, and Cl2, accompanied by oxidation of SOCl2 to form SCl2, S2Cl2, and
recharging after the first discharge is infeasible. Until recently, Dai’s SO2Cl2. As a result, unprecedented high initial capacities of 2810 and
group first developed a rechargeable alkali-metal-Cl2 battery derived 3309 mAh g-1 were achieved for the Na/Cl2 and Li/Cl2 batteries,
from their primary types [29]. This battery employed amorphous carbon respectively (Fig. 10b). When cycling at 100 mA g-1, the Na/Cl2 battery
nanospheres (aCNS) as the cathode, Na metal or Li metal as the anode, delivered a specific cathode capacity of 1800 mAh g-1 for over 15 cycles
13
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 new RFB system employing the highly reversible Cl2/Cl− redox reactions
supply capability of the Na/Cl2 battery, a light-emitting diode (LED) was [30]. Cl2/Cl− redox chemistry offers three distinct advantages: (i)
illuminated under a discharge current of 1563.35 mA g-1 (Fig. 10d). Cl2/Cl− redox couple can provide a high theoretical capacity of 755 mAh
Following this study, the same group developed new graphite positive g-1, which is considerably higher than the VO+ 2 /VO
2+
commonly used in
electrodes for use in Li/Cl2 batteries [107]. Activated by CO2 in a RFB (226 mAh g-1); (ii) the fast single-electron transfer reaction of
high-temperature environment, pristine graphite generated more de Cl2/Cl− makes RFB suitable for high-power applications; and (iii) the
fects, accompanied by an increase of pore volume and specific surface potentially low cost of NaCl as an electrolyte significantly reduces the
area. Consequently, the Li/Cl2 battery delivered a discharge capacity of production cost of RFB. To investigate the Cl2/Cl− redox reaction in the
~1910 mAh g-1 at 50 mA g-1 and remained at 1200 mAh g-1 for more NaCl electrolyte, the authors constructed a concentric cell that
than 35 cycles. Raman spectroscopy in combination with XRD revealed employed RuO2-TiO2 coated porous carbon (RuO2-TiO2@C), activated
the structural evolution of graphite caused by inter carbon, and Ag/AgCl as the working, counter, and reference electrodes,
calation/deintercalation and exfoliation, which creates a capacious, respectively (Fig. 10e). Upon charging, Cl− is oxidized in the working
porelike space for LiCl/Cl2 trapping and reversible redox reactions. electrode to form Cl2 and subsequently is stored in carbon tetrachloride
These works illustrates the attractive application prospects of (CCl4), for which RuO2-TiO2 serve as a catalyst to promote the Cl−
liquid/gas-based materials toward the future rechargeable high-energy oxidation kinetics. Upon discharging, the Cl2 in CCl4 was reduced to Cl−
batteries. 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
4.3. Chlorine flow battery activated carbon counter electrode with NaTi2(PO4)3, a full CFB was
achieved. Benefiting from the membrane-free design and fast reaction
Redox flow batteries (RFB) are critical for large-scale stationary en kinetics, the cell voltage efficiency was calculated as 93.6 % at
ergy storage because of their scalability and flexibility in decoupling 10 mA cm-2 and ~ 77 % at 100 mA cm-2 (Fig. 10g). Thus, the CFB ex
power and energy [108,109]. Currently, RFB can be generally classified hibits a high energy density of 125.7 Wh L-1 with an energy efficiency of
into several types: vanadium-, zinc-, iron-based, etc. However, the >91 % at 10 mA cm-2, which exceeds those of all reported flow batteries
development of these systems has been limited by their high chemical in the past decade. In addition, the battery could provide the peak power
costs and low energy densities. Very recently, Wang’s group reported a
14
density of 325 mW cm-2 at a current density of 350 mA cm-2. Although based battery technologies are still in the preliminary stage. There are
this technology has been considered for future grid-scale energy storage, still several bottlenecks and substantial investigation room for the future
the risk of Cl2 leakage is a major concern. development. We hope that this review offers some insights into future
research on high-performance rechargeable chloride-based batteries
5. Conclusions and perspectives and other anion storage batteries.
Rechargeable chloride-based batteries stand out from a variety of CRediT authorship contribution statement
“post Li-ion” battery technologies for the advantages of resource
affordability and high energy density. Their unique battery chemistry Jinlin Yang: Investigation, Conceptualization, Writing – original
also provides new insights into the exploration of electrode materials draft, Writing – review & editing. Yu Zhang, Guan Wang: Investigation,
and storage mechanisms. In this review, we summarized the latest Visualization. Yuhao Liu, Xiaodong Shi, Hui Zhang: Conceptualiza
research in rechargeable chloride-based batteries, including chloride- tion, Writing – review & editing, Funding Support. Jing Li, Peilin Deng,
based RCBs and DIBs systems, as well as other emerging Cl-based bat Xinlong Tian: Writing – review & editing, Funding Support.
teries. The charge storage mechanism, electrode and electrolyte design
strategies for each technology are fully discussed. Although significant Declaration of Competing Interest
progress has been made in improving the performance of rechargeable
chloride-based batteries, extensive efforts are still required in the The authors declare that they have no known competing financial
following aspects: interests or personal relationships that could have appeared to influence
(1) Chloride-based RCBs share similar working mechanisms with the work reported in this paper.
LIBs, and exploring appropriate electrode materials and optimizing the
electrolyte system are the key to improving electrochemical perfor Data availability
mance. The dissolution of cathode materials in electrolytes and large
volume changes caused by phase transformation are critical issues that Data will be made available on request.
