REVIEW

Zinc Batteries

Fundamental Understanding and Effect of Anionic

Chemistry in Zinc Batteries
Yuxin Gao, Zhexuan Liu, Shan Guo, Xinxin Cao, Guozhao Fang* , Jiang Zhou* , and
Shuquan Liang*

intercalated into the crystal structure of elec-

With the merit of high capacity, high safety, and low cost, zinc-ion batteries trode along specific diffusion paths, inducing
(ZIBs) possess huge application potential in the domain of large-scale energy the valence shift of host cations. In sharp con-
storage. However, due to the relatively narrow voltage window and large trast, anionic redox reaction, such as the interca-
lation of anions into the electrode lattice
lattice distortion of cationic redox reaction, ZIBs tend to present low energy structure and the optimization of electrolyte
density, poor kinetics, and unstable cyclic performance. Anion chemistry composition, hold more feasibility for further
seems to provide a novel strategy to solve these issues from different aspects, breakthrough.
such as enhanced operating voltage, extra capacity contribution, and boosted Anionic chemistry mainly includes anionic
reaction kinetics. Considering the significance of this theory and the lack of redox, anionic modification of electrode and elec-
trolyte. Different from other strategies, anionic
relevant literatures, herein, in-depth comprehension of anionic chemistry and
chemistry can endow the battery system with
its positive effects on zinc storage performance have been emphasized and unique features, and simultaneously maintain the
summarized. This review aims to present a full scope of anionic chemistry pristine state of host material to the greatest
and furnish systematic cognition for rational design of advanced ZIBs with extent.[7] For instance, anionic redox reaction
high energy density. Furthermore, insightful analysis and perspectives based occurring at high potential could increase the zinc
on the current research status also have been proposed, which may point storage capacity and the corresponding energy
density, in which it activates the valence change
out some scientific suggestions and directions for the future research. of O (O2− ↔ O22−),[8] N (N3− ↔ N2−),[9] or I
(I− ↔ I2−),[10] and meanwhile keeps the normal
1. Introduction reaction of cationic redox. Additionally, the anionic doping also could
interact with the nearby cationic lattice framework, and determine the
Zinc-ion batteries (ZIBs), as the most promising candidate for lithium- band structure, electronic density, density of state, and coordination envi-
ion batteries (LIBs) in the field of large-scale energy storage, have ronment, thereby affecting the stability of crystal structure, operating volt-
received widespread attention due to the advantages of environmental age, and diffusion kinetics correspondingly. Besides, the anionic
friendliness and high safety.[1–6] However, ZIBs still suffer from low modification of electrode could offer extra electrochemically active sites to
energy density, sluggish kinetics and inferior cycling stability owing to enhance the ion adsorption and diffusion behavior. Furthermore, the anio-
the low voltage platform and large lattice distortion based on cationic nic modification of electrolyte could contribute to the ion (de)solvation
redox reaction. To address these issues, previous research mainly effect, which helps to strengthen the dynamics of solid–liquid interface
focused attentions on some conventional strategies: 1) promote electro- reactions.[11–13]
chemical activity through cationic doping; 2) enhance the electrical In despite of these remarkable virtues, the further popularization and
conductivity by conductive surface coating; 3) improve the utilization application of anionic chemistry remain a challenge due to the draw-
of active material via morphological control; and 4) widen the operat- backs of anion chemistry itself and the lack of systematic theoretical
ing voltage window by lattice structure regulation. These aforesaid guidance.[14] For instance, anionic framework of electrode crystal lattice
strategies did not break the basic principle that the guest cations were is likely to undergo severe irreversible structural transformation and
even structural collapse, resulting in the rapid capacity decay.[15–18] In
Y. Gao, Z. Liu, S. Guo, Prof. X. Cao, Prof. G. Fang, Prof. J. Zhou, Prof. S. Liang detail, excessive redox of lattice O (O2− ↔ O22− → O2↑) will lead to
School of Materials Science and Engineering, Central South University, the formation and release of oxygen, leading to the battery expansion.
Changsha 410083, China The residual cations with low valence may lose energy storage capability
E-mail: [email protected] and even catalyze the electrolyte decomposition. Meanwhile, excessive
E-mail: [email protected]
transfer and reaction of anions in the electrolyte could also cause its
E-mail: [email protected]
Prof. X. Cao, Prof. G. Fang, Prof. J. Zhou, Prof. S. Liang uneven distribution and excessive consumption, as well as the forma-
Key Laboratory of Electronic Packaging and Advanced Functional Materials tion of by-products, which would accelerate the deterioration of chemi-
of Hunan Province, Central South University, Changsha 410083, China cal reaction environment and the failure of crystal structure. Therefore,
The ORCID identification number(s) for the author(s) of this article just like the rational design of cationic chemistry-based electrodes for
can be found under https://doi.org/10.1002/eem2.12225. ZIBs, criteria and strategies for the feasibility, reversibility, and stability
DOI: 10.1002/eem2.12225 of anionic chemistry-based electrodes also need to be proposed.

