Cathode Strategies To Improve The Performance of Z

Review
1 of 24 Electrochemical Science Advances doi.org/10.1002/elsa.202100090
Received: 19 May 2021

Revised: 17 June 2021
Accepted: 19 June 2021
Cathode strategies to improve the performance of zinc-ion

batteries
Pingge He Shaowei Chen
Department of Chemistry and

Biochemistry, University of California, Abstract
Santa Cruz, California, USA Zinc-ion battery (ZIB) has been attracting extensive attention due to its high the-
Correspondence
oretical capacity, high safety, and low cost. However, the exploration of suitable
Shaowei Chen, Department of Chemistry cathode materials to host Zn ions remains a challenge, owing to the strong elec-
and Biochemistry, University of California, trostatic interactions and large steric hindrance effects between Zn ion and host
1156 High Street, Santa Cruz, California
95064, USA. materials. Great efforts have been devoted to the optimization of the structure
Email: shaowei@ucsc.edu and electrochemical property of the cathode materials. In this review article, we
summarize recent cathode-based strategies to address the issues of performance
Funding information
Beijing Natural Science Foundation, degradation and structural collapse of electrode materials within the context of
Grant/Award Number: 2204086; National microstructure design and ion/charge transport mechanism, and include a per-
Science Foundation, Grant/Award Num-
spective to highlight the challenges and promises in the exploitation of cathode
bers: CHE-1900235, CHE-2003685
materials for further enhancement of the performance of ZIBs.
KEYWORDS
cathode material, energy density, rate capacity, structural engineering, zinc ion battery
1 INTRODUCTION ern era.[8] Among them, zinc-ion batteries (ZIBs) have

gained intensive attention, since zinc-metal anode exhibits
The development of rechargeable batteries plays an essen- a high theoretical capacity (specific capacity 819 mAh/g),
tial role in the area of energy conversion and storage. In a low redox potential (−0.763 V vs. standard hydrogen
the past few decades, lithium-ion batteries (LIBs) have electron [SHE]), and relatively high stability in aqueous
dominated both academic and industrial research, due to electrolytes,[9,10] and has found preferable applications in
their high energy density and long cycle life.[1–3] How- high-performance aqueous batteries due to its environ-
ever, the practical application of LIBs is compromised by mental friendliness, low cost, and high safety.[11]
the safety issues, limited lithium resources, and environ- However, the fabrication of suitable cathode materials
mental concerns.[4,5] Thus, research efforts have also been for ZIBs with a high reversible capacity, wide working
devoted to the development of alternative battery systems voltage, and outstanding cycle stability remains a daunting
based on Na and K ions; nevertheless, safety issues remain challenge.[12] Divalent Zn2+ ions show strong electrostatic
a bottleneck.[6,7] Recently, novel multivalent-ion battery interactions with the host structures and large steric
systems based on aqueous electrolytes rather than organic hindrance effects, leading to poor cyclic stability and
electrolytes have been regarded as promising candidates sluggish intercalation kinetics. Thus, the design rules
as the next-generation power supplies to meet the sus- for the cathode materials of ZIBs are fundamentally
tainable development of renewable energy in the mod- different, as compared to that of monovalent ions-based
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the
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© 2021 The Authors. Electrochemical Science Advances published by Wiley-VCH GmbH.
Electrochem. Sci. Adv. 2022;2:e2100090. wileyonlinelibrary.com/journal/elsa 1 of 24

https://doi.org/10.1002/elsa.202100090
Review
batteries. Various types of materials have been used as

cathodes for ZIBs,[13] such as manganese-based oxides,
vanadium-based oxides, Prussian blue analogues (PBAs),
and organic compounds; however, common issues related
to cathode dissolution, electrochemical performance
degradation, and structural collapse during cycling persist
in these cathode materials.[10] Essentially, the perfor-
mance of the cathode materials is closely related to their
microstructures. Therefore, a profound understanding of
the correlation between the material microstructure and
energy storage mechanism is urgently needed so as to
improve the cathode performance.
Recently, a series of reviews have been published on
ZIBs, e.g., the introduction of cathode materials as well
as their synthetic methods,[14] materials chemistry related
to ZIBs,[15] energy storage mechanism,[16] layered oxide
cathodes,[17] layered vanadium oxides,[18] manganese-
based oxides,[19] microstructural engineering of cathode
materials,[20] etc., while a comprehensive review on the
optimization of cathode materials from the perspective
F I G U R E 1 Cathode strategies to improve the performance of
of structural engineering, and the relationship with elec-
advanced ZIBs. Reproduced with permission from ref. [21],
trochemical property and ion/electron transport remains
copyright 2018, Springer Nature; Reproduced with permission from
elusive and is urgently needed. Thus, in this review, we
ref. [22], copyright 2016, American Chemical Society; Reproduced
will first summarize recent progress where cathode-based with permission from ref. [23], copyright 2020, Wiley-VCH;
strategies are exploited for improved ZIB performance, Reproduced with permission from ref. [24], copyright 2019,
within the context of the cathode material structure and American Chemical Society; Reproduced with permission from ref.
energy storage mechanisms. As schematically shown in [25]; copyright 2021, Elsevier
Figure 1, the discussion will focus on the impacts of inter-
layer spacing, crystal structure, valence state, and mor-
phology on the electrochemical properties of the cathode R-, and ε-type,[10,28] by connecting the fundamental MnO6
materials, and relevant strategies to improve the battery octahedral units that consist of one Mn4+ surrounded by
performance, such as intercalation of pillars, defect engi- six oxygen neighbors via the edges and/or corners. Typi-
neering, composite construction, nanostructure design, cally, α-MnO2 possesses a large tunnel structure of [2×2]
and heteroatom doping. Finally, a perspective is included along the c-axis with four edge-sharing MnO6 octahedral
to highlight future research directions for the development units, β-MnO2 shows [1×1] tunnels along the c-axis, γ-
of cathode materials for high-performance ZIBs. MnO2 shows [1×1] and [1×2] hybrid tunnels along the
b-axis (Figure 2), and δ-MnO2 displays a layered struc-
ture with a large interlayer spacing.[10] Since the electro-
2 TYPES OF CATHODE MATERIALS chemical performance highly depends on the crystal struc-
ture of the materials, the different polymorphs of Mn-
Currently, there are mainly four types of cathode materials based oxides exhibit varied electrochemical properties, and
for ZIBs, Mn-based cathodes, V-based cathodes, PBAs, and the ones with larger tunnels or interlayer spaces usually
organic materials. Among them, Mn- and V-based materi- show a faster ion-diffusion capacity. Yet, the rate capability
als with tunnel or layered structures have been widely used remains low and cycle life short for Mn-based oxide cath-
in ZIBs.[26,27] ode materials, due to their low electronic conductivity and
With a wide voltage window, high theoretical capacity, dissolution of Mn in electrolyte. Efforts to address these
low cost, and environmental benignity, Mn-based materi- issues will be discussed in section 4.