result in poor cycle stability. These issues can be addressed via structural
engineering and/or the development of solid/gel polymer electrolytes. Acknowledgements
Structural engineering is mainly focused on surface coating and
compositing with carbon-based materials or conducting polymers, This work was supported by the Hainan Provincial Natural Science
which have proven effective in enhancing structural integrity. Using Foundation of China (222MS006, 222MS009), National Natural Science
solid/gel polymer electrolytes instead of liquid electrolytes can avoid Foundation of China (22109034, 22109035, 52164028, 62105083,
material dissolution and provide higher safety; however, the matters of 52274297), the Foundation of State Key Laboratory of Marine Resource
low ionic conductivity and poor electrode compatibility should be Utilization in South China Sea (Hainan University, Grant No.
addressed before further research is conducted. MRUKF2021029), and the Start-up Research Foundation of Hainan
(2) Chloride-based DIBs exhibit a different operating mechanism University (KYQD(ZR)-20008, 20082, 20083, 20084, 21065, 21124,
compared to RCBs, which offer higher operating potentials and energy 21125), and the specific research fund of The Innovation Platform for
densities. Previous research has firmly established and demonstrated the Academicians of Hainan Province.
availability and feasibility of Cl-containing species, including single-
chloride ions, dual-halogens, and superhalides, as charge carriers to Appendix A. Supporting information
construct chloride-based DIBs. For metal-based superhalides, there is a
plethora of new research opportunities. By using new formulations of Supplementary data associated with this article can be found in the
“water-in-salt” or deep eutectic solvent electrolytes, many more super online version at doi:10.1016/j.nanoen.2023.108364.
halide charge carriers, except Al-Cl, Zn-Cl, Mg-Cl, and Li-Cl, is expected
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16
Yuhao Liu obtained his Bachelor’s degree from Ludong Uni Hui Zhang is a professor in Hainan University in China. Prior
versity of Physics and Optical Engineering in 2012/06. From to her current appointment, Prof. Zhang worked as a post
2012/09–2017/06, he studied at the College of Physics at doctoral fellow in Okinawa Institute of Science and Technology
Huazhong University of Science and Technology, and he Graduate University in Japan and King Abdullah University of
received his Ph.D. degree in 2017/6. From 2017/06–2020/06, Science and Technology in Saudi Arabia, respectively. She
he worked as the postdoctoral fellow in Wuhan National Lab received her B.E. and Ph.D. from Sichuan University and
oratory for Optoelectronics (WNLO) at Huazhong University of Peking University, respectively. Her research interest is
Science and Technology. Currently, he holds the associate development of advanced materials for high-energy-density
professor position in School of Science in Hainan University. storage systems, including lithium batteries, aqueous batte
His research interest is the fabrication and utilization of metal ries and metal-air batteries.
chalcogenide photocatalysts for the application of photo
catalytic hydrogen evolution.
Yu Zhang obtained her Bachelor’s degree from Hunan Uni Jing Li obtained her Bachelor’s degree from Henan University
versity of Arts and Science in 2022. She is currently a M.S. of Science and Technology in 2009/06. From 2010/09–2013/
candidate in the Chemical Engineering and Technology at 06, she studied at the School of Chemistry and Chemical En
Hainan University. Her research interests focuses on the design gineering at Guizhou University and obtained her master’s
of functional nanomaterials for electrochemical energy storage degree. She received her Ph.D. degree from South China Uni
devices. 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.
Guan Wang received his B.S. degree in Huanghuai University. Peilin Deng received his Ph.D. degree in engineering from
He is now pursing his M.S. degree under the supervision of Huazhong University of Science and Technology in 2020. He is
Prof. Xinlong Tian in School of Chemical Engineering and now an associate researcher in the School of Chemical Engi
Technology at Hainan University. His main interest is the neering and Technology at Hainan University. He mainly fo
design and preparation of nanomaterials for electrocatalysis. 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.
Xiaodong Shi received his PhD degree from Central South Xinlong Tian is currently a full professor in State Key Labo
University, and joined the China State Key Laboratory of Ma ratory of Marine Resource Utilization in South China Sea at
rine Resource Utilization in South China Sea, Hainan Univer Hainan University, China. He received his Ph.D. degree from
sity, as an associate research fellow in 2022. His current South China University of Technology in 2016. Afterwards, he
research focuses on the synthesis and application of nano worked as a postdoctoral researcher in Huazhong University of
materials for energy storage devices, such as seawater batte Science and Technology from 2016 to 2019. Now he is the
ries, sodium/potassium-ion batteries and aqueous zinc-ion Principal Investigator of the Marine Clean Energy Innovation
batteries. 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.
17

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Nano Energy 110 (2023) 108364

Contents lists available at ScienceDirect

Recent advances and future perspectives of rechargeable

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

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

2.2. Anode and aqueous. Non-aqueous, organic solvent-based liquid electrolytes

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

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