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Herein, from the perspectives of electronic structure, chemical reac-
tion thermodynamics and ion diffusion kinetics, the basic principle and Yuxin Gao received her Bach-
understanding of anionic chemistry are proposed and introduced firstly. elor degree (2019) from She-
Referring to the relevant elaborations in other energy storage systems, nyang University of
the fundamental effect and mechanism of the preliminary applications Technology. She is now a mas-
of anionic chemistry in ZIBs are summarized. Furthermore, aiming on ter degree candidate in School
the unknown and limit of this strategy, the further reasonable develop- of Materials Science and Engi-
ment direction and suggestions are put forward. This review not only neering, Central South Univer-
provides a promising guideline to design novel anionic chemistry- sity supervised by Prof. Jiang
based electrodes for ZIBs, but also summarizes and explores the basic Zhou and Guozhao Fang. Her
scientific theories about anionic chemistry. research focuses on the syn-
thesis and application of man-
ganese-based cathode
2. Fundamental Principles and Deep
materials for aqueous zinc-ion batteries.
Understanding of Anionic Chemistry
Zhexuan Liu received his
2.1. Anionic Redox Reaction
Bachelor degree (2019) in
Materials science and Engi-
Generally, the anions with larger ionic radius construct lattice frame-
neering from Central South
work by different stacking patterns, in which the cations are in the
University. He is now a Ph.D.
interstitial sites. During the charge/discharge process, the cation
candidate in School of Materi-
valence mainly depends on the number and location of intercalation
als Science and Engineering,
sites, being provided by the electronic structure and crystal structure
Central South University
of host materials. After the ligand-hole chemistry was proposed in
supervised by Prof. Shuquan
chalcogenides,[19,20] the slight shortening of O–O interplanar distance
Liang. His research focuses on
was discovered, indicating that the O also participated in the redox
the synthesis of electrode
reaction at high voltage.[21] The specific operating voltage caused by
materials and their applica-
the valence state is mainly related to the covalency of M–X bond, in
tions in aqueous zinc-ion batteries.
which M and X represent d band of metal cations and the p band of
anionic elements, respectively. The highest potential represents the
Guozhao Fang received his
higher ionicity. The band structure of M–X consists of low energy
Bachelor degree (2014), and
band, that is, (M–X) bonding state, and high energy band, that is,
Ph.D. degree (2019) from Cen-
(M–X)* anti-bonding state, which is separated by pure non-bonding
tral South University. After grad-
ligand band. Owing to the high ionicity and the strong binding of
uated, he joined Central South
anions to electrons in oxides, the density of states (DOS) of the d band
University as a Professor in Prof.
of metal cations ((M–X)*) is above the p band of anions (Figure 1a).
Shuquan Liang’s group. His cur-
This result means that the metal d band, as the role of redox center,
rent interests include low-cost
contributes to the electron donation or release.
sodium-ion/zinc-ion electrolytes,
However, if two bands are close or overlap, the electrons of the p
electrolyte/electrode interface,
band can be transferred into the d band, thereby the highly covalent lat-
as well as structural regulation
tice framework could accommodate the redox active anion network. In
of electrode materials.
this framework, the anion ligand O2− can be more electropositive than
the central cations. On the other hand, such process will leave holes,
and eventually produce and accommodate (O2)n− by changing coordi- Jiang Zhou received his Bach-
elor degree (2011), and Ph.D.
nation environment. Therefore, in order to induce more feasible anio-
nic redox, many efforts have been made to improve the covalency of degree (2015) from Central
lattice structure, including reducing the electronegativity of anions (re- South University. During
2014–2015, he studied in Prof.
placing O with S, Se, etc.) or increasing the electronegativity of cations
Hua Zhang’s group at
(replacing Mn with Fe, Sn, etc.). This could be referred to the reaction
mechanism and design principle of electrocatalyst materials for water Nanyang Technological
University (NTU) as an
decomposition. The demanded low decomposition voltage is just oppo-
exchange Ph.D. student. After
site to the required stability of batteries. The lattice oxygen can be
released into O2 at potential higher than 1.23 V vs. RHE (Reversible graduated, he carried out his
Hydrogen Electrode) with the activated anionic redox, corresponding postdoctoral research in Prof.
Ju Li’s group at Massachusetts
to the harmful irreversible electrode decay in batteries.
The band structure analysis provides the anionic redox feasibility Institute of Technology (MIT) since 2016. He joined Central
from the perspective of reaction thermodynamics, while the considera- South University as a Professor in the end of 2017. His
research interests are on lithium /sodium-ion batteries and
tion of crystal chemistry is also of great importance to evaluate the pos-
sibility of ion migration and phase transition kinetics. Layered aqueous zinc-ion batteries

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structures allow the formation of more O−O bonds due to the tunable
polyhedrons and lattice parameters, while the spinel, perovskite and Shuquan Liang received his
Prussian blue analogs with corner-shared octahedrons and rigid 3D Ph.D. degree from Central
frameworks are difficult to change. The lattice distortion lowers the South University in 2000. He is
crystal symmetry to allow efficient interactions between (M–X)* and p the winner of Monash Univer-
band of anions, corresponds to the formation of M–(O–O), which sity Engineering Sir John
opens a gap in the material electronic structure.[12,22,23] In other words, Medal. He hosted five State
the introduction of crystal defects (such as substitution and disorder) Research Projects including
may be a promising method to activate the reversible formation of National 973 Sub-project and
O−O. For instance, the substitution of M by additional Li in Li-rich National 863 Project. He has
phase, such as Li2MnO3 or Li2TiO3,[24] results in distortion of the published more than 100
[MO6] coordination environment and lowered symmetry from cubic papers in frontier journals.
structure to C2/m or C2/c, which generate the pure non-bonding O Currently, his main research
2p states with labile electrons and high energy. interests include micro/nanostructured functional materials,
In addition to the electrochemical activation of anions in the elec- nanocomposites and their energy storage as well as conver-
trode lattice, anions in the electrolyte for charge balance can also be sion devices.
introduced into the conversion reaction at the electrode, which deliv-
ers a more intuitive reaction mechanism similar to zinc-based flow
batteries and Zn-halogen (I/Br) batteries.[25,26] Ideally, in despite of anolyte and catholyte, raising the issues of low efficiency and poor
the conventional bulk ion (de)intercalation, the continuous deposi- reversibility. Taking the Zn-I2 flow battery as an example, the Br−
tion/dissolution of other active phases (such as I− → In− → I2) at the additive in electrolyte could stabilize free iodine through anion com-
surface of electrode could contribute considerable capacity. However, plexation and unlock the capacity contribution from iodide.[27] The
it should be noted that the lack of flow pump and ion exchange mem- related reaction equations are listed as follows:
brane in normal ZIBs means the possible direct contact between
2I

2e
$ I2ðaqÞ (1)


I þ I2 $ I

3 (2)

2I
þ Br

2e
$ I2 Br
(3)

Detailedly, the remaining 1/3 of I− is used

to stabilize I2 to form I3− without Br− (Equation
2). After the introduction of Br−, the corre-
sponding capacity of zinc-iodine flow battery
could be released and increased by at least 1/3
(Equation 3), demonstrating that anionic addi-
tives hold great potential to upgrade capacity.

2.2. Anionic Modification of Electrode

Based on the above-mentioned anionic lattice

framework, the adjustment of lattice framework
would also have impact on ion intercalation and
ion diffusion. The electrochemical reaction pro-
cess generally includes two steps, that is,
adsorption and desolvation on the electrode sur-
face, as well as migration and diffusion in the
bulk phase, which are essentially the competi-
tion and change of coordination environment.
Therefore, the anionic modification of electrode
structure is closely related to the coordination
environment in the solid–liquid interface and
the bulk lattice framework.
The ions in the electrolyte need to be par-
tially desolvated before the intercalation process,
Figure 1. Fundamental understanding of anionic redox. a) DOS of the d band of metal cations and which generally requires high desolvation
2+
the p band of anionic elements with polyhedron distortion. b) Effects of anionic chemistry on ion energy due to the high charge density of Zn
(de)solvation and migration in electrolyte, electrode, and interface between electrolyte and electrode. in aqueous electrolyte environment.[28,29] High