als, particularly manganese oxides, have attracted exten- Besides manganese, vanadium also displays rich valence
sive attention as ZIB cathodes.[19] The Mn element shows states varying from +2 to +5, and when used as bat-
rich valance states with various crystalline structures, such tery electrodes, exhibits a high charge/discharge capac-
as MnO2 , Mn2 O3 , Mn3 O4 , and MnO. Among them, MnO2 ity through the multielectron transfer processes. Recently,
exhibits outstanding structural flexibility and can form var- vanadium-based compounds with tunnel-type or layered
ious crystallographic polymorphs, such as α-, β-, γ-, δ-, λ-, structures have been used as promising cathode materials
Review
F I G U R E 2 Crystal structures of different cathode materials, MnO2 (reproduced with permission from ref. [28], copyright 2018,
Wiley-VCH), V2 O5 (reproduced with permission from ref. [29], copyright 2019, Elsevier), V6 O13 (reproduced with permission from ref. [30],
copyright 2019, Wiley-VCH), VS4 (reproduced with permission from ref. [33], copyright 2020, Royal Society of Chemistry), CoFe(CN)6
(reproduced with permission from ref. [35], copyright 2019, Wiley-VCH), C6 Cl4 O2 (reproduced with permission from ref. [39], copyright 2018,
American Chemical Society), MoS2 (reproduced with permission from ref. [41], copyright 2019, American Chemical Society), and ZnMn2 O4
(reproduced with permission from ref. [44], copyright 2019, Elsevier)
for rechargeable ZIBs. In particular, vanadium oxides, such dimensional open framework and large ion-intercalation
as V2 O5 , VO2 , and V6 O13 , with a tunnel framework (Fig- sites for rapid ions transportation (Figure 2),[34] and hence
ure 2), have been widely used for ZIB applications.[29,30] a great potential in aqueous ZIB applications.[35] PBAs like
In addition, mixed valence states in V-based oxides have CoFe(CN)6 [36] are known to exhibit a high rate capabil-
been demonstrated to increase the redox reaction sites and ity, but they suffer a low capacity and short cycle lifes-
thus enhance the capacity of the cathodes.[31] For exam- pan, which severely limits their wide applications in ZIBs.
ple, V6 O13 with alternating single and double vanadium The low capacity of PBAs is attributed to the inactive sites
oxide layers consists of a mixed valence state of V5+ /V4+ , in their structure,[36] and the poor cyclic stability origi-
and offers a high number of active sites for ion storage. nates from phase transformation during cycling.[37] Fea-
As a result, V6 O13 exhibits a high capacity and excellent sible strategies to mitigate these issues will be discussed in
cyclic stability.[30,31] Mixed vanadium valences have also section 4.
been found to improve the electrochemical performance Organic compounds have also been investigated as
of V2 O5 . In comparison to pristine V2 O5 , the incorpo- rechargeable ZIB cathodes, due to their light weight, struc-
ration of V4+ into V2 O5 leads to a higher electrochemi- tural flexibility, sustainability, low cost, multiple electron
cal activity, lower polarization, faster ion diffusion, and reactions, and biodegradable characters.[38,39] More impor-
higher electrical conductivity, which provides an effec- tantly, organic materials with relatively weak intermolec-
tive way to design high-performance V-based oxide cath- ular interactions can offer a sufficient space to accom-
odes for ZIBs.[32] Moreover, V-based sulfides, such as VS4 , modate zinc ions during cycling, leading to outstanding
have also been employed as ZIB cathodes, due to the one- cyclic stability. However, organic compound cathodes usu-
dimensional atomic chain structure (Figure 2).[33] Never- ally suffer a low capacity and unstable voltage plateaus.
theless, similar to Mn-based oxides, vanadium oxide cath- For instance, Chen et al.[40] prepared a quinone (C4Q)-
odes usually experience dissolution and structural degra- cathode for ZIBs which showed a high energy density.
dation during the charge/discharge process, leading to a Unfortunately, to prevent the crossover of the soluble dis-
poor cyclic performance. charge product of the C4Q-cathode in this system, an
PBAs (MFe(CN)6 , with M = Fe, Co, Ni, etc.) typically expensive fluorine-containing membrane (Nafion film)
display a face-centered cubic (fcc) structure with a three- must be used as the separator. Furthermore, the Nafion
Review
separator must be tightly sealed to prevent the mixing For cathode materials with energy storage through
of anolyte and catholyte, which is very difficult to be the (de-)intercalation of Zn2+ , enlarging the interlayer
applied in flexible devices, especially when operated under spacing is a critical route to improve the electrochemical
repeated bending conditions. Further studies are needed performance. Effective methods, such as intercalation of
to develop effective methods to optimize the structure and pillars, have been demonstrated to significantly increase
performance of organic cathode materials. the interlayer spacing of cathode materials and thus
Other cathode materials, such as transition metal enhance their capacity and cyclic stability, which will be
dichalcogenides (TMDs),[41] cobalt-based oxides,[42] discussed in section 4.
molybdenum oxides,[43] and binary metal oxides,[44]
have also been examined for ZIBs (Figure 2). Despite
substantial progress, issues remain with these cathode 3.2 Conversion reaction mechanism
materials, in particular, low capacity, low rate capability,
and short cycle life. Thus, strategies to optimize the struc- Different from materials that serve as hosts for Zn ion
ture and improve the performance of cathode materials insertion/extraction, some cathode materials store energy
are urgently required for the further development of based on conversion reactions. In this mechanism, phase
ZIBs. transformation of the cathode materials usually occurs
during charge/discharge. For example, α-MnO2 cathode
in a MnO2 /Zn battery has been demonstrated to trans-
3 REACTION MECHANISMS OF ZIB form to MnOOH during cycling, and such a phase trans-
CATHODES formation takes place in the presence of water.[53] The
conversion reactions in the cathode can be described as
Understanding the energy storage mechanism is critical follows,
in the rational design of cathode materials for an opti-
mized electrochemical performance. In ZIBs, several reac- 𝐻2 𝑂 ↔ 𝐻 + + 𝑂𝐻 − (1)
tion mechanisms have been proposed for energy storage
of the cathode materials. Herein, the discussion will focus
on three main ones, (1) Zn2+ intercalation/deintercalation
mechanism, (2) conversion reaction mechanism, and (3) 𝑀𝑛𝑂2 + 𝐻 + + 𝑒− ↔ 𝑀𝑛𝑂𝑂𝐻 (2)
H+ /H2 O and Zn2+ co-insertion/extraction mechanism.