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(de)solvation energy leads to slow interfacial reaction kinetics and sev- than that of oxygen. When substituting oxygen with sulfur in tran-
ere polarization, thereby suppressing the electrochemical capacity and sition metal oxides, it could effectively enlarge the lattice spacing
cyclic stability. In addition, bulk diffusion barrier of partially desolvated and reduce the electrostatic repulsion and intercalation energy bar-
ions would require expanded diffusion channels to accommodate rier of Zn2+ ions.[36,37] Additionally, the construction of metastable
excess solvent molecules, which accelerates the destruction and decay intermediate polyhedrons through reducing the crystallinity and
of electrode.[30,31] Hence, the side reaction occurring at the solid–liquid destroying partial anionic framework is also a viable means to buf-
interface conduces to form solid electrolyte interface (SEI) film in the fer the energy fluctuation during ion diffusion process.
first cycle to buffer the subsequent solvation effect in most non-
aqueous secondary batteries.[31] For the batteries without in situ SEI
film, the construction of artificial “SEI” film also could effectively main- 2.3. Anionic Regulation of Electrolyte
tain the compatibility and stability in solid–liquid interface,[32,33]
among which the novel surface modification of anionic groups seems Different from the anionic redox in electrode, anion chemistry also
to be more promising. pays some attentions on the solvation effect in electrolyte. Typically,
The ion diffusion process in the electrode lattice can be regarded as ZnSO4 and Zn(CF3SO3)2 are widely used as electrolytes in aqueous
the long-range diffusion in the periodic framework. The ion storage ZIBs, in which CF3SO3−-based electrolyte shows more stable perfor-
from the surface to the interior of active materials is achieved through mance due to its high steric hindrance, high stability, and low desolva-
constant migration among the interstitial sites of stable or metastable tion energy.[38,39] Additionally, the presences of SO42− ions in ZIBs
coordination polyhedrons. These alternate polyhedrons construct the tend to induce the formation of hydroxyl sulfate by-products in both
ion diffusion paths, while the maximum energy required to traverse side of cathode and anode.[40] As a sharp contrast, ZnCl2 and Zn
these paths is the activation energy barrier, which is closely related to (NO3)2 electrolyte always present abnormal zinc storage performance
the coordination environment around these polyhedrons. In order to due to their instability and electronegativity.[41] The influences of sol-
evaluate the ion diffusion ability in crystals, the diffusion coefficient vation coordination structure of cations and anions in the electrolyte
(D) is introduced to characterize the ion migration in idealized on the cathode reaction also need to be highlighted. From the perspec-
intercalation-type materials:[34] tive of coordination between the ligand anions (L), the reaction is
described as follows:[42]
D ¼ ρλ2 Γ (4)  
MLz L0y ½Lx
z
where ρ is the geometric factor, which is related to the coordina- MLx þ yL0 $ MLz L0y þ ðx
zÞL, K ¼ (6)
½MLx ½L0y
tion number (z) and diffusion channel dimension (d) of the inter-
stitial lattice. λ is the migration distance between adjacent where K is the equilibrium constant, reflecting the stability of the
interstitial sites. Frequency hopping Γ is described by the follow- coordinated ion. According to the relationship between standard
ing formula:[34] enthalpy and equilibrium constant

  ΔG ¼
2:303RTlgK (7)

Ea
Γ ¼ v∗ exp
(5)
kT
Under certain temperature and pressure conditions, it could be con-
cluded that:
where v* is the vibration factor, and Ea is a barrier to migration.
Hence, it is obvious that the anionic framework modification of ΔG ¼ ΔH
TΔS (8)
electrode materials plays an important role in the diffusion kinetics,
especially in improving the diffusion dimension (d) and reducing ΔS ΔH
the diffusion barrier (Ea). lgK ¼
(9)
2:303R 2:303R
The introduction of anion vacancy defects could offer additional
diffusion channels, so that it is not difficult to understand the The stability of coordinated ion mainly depends on entropic
increased diffusion dimension (d). Meanwhile, the diffusion barrier change and enthalpic change. The decreased energy of metal ions
(Ea) is affected by many factors, such as lattice parameters, and ele- under the influence of the coordination field is attributed to enthal-
ment compositions. According to the theory of coordination chem- pic factor to affect the stability constant, while for the entropic fac-
istry, ions in the most suitable coordination state have the lowest tor is the change of the molecules number caused by the
thermodynamic energy. The violent change of coordination envi- coordination reaction.
ronment (polyhedron) along diffusion path would lead to the obvi- Therefore, the species and concentration of anions in electrolyte
ous energy difference of each intermediate site, thus generating could directly determine the coordination ions and Gibbs free
high energy barrier. Although there have various polyhedrons in energy, which further affect the surface desolvation and ion-
different crystal structures, a suitable crystal structure should possess solvent molecular cointercalation. Combined with anionic modifi-
low coordination fluctuation, which is of significance for ion diffu- cation of electrode, rapid ion transport, low desolvation energy
sion kinetics. For example, the coordination polyhedron structure and stable solid–liquid interface could be theoretically achieved by
of some layered vanadium-based cathodes could be kept stable dur- regulating the change of enthalpy and entropy. In fact, most of
ing the (de)intercalation process of Zn2+, likewise presenting good the reported literatures pay more attention on the effects of vari-
diffusion kinetic behavior.[35] For the purpose of choosing appro- ous metal cations and organic additives instead of anions. There-
priate crystal structure and anion framework, anion doping may be fore, the relevant research about anionic chemical regulation in
a feasible strategy. For instance, sulfur holds a larger atomic radius ZIBs is still in infancy and need to be excavated.[43–45]

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3. Positive Effects and Functional Mechanism of the energy difference, and the anionic redox is triggered.[57] Similarly,
Anionic Chemistry as shown in Figure 3d, the energy (ΔEu) of S8 + Zn (−1.451 eV) was
much smaller than that of SeS7 + Zn and Se2S6 + Zn. The lower ΔEu
Anionic chemistry has gradually drawn the concerns of researchers due value represented the higher stability and lower reactivity, indicating
to its guiding significances for the exploitation of high-performance the introduction of selenium into elemental sulfur could break the
batteries. Herein, positive effects of anionic chemistry on the ZIBs have structure stability of S8, and enhance the reaction kinetics, which is
been summarized and highlighted in Figure 2, which may provide sci- beneficial to the energy density of batteries.[58]
entific references and guidance for its further research and future appli- Conversely, the strongly electronegative anionic element (F) could
cations. increase the operating voltage of cations, forming M–F bonds (M repre-
sents transition metal element) to provide larger energy difference and
higher voltage.[59] Therefore, the introduction of F is also an effective
3.1. Increasement of Energy Density method in modifying the electrode and improving the energy density,
especially for fluorophosphates.[60]
High energy density could be achieved by the simultaneous catio- In addition to the intrinsic anionic reaction of electrode, the anions
nic and anionic redox reactions of electrode, which mainly in the electrolyte can also provide additional capacity. For example, the
depends on whether the non-bonding O 2p band is formed. For I− anion and even the dual halogen anions (Br/Br− and Cl/Cl−) in
example, Li1/3M2/3O2 slab in Li-rich layered Li2MO3 could cause electrolyte could contribute capacity according to anionic redox reaction
the distortion of [MO6] polyhedron, in which Li and O atomic (Figure 3e).[27,47] In this zinc-dual halogen battery system with molten
orbitals do not overlap effectively and form a non-bonded orbi- hydrate electrolyte, the graphite electrodes can sequentially accommo-
tal.[55] As shown in Figure 1a, this non-bonded orbital partially date intercalated Br− and Cl−, improving the capacity from 78 to
overlaps with the lower-Hubbard bands, which are formed by par- 257 mA h g−1 compared with the conventional zinc-bromine batteries.
tially filled splitting (M-O)* bands. On this basis, electrons could There are also applications in aqueous ZIBs, which provide a new ave-
be gained and lost from the non-bonded orbital of O 2p, resulting nue for building high voltage batteries through using dual-ion battery
in the reversible redox reaction of oxygen. system and “water-in-salt” electrolyte.[46,62]
The redox reaction of oxygen involves the repetitive migration of Recent reports have also highlighted the significant importance
transition metals and the continuous formation and rupture of O-O of electrode-electrolyte interface, which is not limited to the SEI
bands. Therefore, the anionic redox requires relatively flexible and layer with expanded voltage window.[63] For instance, the
weak O bonding environment, otherwise it won’t happen. Taking electrolytic-anionic-redox adsorption pseudocapacitance mecha-
Na3V2PO4 electrode as an example, the internal P–O bonds are so firm nism improves the capacity via reversible anions adsorption/des-
and tight that the redox reaction of oxygen could not occur.[56] Mean- orption (such as Mn3O4 and PF6− as shown in Figure 3f), which
while, for most vanadium-based metal oxides, such as V2O5, V3O7, the constructs Mn–F bonds for charge transfer and provides fluoride
lack of PO43− electron group also lead to a lower operating voltage. ions as extra redox centers.[61,64] The crucial factors for this mech-
Benefitting from the oxygen redox reaction, VOPO4 cathode could dis- anism to achieve high capacitance include: 1) suitable anions in
play excellent zinc storage performances due to the high operating volt- electrolyte and 2) elaborate electrode with high specific surface
age, flexible framework of [VOx] polyhedron, as well as structural area. Hence, in order to further achieve the high compatibility of
stability provided by PO43−.[46] Detailedly, the structural distortion of the electrode-electrolyte interface, anionic groups such as hydrox-
[VOx] polyhedron causes the partial release of oxygen atoms and gener- ide, phosphate and oxygen ions are tried to connect to the dan-
ate some unbonded electrons. Based on the above principles (Figure gling bonds on the surface of the crystal grains. This mainly
3a), the corresponding cationic and anionic redox of VOPO4 cathode includes carbon materials (such as graphene oxide and carbon
could be describedbelow:[46] paper containing oxygen groups on the surface) and MXene with
no or low electrochemical activity,[65–67] endowing them surpris-
Znx VOPO4
xZn2þ
2xe
$ VOPO4 ðvanadium redoxÞ (10) ing performances in ZIBs.[48] Typically, the oxygen-rich groups
were connected on carbon paper by using hybrid acid treatment,
VOPO4
ye
$ VOyþ PO4 ðoxygen redoxÞ (11) which significantly improved electrode hydrophilicity, specific
capacity and rate performance.[65] For the electrochemical inert
Besides the additional capacity, the average operating voltage of Zn/ material NiCo2O4, the phosphate ion was also tried to anchored on
VOPO4 batteries also has been raised to 1.56 V. The reason is that oxy- the electrode surface.[48] Compared with O2−, the phosphate ions
gen redox occurs at a high potential, in which O2− is oxidized to O− at have a longer bond length and lower electronegativity, which
2.1 V in the charge process (Figure 3b). could reduce the energy barrier of electron transport and enhance
On basis of theoretical perspective, the increased operating voltage reaction kinetics.
of anionic redox results from the high overlaps of the d orbital and p In short, it can be noted that the increased energy density is usually
orbital in its transition metal ion. (M-O) orbitals have strong ligand, based on the activation of additional reactions, which requires the con-
while (M-O)* hold metal-like properties. The energy difference struction of thermodynamic metastable state of electrode bulk or
between bonding (M-O) and antibonding (M-O)* is huge. Addition- electrode-electrolyte interface. These metastable reaction sites are not
ally, introducing non-metallic elements with lower electronegativity only conducive to high specific capacity and energy density,[68–71] but
than O element, such as N, S, Se, could improve the covalency of the also can reduce the barrier during ion diffusion process. The improve-
bond and reduce the threshold of anionic redox (Figure 3c).[55] In ment of reaction kinetics is significantly important to the rate perfor-
recent report, the O in V2O5 was partially replaced by N to prepare the mance and output power density, which will be discussed in the bulk
VNxOy electrode, in which the high covalency of V–N bond reduces anion defect regulation, mainly including anionic doping and vacancy.

Energy Environ. Mater. 2022, 5, 186–200 190 © 2021 Zhengzhou University

 25750356, 2022, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12225 by Korea Advanced Institute Of, Wiley Online Library on [22/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Figure 2. Positive effects of anionic chemistry on ZIBs. a) Elevated voltage platform of Zn/VOPO4 batteries. (Reprinted with permission from Wan et al.[46]
Copyright 2019 WILEY-VCH.) b) Increased voltage platform and specific capacity of dual-halogen redox couples. (Reprinted with permission from Liu et al.[47]
Copyright 2020 Wiley-VCH GmbH.) c) Increased specific capacity by the introduction of oxygen vacancies and surface phosphate ions. (Reprinted with
permission from Zeng et al.[48] Copyright 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.) d) Ion diffusion paths broaden by oxygen vacancies of
Ocu-Mn2O3. (Reprinted with permission from Liu et al.[49] Copyright American Chemical Society.) e) Ion mobility enhanced by anionic substitution.
(Reprinted with permission from Wu et al.[50] Copyright 2014 The Royal Society of Chemistry.) f) Fast migration kinetics of Li-S cells by the synergistic effect
of cathode design, Se doping and lead electrolyte (Reprinted with permission from Zhao et al.[51] Copyright 2020 WILEY-VCH.) g) Electrochemical stability of
both Zn and Li metal batteries endowed by using MXene@Zn paper as current collector. (Reprinted with permission from Tian et al.[52] Copyright 2019
American Chemical Society.) h) Cycling stability of organic electrode. (Reprinted with permission from Wan et al.[53] Copyright 2018 WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim.) i) Mechanical stability enhanced by the insertion of nitrate ion in graphene layers. (Reprinted with permission from Yan
et al.[54] Copyright 2018 Macmillan Publishers.)