3.1 Zn2+ intercalation/de-intercalation 1∕2𝑍𝑛2+ + 𝑂𝐻 − + 1∕6𝑍𝑛𝑆𝑂4 + 𝑥∕6𝐻2 𝑂

mechanism [ ]
↔ 1∕6𝑍𝑛𝑆𝑂4 𝑍𝑛(𝑂𝐻)2 3 ⋅ 𝑥𝐻2 𝑂 + 𝑒− (3)
Similar to LIBs, the energy storage in most cathodes of ZIBs
depends on the intercalation/de-intercalation of Zn ions Such a conversion reaction mechanism has also been
into/from cathode materials. Due to the small ionic radius reported in other materials. For example, Chen et al.[42]
(0.75 Å) that is comparable to that of Li+ , Zn2+ can effec- prepared a Co3 O4 /Zn battery based on Co(III) rich-Co3 O4
tively diffuse into/extract from a range of layered or tunnel- nanorods as cathode. During charge/discharge, the Co3 O4
type host structures.[45,46] For example, in γ-MnO2 (1×1 nanorods were transformed into CoO in aqueous elec-
and 1×2 tunnels) cathode, during the insertion of Zn2+ , trolytes, and the Co(III) rich state in the cathode mate-
spinel-type ZnMn2 O4 is initially produced, followed by rials led to a highly effective reaction. Besides the struc-
tunnel-type γ-Znx MnO2 , and finally layered Znx MnO2 .[47] ture of cathode materials, the operation voltage and elec-
Besides MnO2 , Zn2+ intercalation/de-intercalation can trolyte media (including ion concentration, pH, additive,
also occur in layered or tunnel-type vanadium-based and so on) also show significant influences on the conver-
oxides, owing to their large ion-transfer channels, multiple sion reaction process. Cathode materials based on the con-
oxidation states of vanadium, and high capacities (gener- version reaction mechanism can be engineered to exhibit a
ally > 300 mAh/g).[48,49] Other materials, such as MoS2, [50] large specific surface area, mixed valence-states, and con-
MoO3 ,[43] VS2 ,[51] PABs with open frameworks, as well trollable porous structure, so as to increase the accessibility
as NASICON-type phosphates,[52] have also been demon- by electrolytes, improve the reaction kinetics, and conse-
strated as electroactive hosts for Zn2+ intercalation/de- quently enhance the discharge capacity and rate capability
intercalation. of the cathodes.
Review
3.3 H+ /H2 O and Zn2+ co-insertion 4 STRATEGIES TO IMPROVE THE

mechanism ELECTROCHEMICAL PERFORMANCE OF
CATHODES
Besides Zn2+ , protons (H+ ) in an aqueous ZIB have
been recognized as the main charge carrier, due to their In ZIB applications, many cathode materials suffer
small ionic radius and low atomic mass, and inser- electrochemical performance degradation during
tion/extraction of both H+ and Zn+ takes place con- charge/discharge, due to dissolution, structural col-
currently during charge/discharge.[54,55] For instance, a lapse, poor electrical conductivity, and sluggish transport
unique H+ and Zn2+ co-insertion mechanism has been kinetics.[59–61] To mitigate these issues and enhance the
proposed to account for the performance of a Zn/MnO2 ZIB performance, a number of strategies have been exam-
battery using a ZnSO4 -based aqueous electrolyte,[56] as ined to engineer the structure of the cathode materials.
ZnMn2 O4 and MnOOH phases are both observed after dis-
charge, due to the insertion of Zn2+ and H+ , respectively.
As compared to Zn2+ , the smaller size of H+ enables faster 4.1 Intercalation of pillars
insertion kinetics, resulting in a big difference in the gal-
vanostatic intermittent titration technique (GITT) profiles, Based on the Zn2+ insertion/extraction mechanism, cath-
where the H+ intercalation process shows a much lower ode materials are required to exhibit a large interlayer spac-
overvoltage at the first discharge platform than that of ing to accommodate Zn ions. However, traditional cath-
Zn2+ at the second platform.[56] odes usually exhibit only a limited interlayer spacing and
Furthermore, H2 O has also been demonstrated to unstable structure during Zn ion de/intercalation,[10,14]
play an essential role in the Zn2+ storage process. A compromising their application as high-performance cath-
unique Zn2+ /H2 O co-insertion storage mechanism has odes for ZIBs. Great efforts have been devoted to these
been revealed in a Zn0.25 V2 O5 ⋅nH2 O/Zn battery.[57] When issues, among which the most effective way is to interca-
the cathode materials were immersed into the aqueous late metal ions,[62,63] polymers,[64,65] or molecular water
electrolyte, H2 O molecules would intercalate into pristine (H2 O)[66,67] as pillars into the cathode materials to enlarge
Zn0.25 V2 O5 ⋅nH2 O, leading to an increment of the inter- the interlayer spacing and enhance the structural stability
layer distance. Then, in the discharge process, the H2 O during the charge/discharge process.
molecules were de-intercalated from the cathode accom-
panied by Zn2+ intercalation, whereas during charging,
intercalation of H2 O molecules occurred along with Zn2+ 4.1.1 Metal-ion intercalation
de-intercalation, leading to highly reversible and stable
electrochemical operation. Metal-ion intercalation can be classified based on the kind
Based on the co-insertion mechanism of energy stor- of intercalated metal ions, i.e., transition metal ions, alkali
age, cathodes with structural H2 O and selection of suitable metal ions, alkali-earth metal ions (Mg2+ , Ca2+ , etc.),
aqueous electrolytes are expected to enhance the electro- and even aluminum ions (Al3+ ). Wang et al.[63] reported
chemical performance of ZIBs. that pre-intercalation of Zn2+ transformed layered δ-MnO2
Other reaction mechanisms have also been proposed nanosheets into highly stable, tunnel-structured Znx MnO2
for ZIBs. For example, an “ion-coordination” mecha- nanowires (Figure 3A). This enabled fast kinetics and sig-
nism was proposed by Chen et al.,[40] where C4Q was nificantly improved the cycling performance of ZIBs with
used as the cathode material and the carbonyl groups a high capacity-retention rate of 83.1% after 5000 cycles at
in C4Q acted as the active sites for Zn ion storage, 15 mA/cm2 (Figure 3B).[63] Zn ions can also act as pillars
as Zn2+ ions were coordinated to the electronegative for vanadate cathodes to enhance the cycle life and low-
oxygen atoms. In another study,[58] an anion temperature behaviors.[68] After the first discharge pro-
intercalation/de-intercalation mechanism was revealed cess, the NH4 ions in the (NH4 )2 V6 O16 ⋅1.5H2 O (NVO) cath-
in a Zn/graphite battery system consisting of a ode were transferred into the aqueous electrolyte leav-
zinc metal anode, graphite cathode, and 1 M zinc dibis ing enough vacancies behind for Zn ion intercalation.