3.2. Improvement of Reaction Kinetics ion diffusion kinetics owing to the strong interaction between
host and guest ions, thereby resulting in unsatisfactory rate per-
The improvement of reaction kinetics is attributed to the change formances.[60] Typically, anionic vacancies can broaden or pro-
of crystal coordination environment (dopants, vacancies) to vide ion diffusion path, such as O, N, S vacancies.[11,16,72,73] In
accelerate ion diffusion kinetics. Considering the coordination addition to the lattice distortion, anion substitution and doping
change between guest ion and lattice framework during diffu- also can introduce local electric field to accelerate diffusion
sion, the polyhedron fluctuation and distortion would break the kinetics. Two principles should be noticed for selecting suitable
symmetry of crystal and cause thermodynamic metastability. For anionic species: 1) replacing anions with low electronegativity
example, though the introduction of F can increase the energy to weaken the strong interaction; 2) doping anions with low
density of polyanion-type cathodes, they still suffer from slow valence to reduce charge interaction.[74]

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Figure 3. Anionic chemistry improves energy density. a) Diagram of energy vs. density of states and b) Comparison of the second charge/discharge curves of
VOPO4/SWCNT cathode. (Reprinted with permission from Wan et al.[46] Copyright 2019 WILEY-VCH.) c) Influences of low electronegativity elements on
energy band. (Reprinted with permission from Assat et al.[55] Copyright 2018 Springer Nature.) d) The energy (ΔEu) of bond break and combination with Zn
in SeS7, Se2S6 and S8 rings. (Reprinted with permission from Li et al.[58] Copyright 2021 Wiley-VCH GmbH.) e) Schematic diagram of composition and
working principle of zinc-dual-halogen batteries. (Reprinted with permission from Liu et al.[47] Copyright 2020 WILEY-VCH.) f) Schematic illustration of the
electrolytic-anion-redox adsorption pseudocapacitance mechanism. (Reprinted with permission from Li et al.[61] Copyright 2020 Elsevier Ltd.)

Generally, the issue of slow ion diffusion kinetics is caused by As similar to the cationic doping, anionic doping also could generate
the limited diffusion path and strong electrostatic repulsion in the the crystal structural defects and improve the reaction kinetics. Gener-
host crystal structure. For manganese-based cathode materials, the ally, anionic doping elements include N, O, S, Se, and F. According to
[MnO6] framework is relatively stable. However, the disproportion- the density of state results in Figure 4d, the bandgap of N-MnO2–x
ation of Mn3+ will directly lead to the dissolution and destruction was smallest, indicating that electronic conductivity could be
of crystal structure. Therefore, different cations are generally intro- greatly improved by N doping and oxygen vacancies. As a result in
duced to create oxygen-defects, such as Li(Li1/3Mn2/3)O2, Figure 4e, N-MnO2–x cathode also presented significantly pseudo-
Nax(Mg1/3Mn2/3)O2, in which the disordered atomic arrangement capacitive zinc storage capacity, demonstrating that N-doping
could promote ion migration and ion diffusion behavior. As pre- could enhance the capacitive adsorption behavior.[77] Additionally,
sented in Figure 4a, [MnO6] polyhedron walls were broken doping oxygen atoms into layered MoS2 could enlarge the inter-
through the introduction of oxygen vacancies in K0.8Mn8O16, and layer spacing, modify the hydrophilicity and thus markedly reduce
thus extra paths for H+ diffusion were opened. These oxygen the intercalation energy barrier of Zn2+, guaranteeing fast Zn2+
vacancies guaranteed fast diffusion behavior and high electrochemi- diffusion kinetics (Figure 4f).[78] Additionally, N-doping into
cal reaction activity.[11] Similarly, as shown in Figure 4b, extracting V2O5 also contributed to form defective disordered rocksalts
oxygen anions from ZnMn2O4 could effectively reduce electrostatic through charge-compensating function. Consequently, the disor-
repulsion.[75] Additionally, introducing heterovalent cations into the dered rocksalts generated lots of active sites for zinc storage, which
crystal lattice also could modulate the charge distribution. As dis- were conducive to the diffusion kinetics of Zn2+ (Figure 4g).[79]
played in Figure 4c, inducing oxygen vacancies through high- Fluorine element with the highest electronegativity, could affect
valence Ti doping led to the formation of a local inplane electric phase and electronic structure of metal oxide/hydroxide deeply,
field, and unlocked the [MnO6] octahedral walls, availably enhanc- and further determine the reaction kinetics.[80] The fluorine could
ing ion diffusion/electron transfer behavior.[76] bond with metal atoms to form firm metal-F bonds, which could

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prevent electrode dissolution, improve structural stability and the electrolyte has not been studied in detail until now. The anions
reduce polarization effectively. Hence, the F-doped NiCo-CH cath- in the electrolyte usually form special solvation structure and may
ode exhibited significantly improved robustness and conductivity participate in the reaction at the electrode interface. Therefore, the
as flexible batteries.[81] properties in Zn-Zn symmetrical half-cell could not be applied to
Although the anionic chemistry in electrode is highlighted its the full-cell directly. The compatibility between electrolyte and
profound influence on the reaction kinetics, the anionic effect in cathode should be the prime consideration. For instance, the

Figure 4. Anionic chemistry promotes reaction kinetics. a) Schematic illustration of H+ diffusion into KMO with perfect structure and oxygen-defect
structure. (Reprinted with permission from Fang et al.[11] Copyright 2019 WILEY-VCH.) b) Free energy comparison of ZMO and OD-ZMO during Zn ion
diffusion process. (Reprinted with permission from Zhang et al.[72] Copyright 2019 Published by Elsevier Ltd.) c) Charge density differences and the
corresponding charge transfer behavior during charge/discharge process of Ti-MnO2 and MnO2. (Reprinted with permission from Lian et al.[76] Copyright
2019 Elsevier Ltd.) d) DOS of MnO2, MnO2−x, and N-MnO2−x cathode. (Reprinted with permission from Zhang et al.[77] Copyright 2019 WILEY-VCH.) e)
Surface capacitive contribution ratio of N-MnO2−x cathode (Reprinted with permission from Zhang et al.[77] Copyright 2019 WILEY-VCH.) f) Zn2+ diffusion
coefficients of MoS2 and O-doped MoS2. (Reprinted with permission from Liang et al.[78] Copyright 2019 American Chemical Society.) g) Zn2+ diffusion
coefficients of stoichiometric VN0.9O0.15 and disordered rocksalt VNxOy (x ≈ 0.2, y ≈ 2.1). (Reprinted with permission from Ding et al.[79] Copyright 2019
WILEY-VCH.)

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reaction of Zn-MnO2 batteries may involve specific solvation detected on the electrode surface in ZnSO4 electrolyte, indicating
sheath and interface reaction, which shows unsatisfactory perfor- that SO42− participated in the process of forming SEI.[82,92]
mance in other organic and ionic liquid electrolytes.[82,83] More- Different from the Zn-I2 or Zn-S batteries, the anion intercalation
over, different anions will play different roles even in the same reaction from electrolyte to bulk electrode generally belongs to anionic-
aqueous electrolyte system and the mechanism is not clear, which type or dual-ion batteries.[93,94] As an instance in Figure 5f, intercalat-
will be mentioned in next section. ing NO3− into the graphite layer could tighten the structure of
NiCeOxHy electrode, which significantly improved the mechanical sta-
bility.[54] If there is no intercalation of NO3−, the electrode material
3.3. Enhancement of Battery Stability would be deposited on the graphite substrate and generate obvious
interface gaps, resulting the failure of mechanical properties.
Owing to the charge redistribution effect and high electronic conduc- The anionic chemistry shows great potential in improving the elec-
tivity of MXene material, it could guarantee a uniform electric field dis- trochemical and mechanical stability of batteries, which will promote
tribution and a low Zn nucleation energy barrier as the 3D collector, the development of novel flexible batteries and wearable batteries.
interlayer, or zinc container. As the thin interlayer, the MXene in situ However, for the novel Zn-based batteries, such as quasi-solid and all-
grown on zinc foil could effectively inhibit the formation of zinc den- solid electrolyte, the role and mechanism of anions still has not been
drites and the corrosion of zinc metal, thereby improving the electro- researched. It is also an urgent need to conduct related research in this
chemical stability.[84] Additionally, MXene could be decorated with field to further improve the energy density as well as cycling perfor-
different surface terminations, such as O, N, S, Se, Br and Te, through mance, and promote the actual applications of ZIBs.
covalent modification method.[85] As the zinc container, Ti3C2Tx MXe-
ne@Zn paper was employed as anode for ZIBs,[52] which also could
suppress the growth of zinc dendrites (Figure 5a). Therefore, MXene- 4. Issues Facing Promotion and Optimization
modified zinc anode could display long cycle stability and low voltage Strategies
hysteresis with dendrites-free on the surface, ensuring high-capacity
retention ratio. Despite the above-mentioned advantages and positive effects of anionic
Compared with inorganic electrode, organic electrodes hold minor chemistry, there are still some barriers hindering the practical applica-
structure changes during the reaction process, and it is also not affected tions and further popularization of ZIBs. Firstly, the unstable anionic
by the ionic radius and the counterion charge.[86] As shown in Fig- redox reaction may lead to the irreversible structural changes or struc-
ure 5b, the reaction mechanism of Zn-polyaniline (PANI) batteries tural collapse, bringing about the sharp capacity decay of electrode. For
mainly depended on the redox of electrolyte and Zn foil to ensure elec- instance, excessive redox reaction of lattice-oxygen will result in the
trical neutrality.[53] In this process, the structure of PANI has little release of oxygen from crystal structure, while the residual cations in
change, endowing it with superior cycling stability. Moreover, this the crystal lattice may lose energy storage capability.[95,96] Secondly,
supercapacitor-liked mechanism also offers fast ion diffusion dynamics anionic redox reactions generally occur at higher potential conditions,
for Zn-organic batteries. which easily causes the decomposition of electrolyte.[46] Thirdly, the
Different zinc salts in aqueous electrolyte usually possess differ- stability of anion vacancies and surface modifications in the electrode is
ent solvation or desolvation energy between anions and cations, inferior,[97] and both of them may gradually disappear during the reac-
which have significant influences on the cycling performance of tion process. For example, sulfur element may precipitate into the elec-
ZIBs. Zinc storage performances of zinc salts with the same concen- trolyte and passivate the metal anode for the sulfur-containing anion
tration and different anions, such as Cl−, NO3−, CH3COO− and framework.[98,99] Fourthly, excessive anion transfer and reaction in the
SO42−, were presented in Figure 5c. As a result, 3 M ZnSO4 elec- electrolyte may cause uneven charge distribution, continuous electrolyte
trolyte hold the highest specific capacity and best cycling stability consumption as well as the formation of by-products, which will accel-
based on the commercial V2O5 cathode.[87] Similar electrochemical erate the deterioration of chemical reaction environment and the failure
behaviors were also detected in Zn-TiN capacitors, in which SO42− of crystal structure. In response to these issues, a series of correspond-
anions took part in a two-step adsorption and intercalation process, ing optimization strategies are listed as follows:
boosting the anti-self-discharge ability and stable capacitance per-
formance.[90] Furthermore, the electrochemical differences
between ZnSO4 and Zn(CF3SO3)2 electrolyte based on ZnMn2O4 4.1. Optimization of Electrode Structure
cathode have been deeply explored. In consequence, [Zn(N
(SO2CF3))3]− and [Zn(SO3CF3)3]− cluster models in Zn(CF3SO3)2 The electrode structure directly affects the reaction stability of anionic
electrolyte have a higher Zn–O Mayer bond order values (Fig- chemistry. Although the crystal structure constructed by anions is con-
ure 5d), which contributes low solvation effect, stable structure, ducive to ion diffusion, it is not always stable. In this case, the intro-
and high dissolution energy. These merits ensure the stable duction of heterogeneous ion doping could effectively support the
reversibility and fast deposition/dissolution kinetics.[88,91] In addi- main structure, and then enhance the stability of electrochemical reac-
tion to the solvation structure, the anions in the electrolyte also tion. Besides, structure induction and antisite occupation induction also
could directly participate in the interface reaction between elec- could improve the stability and reversibility of anionic redox reaction.
trode and electrolyte. In Wang’s report, ZnCl2-H2O-dimethyl sul- For heteroatomic doping, it is of significance to select appropriate dop-
foxide (DMSO) electrolyte was applied to Zn-MnO2 batteries, in ing elements. The anion redox of oxygen element under high potential
which Cl− tightly combined with DMSO molecule to form SEI on is prone to undergo irreversible oxygen loss, while the choice of transi-
the surface of MnO2 cathode to maintain the cycling stability (Fig- tion metal cations with low mobility as the electrode material could
ure 5e).[89] Similarly, Zn4SO4(OH)6nH2O product also could be effectively suppress the issue of oxygen loss. Additionally, organic

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Figure 5. Anionic chemistry enhances electrochemical stability. a) Morphology evolution of 2D planar Zn anode and MXene@Zn anode during the
stripping/plating process. (Reprinted with permission from Tian et al.[52] Copyright 2019 American Chemical Society.) b) Schematic illustration of Zn-PANI
cells during charge/discharge process. (Reprinted with permission from Wan et al.[53] Copyright 2018 WILEY-VCH.) c) Cycling performances of Zn–V2O5 cells
using different electrolytes, including ZnSO4, Zn(CH3COO)2, Zn(NO3)2 and ZnCl2. (Reprinted with permission from Zhou et al.[87] Copyright 2018 The Royal
Society of Chemistry.) d) Cyclic voltammograms of Zn anode in aqueous electrolyte of 1 M Zn(CF3SO3)2 and 1 M ZnSO4 at the scan rate of 0.5 mV s−1
within −0.2 to 2.0 V. (Reprinted with permission from Zhang et al.[88] Copyright 2016 American Chemical Society.) e) Cyclic stability and coulombic
efficiency of Zn-MnO2 cells in ZnCl2−H2O and ZnCl2−H2O−DMSO electrolytes with 0.1 M MnCl2 to suppress Mn2+ dissolution at 8 C. (Reprinted with
permission from Cao et al.[89] Copyright 2020 American Chemical Society.) f) A schematic two-step synthesis using graphite g) substrate and nitrate
precursors (Reprinted with permission from Yan et al.[54] Copyright 2018 Macmillan Publishers.)