(trifluoromethylsulfonyl)imide (Zn(TFSI)2 )/acetonitrile The trapped Zn(H2 O)6 2+ ions in the interlayer not only
electrolyte. Energy storage in such a Zn/graphite battery helped stabilize the vanadium oxide layer but also pro-
was based on the (de)intercalation of TFSI− anion into vided enough interlayer spacing for fast ion kinetics during
the graphite (graphite[TFSI– ]x ) and the electrochemical the subsequent insertion/extraction. As a result, the NVO
plating/stripping of Zn2+ on the anode. cathode displayed a high specific capacity of 385 mAh/g,
Review
F I G U R E 3 (A) Schematic diagram of the formation of Znx MnO2 nanowires and their crystal structure. (B) Cycling performance of
MnO2 and Znx MnO2 based ZIBs at 15 mA/cm2 (reproduced with permission from ref. [63]; copyright 2020, Wiley-VCH). (C)
Charge/discharge curves of a Zn/NVO battery in the 2nd cycle at varied current densities at a low temperature of −20°C (reproduced with
permission from ref. [68]; copyright 2019, Elsevier). (D) TEM-EDX elemental mapping images and (E) XPS spectra of CuVO-300. (F)
Long-term cycling performances of TVO-300 and VO-300 at 10 A/g with insets showing a lamp panel illuminated by four Zn/CuVO-300 coin
cells (reproduced with permission from ref. [69]; copyright 2019, Elsevier)
and a good electrochemical performance even at low tem- Meanwhile, alkali metal ions, such as Li, Na, and K,
peratures (Figure 3C).[68] have also been demonstrated to improve the electrochemi-
Besides Zn ions, other transition metal ions have cal performance of cathodes by tuning the electronic struc-
also been used as effective pillars for cathode structure ture and stabilizing the material’s layered structure. In a
enhancement. Zhou et al.[69] demonstrated that chemical recent study,[70] Geng et al. fabricated K+ pre-intercalated
pre-intercalation of transition-metal ions (e.g., Fe2+ , Co2+ , layered V2 O5 (K0.5 V2 O5 ) electrodes with metallic features
Ni2+ , Mn2+ , Zn2+ , and Cu2+ ) into the interlayer of V2 O5 and observed an excellent zinc storage performance. The
(TVO) could effectively improve the electrochemical per- optimized K0.5 V2 O5 exhibited a Pmm2 symmetry structure
formance of aqueous ZIBs, in terms of high capacity, rate with the K atom occupying the hollow site between two
capability, long-term cycling stability, as well as excellent V2 O5 layers (Figure 4A). Compared with pristine V2 O5 ,
broad temperature adaptability. The successful introduc- K0.5 V2 O5 expanded along the a and c directions, but shrank
tion of metal ions (particularly Cu ions, Figure 3D and along the b direction, with a final volume of V2 O5 slightly
E) into the V2 O5 (VO) interlayers can not only drastically increased from 177 Å3 to 187 Å3 after the insertion of K
enhance the specific capacity, but also improve the struc- ions. By analyzing the density of states (DOS), both the
tural stability during cycling, thus leading to a long cycle valence band edge and conduction band edge of K0.5 V2 O5
life and an ultrahigh capacity retention of 88% over 10,000 showed a significant blue shift, resulting in the polarized
cycles (Figure 3F). and metallic band structure, as compared to that of V2 O5
Review
F I G U R E 4 (A) Top and side views of V2 O5 and K0.5 V2 O5 . The green frames indicate the unit cell. The red, grey, and purple spheres
denote O, V, and K atoms, respectively. (B) DOS of V2 O5 . (C) DOS of K0.5 V2 O5 (reproduced with permission from ref. [70]; copyright 2021,
Royal Society of Chemistry). (D) SEM-EDX elemental maps of NVO nanowires. (E) Schematic illustration of the zinc-storage mechanism in
the NVO electrode (reproduced with permission from ref. [71]; copyright 2018, Wiley-VCH). (F) Long cycling performances at 10 A/g of
LVO-250 and VO-250 (reproduced with permission from ref. [72]; copyright 2018, Royal Society of Chemistry)
(Figure 4B and C). That is, the band structure of V2 O5 egy based on chemical intercalation of Li+ into the inter-
was readily manipulated by K ion intercalation.[70] K+ layer of V2 O5 ⋅nH2 O (VO), i.e., Lix V2 O5 ⋅nH2 O (LVO), to
ions have also been employed as pillars for MnO2 , and enlarge the layer spacing and enhance Zn2+ diffusion.
the pre-intercalated K ions in the layered-type matrix have As a cathode in aqueous ZIBs with a 2 M ZnSO4 elec-
been demonstrated to stabilize the layered structures and trolyte, the LVO thermally annealed at the temperature
expand Zn2+ migration channels, facilitating the diffusion of 250 °C (LVO-250) demonstrated a high rate capacity
of Zn2+ in the MnO2 cathodes.[62] and excellent cycling performance, with a high capac-
In another study,[71] Mai’s group prepared a Na0.33 V2 O5 ity retention of 192 mAh/g after 1,000 cycles at 10 A/g
cathode for ZIBs and observed improved electrical conduc- (Figure 4F).