electrodes with strong structural tolerance, are of great benefit for its factor is the lack of alkali metals, which leads to unbonded oxygen
application in anion chemistry-based batteries. (fewer than 3 cations coordinating oxygen) and the loss of surface
On the one hand, the stability of anionic defects in suitable transi- oxygen. Thus, introducing alkali metal elements with lower mobil-
tion metal-based materials may be different. For the fixed [MnO6] ity (replacing Li with Mg) could avoid the generation of unbonded
polyhedron in most manganese-based materials, any oxygen vacan- oxygen, thereby inhibiting irreversible oxygen loss.[104] Other
cies would cause its distortion and collapse. However, the geometric effective methods also have been taken to suppress the irreversible
structure of [VOx] polyhedron varies,[100] indicating that the stabil- oxygen release. For instance, both Fe substitution (Figure 6a),[105]
ity of electrochemical performance and the integrity of lattice struc- and Ti substitution (Figure 4c),[106] could stabilize the oxygen ele-
ture can be guaranteed during the reaction. The high tunability of ment, thereby inhibiting the release of oxygen. In addition to the
polyhedron, especially in vanadium-based materials, also should heteroatoms doping in the lattice, the synergistic effect between the
meet the requirements of rich active sites, spacious diffusion paths multiphase and anionic defects also needs to be carefully concerned.
and robust framework, generally exhibiting high energy density and Typically, the carbon coating not only provides conductive network
long cycle life.[101–103] Therefore, in order to endow other materials and ion transport path,[102] but also inhibits the agglomeration and
with similar properties, such as manganese-based oxides, the intro- dissolution of internal material due to the thermodynamic instability
duction of heteroatoms with bonding may be a promising method. of defects to some extent.[75,107]
K ions were introduced into [MnO6] polyhedron to stabilize the On the other hand, the circumstance that other non-oxygen anions
cathode structure (Figure 4a), inducing the formation of oxygen- (N, S, Se, P) as well as these anions in organic or polyanionic elec-
vacancies easier without structure collapse.[11] For the irreversible trodes, directly involved in the redox reaction, also should be consid-
oxygen loss at high voltage during oxygen redox process, the key ered. For instance, metal sulfides, including CoS2,[108,109] FeS2,[110,111]

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and VS4,[112,113] served as sulfur redox-active cathode, could provide application of ion selective membrane have made high voltage reaction
high energy density for secondary batteries. Meanwhile, the sulfide ions possible in low concentration electrolyte.[120] However, the high com-
in the layered sodium chromium sulfide can be reversibly insertion/ plexity and cost of these methods hinder their practical applications.
desorption without destroying the crystal structure or changing the lat- Usually, oxygen redox occurs at high potential (2.0 V vs. Zn2+/Zn as
tice parameters. Furthermore, it will trigger the redox of sulfur, which well as 4.3 V vs. Li+/Li) in both aqueous ZIBs and non-aqueous
corresponds to the vacancy antisite of chromium/sodium. Such an LIBs.[121,122] Therefore, it cannot be triggered in traditional low concen-
inversion induction method enables anion energy storage to be better tration electrolyte (such as 1 M Zn(CF3SO3)2) of aqueous ZIBs due to
carried out in layered intercalation compounds.[114] Another special the oxygen evolution reaction occurring at 1.98 V. After adopting “wa-
non-oxygen anion is fluorine, which is usually introduced into polyan- ter in salt” electrolyte of 21 M LiTFSI/1 M Zn(CF3SO3)2, its voltage
ionic cathodes and widely reported in ZIBs, LIBs, and sodium-ion bat- window is much higher than the oxygen evolution reaction voltage
teries (SIBs).[115,116] However, there are still some obstacles hindering (Figure 6b), while the electrolyte decomposition is also effectively sup-
the practical applications of metal sulfides and polyanionic cathodes, pressed.[46] However, the low solubility of zinc salts (below 21–
such as low electrical conductivity, poor cycle stability, and inferior rate 32 mol kg−1) restricted the concentration of aqueous electrolytes.
capability. Based on the previous research, the decorations of conduc- Recently, a mixed electrolyte of ZnCl2/ZnBr2/Zn(OAc)2 with a super-
tive polymers or carbon coatings and the constructions of core-shell solubility up to 75 M was elaborately prepared. Its record-breaking con-
structure could effectively solve the above problems.[51] centration could be ascribed to the formation of acetate capped water-
Additionally, compared with inorganic electrode, organic electrode salt oligomers bridged by Br−/Cl−-H and Br−/Cl−/O-Zn2+ interactions,
possesses the advantages of wide operating voltage window, stable demonstrating that the high-performance electrolyte could be obtained
structure, and molecular-level controllability. These merits endow by adjusting the proportion of anions in the electrolyte (Figure 6c).[117]
organic electrode with minor structure changes and long cycle stability In addition to the concentration, the choices of different zinc salts and
during reaction process. Among the organic electrode materials, solvent also have great influence on the properties of electrolyte.[123,124]
polyaniline, p-type organic compounds as well as conjugated N-
heterocycles could undergo oxidation reaction, bind with anions and
present high redox potential in the electrolyte,[86] which could be pref- 4.3. Regulation of Voltage Window
erentially considered the applications in ZIBs.
The operating voltage is also an important limiting factor for anionic
chemistry reaction. The controllable preparation of high-stability mate-
4.2. Modification of Electrolyte Composition rials and the binding potential can relax the range of conditions for
anionic chemistry.[22] The voltage can raised by engineering molecular
In order to achieve high energy density, zinc storage reaction occurs at structures (Figure 6d).[118] The lowest unoccupied molecular orbital
higher potential is essential. The optimization of collector and the (LUMO) energy level can be reduced by introducing electron-

Figure 6. Issues and strategies of anionic chemistry. a) Effects of Fe substitution on inhibiting oxygen release. (Reprinted with permission from Zhang et al.[105]
Copyright 2019 American Chemical Society.) b) First charge/discharge profiles of Zn-VOPO4 batteries in 1 M Zn(Tr)2 and 21 M LiTFSI + 1 M Zn(Tr)2. (Reprinted
with permission from Wan et al.[46] Copyright 2019 WILEY-VCH.) c) Schematic illustration of dual-ion battery assembled by PGA cathode, WSOE45-1 electrolyte
and Zn/GFF anode. (Reprinted with permission from Cai et al.[117] Copyright 2021 WILEY-VCH.) d) Design strategy for increasing operating voltage of organic
electrode. (Reprinted with permission from Tie et al.[118] Copyright 2020 Wiley-VCH.) e) Design strategy of EMC-based electrolyte with a micro-heterogeneous
anion solvation network. (Reprinted with permission from Chen et al.[119] Copyright 2020 WILEY-VCH.)