tivity, which was attributed to the intercalation of Na+ into Moreover, alkali-earth metal ions have also been
V2 O5 . From Figure 4D, one can see that the Na, V, and employed as pillars for cathodes with improved electro-
O elements were uniformly distributed, and no other ele- chemical performance. For instance, Alshareef et al.[73]
ment was detected. During charge/discharge (Figure 4E), prepared a layered Mg2+ -intercalated V2 O5 as the cathode
Zn ions reversibly de/intercalated into the cathode struc- material for aqueous ZIBs. The large radius of hydrated
ture, where the interlayer spacing was enlarged by the Mg2+ led to an increased interlayer spacing of 13.4 Å,
Na+ pillars. Zhou et al. [72] proposed an effective strat- enabling efficient Zn2+ (de)insertion. As a result, the
Review
F I G U R E 5 (A) Schematic illustration of the expanded intercalated structure of PANI-intercalated MnO2 nanolayers (reproduced with
permission from ref. [21]; copyright 2018, Springer Nature). Differential charge density with Zn-ion intercalation in (B) pristine V2 O5 and (C)
PANI-V2 O5 . The yellow and cyan regions represent charge accumulation and depletion, respectively. Blue, red, brown, light blue, gray, and
white balls represent V, O, C, N, Zn, and H atoms, respectively. (D) Calculated binding energy of Zn ions inserted in V2 O5 and PANI-V2 O5
(reproduced with permission from ref. [78]; copyright 2020, Wiley-VCH). (E) In situ XRD tests of PANI100–V2 O5 and the corresponding
time–voltage curves (reproduced with permission from ref. [79]; copyright 2020, Wiley-VCH)
obtained porous Mg0.34 V2 O5 ⋅0.84 H2 O cathodes worked in various types of cathode materials (e.g., MnO2 , V2 O5 , etc.)
a wide potential window of 0.1 to 1.8 V versus Zn2+ /Zn, and and advanced battery systems.
can deliver high capacities of 353 and 264 mAh/g at cur-
rent densities of 100 and 1000 mA/g, respectively, along
with long-term durability. Additionally, Zhang et al.[74] 4.1.2 Polymer intercalation
demonstrated that insertion of Ca2+ into hydrated vana-
dium oxide cathode expanded the layer spacing, greatly Besides metal ions, polymers have also been used as
reduced the electrostatic interactions, and increased the promising pillars to engineer the cathode structure.[77]
reversibility of the vanadium oxide. Besides these alkali- For instance, Wang et al.[21] designed a polyaniline
earth metal ions, Al3+[75] and even non-metallic NH4+[76] (PANI)-intercalated layered manganese dioxide as ZIB
ions have also been reported as effective pillars to optimize cathode and observed significantly improved cyclic sta-
the structure of cathode materials. bility. The sample was prepared via a one-step pro-
Notably, these universal strategies based on pre- cedure where oxidative polymerization of aniline and
intercalated metal ions in the host materials have indeed reduction of 𝑀𝑛𝑂4− occurred simultaneously at the
been confirmed to enlarge Zn2+ diffusion channels, organic/inorganic interface, leading to the layer-by-layer
improve electrical conductivity, and stabilize the structure assembly of MnO2 and PANI (Figure 5A). Such a PANI-
during cyclic charge/discharge, leading to fast Zn2+ reinforced layered structure with nanosized MnO2 parti-
diffusion, and long cycle life,[69] and can be applied to cles (∼10 nm) efficiently eliminated the hydrated H+ /Zn2+
Review
insertion-induced phase transformation and subsequent the VOH sheets, and hence the formation of a graphene-
structural collapse, resulting in a long cycle life.[21] like nanosheet morphology. The obtained PANI−VOH
Zhang et al.[65] designed a PANI-intercalated hydrated nanosheets possessed a greatly boosted total charge stor-
V2 O5 composite (PANI/V2 O5 ), in which PANI not only age capacity, due to abundant surface sites for reversible
expanded the interlayer spacing (as large as 14 Å) of V2 O5 V5+ to V3+ redox reactions. Electrochemical impedance
for fast and reversible Zn2+ ion (de)intercalation, but also spectroscopy (EIS) and GITT analyses showed that with
improved the specific capacity of the cathode materials. the PANI−VOH nanosheets, the charge-transfer resistance
The as-assembled Zn//PANI/V2 O5 battery exhibited a high (RCT ) decreased and concurrently the diffusion coefficient
specific capacity up to 353.6 mAh/g at 0.1 A/g, and a sta- of Zn2+ increased (by a factor of 10∼100), as compared to
ble cycling performance. In another study,[78] Li’s group the VOH baseline. Besides PANI, polypyrrole (PPy) has
developed an in-situ PANI intercalation strategy to facil- also been used as intercalation pillars. Srinivasan et al.
itate the Zn2+ (de)intercalation kinetics in V2 O5 . They [81] studied the effect of PPy intercalation on the lay-
found that not only the interlayer spacing was significantly ered VOPO4 host, and observed that the enlarged inter-
enlarged, but more importantly, the electrostatic interac- layer space made Zn2+ cation (de)intercalation feasible,
tions between Zn2+ ions and O2− hosts, which are known leading to a high capacity and long cycle life. Moreover,
to hinder Zn2+ diffusion, were effectively reduced by the Xia et al.[77] prepared poly(3,4-ethylenedioxythiophene)
unique π-conjugated structure of PANI. Differential charge (PEDOT) intercalated NH4 V3 O8 (PEDOT-NVO) as a cath-
density was then calculated for both pristine V2 O5 (Fig- ode material, leading to an increased interlayer spacing of
ure 5B) and PANI-V2 O5 (Figure 5C) as a single Zn2+ was 10.8 Å (from 7.8 Å for pristine NVO). This cathode mate-
inserted into the frameworks. Substantial charge deple- rial exhibited an improved capacity of 356.8 mAh/g at 0.05
tion and accumulation could be identified around Zn and A/g and 163.6 mAh/g, even at the highest current den-
adjacent O atoms, respectively. The charge redistribution sity of 10 A/g (with a high retention from 0.05 to 10 A/g),
patterns were very similar between Zn and the four adja- and featured an ultra-long lifetime of over 5,000 charge-
cent O atoms for both systems. However, charge accumula- discharge cycles with a capacity retention of 94.1%. Addi-
tion was observed around the next-nearest O atoms in bulk tionally, Sun et al.[82] demonstrated that the introduction
V2 O5 (Figure 5B), indicating strong binding interaction of of PEDOT contributed to the formation of oxygen vacancy
Zn and sluggish Zn2+ diffusion in the pristine V2 O5 . From in V2 O5 , and meanwhile led to an enlarged interlayer spac-
Figure 5D, the calculated binding energy of Zn ion inserted ing. The as-prepared cathode materials exhibited a high
in PANI-V2 O5 was markedly lower than that in pristine capacity of 449 mAh/g at a current density of 0.2 A/g, with
V2 O5 (1.67 vs 2.06 eV), suggesting that it was much eas- an excellent cyclic performance of 94.3% after 6,000 cycles.
ier for Zn ions (de)intercalation in PANI-V2 O5 . As a result, From these studies, one can see that intercalation of
the PANI-intercalated V2 O5 electrode exhibited a high rate select polymers into host cathodes can not only enlarge the
capability of 197.1 mAh/g at the current density of 20 A/g interlayer spacing, but also weaken the electrical interac-
with a capacity retention of 97.6% over 2000 cycles. Sim- tions between Zn ions and host materials, and hence sig-
ilarly, Zhang et al.[79] fabricated a cathode structure with nificantly improve the Zn2+ diffusion kinetics. To optimize
PANI in situ intercalated into layered vanadium oxide in the performance, further studies should be extended to the
order to enlarge the lamellar spacing and enhance the bat- wide variety of other conducting polymers, along with the
tery performance. As shown in Figure 5E, the in-situ XRD development of suitable fabrication methods. Additionally,
results revealed that the crystal structure of PANI100–V2 O5 the effects of electrolyte on the polymers should be taken
is fully reversible during the intercalation and extraction into consideration for cathode design.
of Zn2+ ions. More importantly, the accumulation of more
Zn2+ ions can be achieved via the enlarged interlayer spac-
ing from 1.42 to 1.62 nm, as calculated from the variation 4.1.3 Water intercalation
of diffraction peaks, leading to a larger specific capacity.
The in-situ characterizations in this work demonstrated Water intercalation includes structural water molecules in
that PANI as the guest materials not only enlarged the host materials and intercalated water occurring during the
lattice spacing for ready accumulation of Zn2+ ions and charge/discharge process in aqueous ZIBs, where water
improved the specific capacity, but also buffered the vol- molecules are co-intercalated with Zn ions upon discharge.
umetric expansion and improved the stability due to the Mai’s group[83] has recently discussed the impacts of water
flexible molecular nature. on the electrochemical performance of ZIBs, where the
Furthermore, Mutlin et al.[80] found that intercalation water molecules could affect the electrode, active material,
of PANI into vanadium oxygen hydrate (VOH) led to not electrolyte, and the overall battery performance of ZIBs
only an enlarged interlayer spacing, but also exfoliation of from different aspects.
Review
F I G U R E 6 (A) Charge–discharge curves for the first three cycles of the as-prepared VOG. (B) Cycling performance of VOG and
VOG-350 (without structural water) at 6 A/g (reproduced with permission from ref. [84]; copyright 2017, Wiley-VCH). Diffusion paths of Zn
ion in V6 O13 (C) with and (D) without water (projected down [001]). (E) Calculated diffusion barriers for paths in (C) and (D) (reproduced
with permission from ref. [67]; copyright 2019, Wiley-VCH)
In terms of the cathode materials, optimization strate- rearranged to minimize electrostatic repulsion from the
gies have been developed by exploiting the influence of lattice oxygen atoms. In the anhydrous case (Figure 6D),
water molecules on the crystal structure, type of com- although Zn ion diffusion took a more straightforward
pound bond, electronic structure, and valence state. Mai path, it tended to skew toward one side at the end. As
et al.[84] found that structural water molecules acted as shown in Figure 6E, the kinetic barrier for Zn ion diffusion
“lubricants” and facilitated the reversible mobility of Zn2+ for the case with water was much lower than that with-
into the layered V2 O5 ⋅nH2 O/graphene structure (VOG), out water, demonstrating easier diffusion of Zn ions in the
consequently leading to the high capacity of 381 mAh/g cathode materials with the assistance of water.[67] There-
at 60 mA/g (Figure 6A) and outstanding cycling stabil- fore, water co-intercalation provides a low kinetic energy
ity with a capacity retention of 71% after 900 cycles (Fig- barrier by expanding the cross-sectional area along the dif-
ure 6B). Furthermore, the interlayer water could act as fusion path and lowering the charge of Zn, and the com-
an electrostatic shield to modulate the polarization effects, bined effects may contribute to the high-rate performance.
especially in multivalent ion batteries. The wide applica- Similar to metal ions and polymers, either structural
tion of layered vanadates in ZIBs, such as V6 O13 . nH2 O,[85] water or intercalated water can act as effective pillars to
Na2 V6 O16 . 3H2 O,[86] V10 O24 . 12H2 O,[87] and H2 V3 O8 ,[88] improve the structural stability of cathode materials dur-
indicate the great potential of layered vanadium oxides ing the charge/discharge processes, as well as provide fast
containing structural water as ZIB cathode materials. Zn2+ diffusion paths. More importantly, water can be used
Moreover, upon discharge, water usually co-intercalates as a “lubricant” to lower the Zn2+ migration energy barrier
with Zn ions into the cathode materials in aqueous elec- and thus facilitate Zn2+ diffusion. To further improve the
trolytes. For instance, H2 O in the aqueous electrolyte performance, co-intercalation of multiple pillars into cath-
can buffer the large charge density of divalent Zn2+ and ode materials can be conducted to exploit their synergis-
enhance Zn diffusion, which endows the anhydrous V2 O5 tic interactions. Yet, it remains a challenge to optimize the
electrode with a high ion-diffusion coefficient of 10−10 - loading ratios of the various pillars in the cathode materi-
10−11 cm2 s−1 .[89] Choi et al. [67] demonstrated that the als for maximal performance.