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withdrawing groups (such as -CN, -F, -Cl and -Br), and then achieve 5.1. In Depth Exploring the Basic Principle of Anionic Chemistry
the high operating voltage.[118,125] Additionally, the voltage of Zn/or-
ganic batteries can also be affected by the position of active groups. For In addition to the knowledge of band structure, crystallography, and
example, quinone compounds with two carbonyl groups in ortho- coordination chemistry, the intrinsic relations between fundamental
position (1,2-NQ and 9,10-PQ) have a higher voltage than the para- theory of materials science and electrochemical properties needs to be
position (1,4-NQ and 9,10-AQ).[126] further explored. At present, zinc storage mechanisms depended on the
The generation of SEI film derived from high concentration elec- valence change of cations, especially vanadium-based and manganese-
trolyte is also an important approach to broaden the voltage win- based metal oxides, are relatively mature. However, there is still lack of
dow.[127] As shown in Figure 3e, the voltage window of battery corresponding references to truthfully demonstrate the valence change
(LiMn2O4 cathode∣Mo6S8 anode) is significantly widened by the for- of anions and reveal the zinc storage mechanism based on anionic
mation of SEI film in high salt concentration.[128] Therefore, the chemistry.
applications of organic electrode and “water-in-salt” electrolyte are
valid means to broaden the voltage window and increase the operat-
ing voltage platform. However, it still requires further research about 5.2. Adopting Advanced Characterization and Theoretical
the effects of anion groups on the organic electrode and “water-in- Calculation Techniques for the Measurement of Electrode and
salt” electrolyte.[129] Electrolyte
Besides, divalent metal ions are more likely to combine with anions
to form ion pairs. In recent report, trimethyl phosphate (TMP) solvent Accurate mechanism analysis always needs to use advanced characteri-
with strong electron donation ability is employed to prepare Zn zation means. For the electrode material, currently, the valence change
(TFSI)2/EMC electrolyte. These TFSI− anions are tightly confined to the of anions only could be qualitatively analyzed by X-ray photoelectron
TMP solvation region in the form of associated ion pairs (Fig- spectroscopy. If the exact valence change of anions could be quantifica-
ure 6e).[119] Thus, the separation of anions and EMC solvent molecules tionally confirmed, the zinc storage mechanism based on anionic chem-
is realized, which effectively conduces to increase the voltage window istry could be easily revealed. For the electrolyte system, both the
and improve the cycle stability. This method provides new reference to desolvation and solvation process are very abstract concept, which need
widen the voltage window by modifying the electrolyte composition. to be demonstrated by first principles and molecular dynamics calcula-
Presently, the electrochemical reaction mechanism based on the tion in most cases. However, it is still lack of intuitive characterization
anionic chemistry is still imperfect and immature. Especially for ZIBs, methods to observe and reflect the action mechanism of electrolyte on
anions are in an unstable state, easily causing the formation of by- battery performances. Synchrotron radiation X-ray absorption fine
products and uncontrolled reactions. When the anionic reaction occurs, structure spectroscopy (XAFS), small angle neutron scattering (SANS)
it is always accompanied by the release of oxygen and irreversible struc- technique and cryo-electron microscopy technique may be potential
tural collapse.[17,130,131] means to achieve these targets. Therefore, advanced in situ or character-
These practical barriers seriously hinder the promotion and applica- ization techniques should be developed to capture the reaction informa-
tions of anionic chemistry. Herein, both the design of electrode struc- tion in real time for both electrode and electrolyte, including qualitative
ture and the optimization of electrolyte composition could have and quantitative information.
positive effects on these issues, such as widening the voltage window,
increasing the energy density, enhancing the cycling stability, and pro-
moting the reaction kinetics. 5.3. In Detail Elaborating the Solid-liquid Interface Reaction
Mechanism

5. Summary and Perspectives In addition to the exploration of anionic reactions in electrode or elec-
trolyte, the redox reactions occurring at the interface between electrode
In summary, the fundamental principles of anionic chemistry are detail- and electrolyte also should be specially concerned. Owing to the differ-
edly illustrated from the basic theories of bonding structure, crystal lat- ent state of anions in electrolyte and electrode, it is harder to character-
tice and coordination environment. Meanwhile, the positive effect and ize and elaborate the complex chemical reactions at the interface. The
functional mechanism of anionic chemistry for ZIBs are summarized detections of interfacial reaction state could be favorable to comprehen-
and listed item by item, indicating its potential superiority. In spite of sively understand the electrochemical behaviors of batteries, such as ion
the advantages of anionic chemistry, a series of feasible strategies about diffusion kinetics, formation of SEI layer, and charge transfer rate. These
electrode modification and electrolyte modulation have been proposed behaviors have significant effect on the cycling stability, rate capability,
to address the facing issues of anionic chemistry, improve the energy and pseudocapacitive contribution of the batteries. Therefore, the inter-
density and facilitate the further development of ZIBs. These critical facial reaction between electrode and electrolyte deserves more attention
issues mainly include the irreversible structural changes caused by the for the intensive study of anionic chemistry, which is a critical factor
unstable anionic redox reaction, the uncontrollable electrolyte decom- for the electrochemical performances of batteries.
position arised from the higher potential conditions of anionic redox
reaction, and the inferior stability of anion vacancies and surface modi-
fications in the electrodes. Besides, there are also some other obstacles 5.4. Developing Quasi-solid-state or All-solid-state Electrolytes
hindering its further applications, such as the unclear fundamental prin- for ZIBs
ciple and ambiguous redox reaction mechanism of anionic chemistry.
Hence, the outlook and prospective research directions about anionic Current research on ZIBs have been focused on exploring cathode
chemistry may mainly focus on the following aspects: materials with high capacity and optimizing the cycling stability of

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zinc anode. However, taking the practical applications of ZIBs into [13] H. Koga, L. Croguennec, M. Ménétrier, K. Douhil, S. Belin, L. Bourgeois,
concern, people have long neglected the battery’s shelf life. Unfortu- E. Suard, F. Weill, C. Delmas, J. Electrochem. Soc. 2013, 160, A786.
nately, ZIBs using aqueous electrolytes exhibit rapidly deteriorating [14] G. Assat, J. M. Tarascon, Nat. Energy 2018, 3, 373.
properties due to the high temperature sensitivity of water and the [15] J. Vergnet, M. Saubanère, M. L. Doublet, J. M. Tarascon, Joule 2020, 4, 420.
[16] Y. Zhao, W. Cai, Y. Fang, H. Ao, Y. Zhu, Y. Qian, ChemElectroChem
inevitable side reactions between zinc metal and aqueous electrolytes
2019, 6, 2231.
(including corrosion, hydrogen evolution reaction (HER) and passiva- [17] Y. Zuo, B. Li, N. Jiang, W. Chu, H. Zhang, R. Zou, D. Xia, Adv. Mater.
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