water co-intercalation mechanism facilitated Zn ion diffu-
sion throughout the host lattice and electrode-electrolyte 4.2 Heteroatom doping
interface via electrostatic shielding and concurrent struc-
tural stabilization. Based on the simulation results of water Heteroatom doping can effectively modify the structure
co-intercalation (Figure 6C), it was observed that Zn pre- of the cathode materials, such as tuning the electronic
ferred to follow a zigzag route along the b axis from one structure, enhancing the electrical conductivity, and
octahedral site to the adjacent one, with water molecules facilitating ion diffusion, all conducive to performance
Review
F I G U R E 7 (A) Charge distribution of Mn2 O3 and NM20. GITT profiles and diffusion coefficients of (B) NM20 and (C) Mn2 O3 . (D) ICP
measurement of manganese dissolution in 2 m ZnSO4 electrolyte after different cycles. (E) Calculated formation energy (in eV) of Mn2 O3 and
NM20 (reproduced with permission from ref. [23]; copyright 2020, Wiley-VCH). (F) Rate performance of MZO at various current densities
from 0.5 to 5 A/g. (G) Cycle performance and Coulombic efficiency of MZO at a current density of 5 A/g (reproduced with permission from
ref. [91]; copyright 2021, Elsevier)
improvement. There are generally two types of dopants, 10–102 times higher than that of Mn2 O3 (Figure 7C), indi-
metal ions, and nonmetal atoms. cating enhanced diffusion in NM20. Moreover, the evo-
Metal-ion dopants are expected to optimize the elec- lution of manganese concentration in the electrolyte was
tronic state and stabilize the structure of the host materials, detected via the inductively coupled plasma (ICP) mea-
consequently addressing the issues of dissolution during surement and the results were displayed in Figure 7D. The
the cycling process, low electrical conductivity, and struc- dissolution of manganese could be effectively alleviated
tural degradation of cathodes during charge/discharge. to only 2 mg/L with the NM cathodes; in sharp contrast,
Huang et al. [23] prepared a Ni-doped Mn2 O3 (NM) to the manganese in pure Mn2 O3 displayed a fast dissolu-
suppress the dissolution of manganese. The incorporation tion in the first few cycles. The suppression of manganese
of Ni2+ was found to promote electronic rearrangement, dissolution originated from stabilizing the Mn-O bond
enhance electrical conductivity, and improve the reaction of Mn2 O3 by reducing the formation energy (from 417.5
kinetics and electrochemical performance. Moreover, the to 416.1 eV) after Ni2+ steadily intercalated into Mn2 O3
extra electrons in NM with an atomic ratio of Ni and Mn in (Figure 7E), which effectively strengthened the inherent
the precursor of 1:20 (NM20) were accumulated around the stability. In another study,[90] Wang et al. loaded nickel
Mn atoms adjacent to the inserted Ni atoms (Figure 7A), and cobalt co-substituted spinel ZnMn2 O4 nanoparticles
which generated a strong interaction between the inter- homogeneously onto N-doped reduced graphene oxide
connected manganese and oxygen atoms (Mn-O), thus (ZnNix Coy Mn2-x-y O4 @N-rGO), and observed that the co-
enhancing its structural stability. As shown in Figure 7B, substituting of nickel and cobalt effectively facilitated Zn2+
the Zn ion diffusion coefficient (DZn 2+ ) of NM20 during de-intercalation and stabilized the spinel structure that
discharging was estimated to be 10−7 –10−9 cm2 /s, about productively prevented the Jahn-Teller distortion of Mn3+ .
Review
Mn has also been used to dope ZnO as a high- to 1600 cycles. The outstanding electrochemical perfor-
performance cathode, which not only adjusts the elec- mance was attributed to the amorphous carbon shell and
tronic structure, but also enhances the electrical conduc- the onion-like N-doped carbon derived from the carboniza-
tivity, thereby upraising the reaction kinetics.[91] Conse- tion of ZIF-8 in such hybrid structures, which significantly
quently, the Mn-doped ZnO cathode (MZO) displays an enhanced the overall electrical conductivity and facilitated
appreciable rate performance, with a capacity of 268.1 effective electron transport. In a recent study,[98] a hybrid
mAh/g at 1 A/g, and retains 163.8 mAh/g at 5 A/g structure consisting of Mn-doped V6 O13 nanoribbons and
(Figure 7F). Most importantly, a high energy density N-S modified porous carbon structure (MnVO/(SN)-C)
(206.9 Wh/kg), power density (6896.7 W/kg), and supe- was fabricated, where the doping of Mn ion into V6 O13 was
rior cycle durability (146.7% after 10,000 cycles relative to found to optimize the electronic structure, and the rigid
the first cycle, Figure 7G) endow this material with a high and conductive N-S doped carbon structure boosted the
potential for energy storage. electron transport rate in electrochemical reactions, and
Other ions, such as Al, and Ag,[92,93] have also been suppressed the huge volume expansion. As a result, this
used as dopants to productively tune the electrochemi- electrode exhibited a high capacity of 414.2 mAh/g, high
cal properties of cathode materials, leading to significantly rate capability (with a 67.37% capacity retention from 1 to
improved energy density, rate capability, and cyclic stabil- 10 A/g), and outstanding long-term cycle stability (100.1%
ity. after 1000 cycles at 10 A/g).
Doped host materials with nonmetal atoms, such as N, Doping is expected to apply to a wide range of cathode
O, P, and S, represent another promising route to improve materials of ZIBs, in comparison with the interlayer inter-
the electrochemical properties.[94,95] In ZIBs, nonmetal calation method that is only available for layered materi-
atom-doped carbons have attracted extensive attention as als. Notably, doping is not limited to active materials. It
both conductive substrate and modification coating for can also be applied to the substrates and coating materi-
active materials to improve the electrical conductivity and als in the composite cathodes. Upon doping modification,
alleviate volumetric change of the cathodes. For instance, the intrinsic properties (electrical conductivity, structure
N-doped graphene has been used to support ZnMn2 O4 stability, etc) of the cathode materials can be significantly
nanoparticles, forming high-performance nanocompos- enhanced, due to manipulation of the electronic structure
ite cathodes for ZIBs.[44] These cathodes with ultrafine and even the phase transformation path. Furthermore,
ZnMn2 O4 nanoparticles anchored on N-doped graphene doping can lead to an imbalanced charge distribution and
exhibit an ultralong cycle life with 97.4% capacity reten- local electric field inside the crystal structure of the cath-
tion after 2,500 cycles at 1000 mA/g, which is attributed to ode materials, thus boosting their ion/electron migration
the synergistic effect of superfine ZnMn2 O4 nanoparticles rates. Yet, currently most research mainly focuses on the
that provide rapid surface capacitive reaction and short choice of dopants and their synthesis methods, whereas
electron/ion transport path lengths, as well as the highly the doping mechanism and the effects of dopant concen-
conductive N-doped graphene medium that facilities fast tration and occupation position have been rarely reported.
electron transport and stabilizes the composite structure to Further studies are desired to address these important
tolerate volume expansion during charge/discharge. More- issues.
over, N-doped hollow carbon spheres (NHCSs) have been
employed as growth substrates to effectively promote the 4.3 Defect engineering
uniform distribution of active MnO2 nanosheets, increase
the total contact area at the electrode-electrolyte interface, Defect engineering has been recognized as an essential
and facilitate exposure of active sites for maximum utiliza- way to modify the electronic properties of materials, in
tion of the active materials.[96] The combination of NHCSs particular, cathode materials for ZIBs. Typically, there are
also significantly enhances the conductivity of the posi- four types of material defects,[99,100] (1) oxygen vacancy, (2)
tive electrode. Meanwhile, the MnO2 -NHCSs hybrid with cation vacancy, (3) cationic doping, and (4) anionic dop-
a hollow structure possesses a large specific surface area, a ing. Since doping has been discussed in the previous sec-
large cavity volume, and a short ion diffusion path, which tion, this section mainly focuses on the oxygen and cation
is kinetically favorable for ion and electron transport. vacancies.
Besides being used as the substrates for active material
support, doped carbons can also act as a modification layer 4.3.1 Oxygen vacancy
for cathode materials. Sun et al. [97] prepared an onion-like
N-doped carbon modified MnOx nanorod (MnOx @N-C) Due to the low formation energy, oxygen vacancy has
as cathode, which exhibited a high capacity of 305 mAh/g been considered as a major defect to tune the electronic
after 600 cycles at 500 mA/g and retained a capacity of structure and physicochemical properties of cathode mate-
100 mAh/g at 2000 mA/g after long-term cycling of up rials. Xia et al.[101] developed a low-temperature defect
Review
F I G U R E 8 DOS of (A) MnO2 , (B) MnO2–x , and (C) N-MnO2–x (reproduced with permission from ref. [101]; copyright 2019, Wiley-VCH).
(D) Atomically resolved scanning transmission electron microscopy-annular bright-field (STEM-ABF) image of a C-MnO2 nanosheet, with a
larger view of the straight nanosheet in the inset. (E) Atomically resolved STEM-ABF image of one curved Od-MnO2 nanosheet, with a larger
view of the nanosheet in the inset. (F) Schematic illustration of oxygen-deficient σ-MnO2 for Zn ion storage. (G) Calculated adsorption
energies for Zn2+ on the surfaces of pristine and oxygen-deficient σ-MnO2 . Four possible sites for Zn adsorption are selected with a different
distance from oxygen vacancy (VO). (h) Schematic illustration of Zn2+ adsorption/desorption on pristine and oxygen-deficient MnO2
(reproduced with permission from ref. [99]; copyright 2019, Wiley-VCH)
engineering method to fabricate N-doped MnO2 cathode adsorption were close to the thermoneutral value of ca.
with abundant oxygen vacancies. The N dopants and oxy- 0.05 eV at the vicinity sites to oxygen vacancy in Od -
gen vacancies in MnO2 were confirmed by synchrotron MnO2 , which was energetically conducive to reversible
spectroscopy measurements, and density functional the- Zn2+ adsorption/desorption; by contrast, Δ𝐺𝑍𝑛2+ became
ory (DFT) calculations were conducted to investigate the markedly more negative at ca. −3.31 eV on pristine MnO2 ,
effects of N dopants and oxygen vacancies on the elec- indicating much stronger adsorption of Zn2+ . This would
tron densities and electrochemical properties of MnO2 . render desorption difficult, mask the electrochemically
As shown in Figure 8a-8b, MnO2–x (0.12 eV) exhibited active surface area (Figure 8H), and eventually compro-
a much lower bandgap than pristine MnO2 (1.83 eV), mise the capacity performance.
indicating that the formation of oxygen vacancies could Oxygen vacancy has also been exploited for perfor-
greatly improve the electrical conductivity. After N dop- mance enhancement in V-based oxides. Peng et al.[102] pre-
ing, the bandgap of N-MnO2–x further decreased to 0.1 eV pared oxygen-deficient V6 O13 (Od -VO) to increase divalent
(Figure 8C), which further enhanced the electrical con- cation-intercalating sites and thereby the capacity. The Od -
ductivity. In another study,[99] Xue et al. optimized the VO structure showed a thermoneutral Gibbs free energy of
electrochemical performance of MnO2 cathode materials Zn2+ desorption, which suggests an effortless Zn2+ release
by the formation of oxygen vacancies (Od -MnO2 ). As com- by the cathode in its discharge state, fully accessible for
pared to pristine MnO2 that possessed an interlayer spac- the next charging process. In contrast, pristine VO (p-VO)
ing of ca. 0.69 nm (Figure 8D), the Od -MnO2 nanosheets exhibited a much higher Gibbs free energy of desorption,
exhibited a slightly shorter interlayer spacing of ca. 0.68 nm again, indicating a difficult Zn2+ release, thus leading to a
and were mostly curved, thinner, and shorter (Figure 8E). deterioration in cycling stability. As shown in Figure 9A,
Notably, Zn2+ storage in σ-MnO2 arose from diffusive and the average diffusion coefficient of Zn2+ (𝐷𝑍𝑛2+ ) in Od -VO
capacitive contributions (Figure 8F). From Figure 8G, one at the discharge and charge plateaus were approximately
can see that the Gibbs free energies (Δ𝐺𝑍𝑛2+ ) of Zn2+ 1.1 × 10−11 and 0.4 × 10−11 cm2 /s, respectively, which are
Review
F I G U R E 9 (A) GITT profiles of p-VO and Od -VO electrodes, and the corresponding charge distribution of (B) p-VO and (C) Od -VO
(reproduced with permission from ref. [102]; copyright 2019, Wiley-VCH). (D) Schematic illustration of the synthesis process of VO •• −VO2 . (E)
SEM images of VO •• −VO2 . Projected density of states (PDOS) of (F) VO2 and (G) VO1.75 . (H) Calculated Zn ion diffusion energy barriers in
VO2 and VO1.75 (reproduced with permission from ref. [103]; copyright 2020, American Chemical Society)
comparable to that of Li+ and much higher than that of been employed, such as hydrothermal/solvothermal pro-
p-VO. Additionally, p-VO exhibited a uniform charge dis- cess, chemical etching, electrochemical treatment, etc.,
tribution (Figure 9B), while electrons were accumulated which show great potential in cost-effective, large-scale
around Od -VO (Figure 9C). These observations indicate industrial applications. However, it is difficult to control
that when the oxygen atoms are extracted from the vana- the precise location and concentration of oxygen vacancy
dium oxide lattice, defective sites form with spare elec- in the cathode materials. In addition, advanced character-
trons, which can then contribute to the delocalized elec- ization techniques are needed to investigate the influences
tron cloud of Od -VO, leading to an increased capacity. of oxygen vacancy on the Zn ion diffusion process.
Furthermore, Cao et al. [103] introduced oxygen vacancy
into VO2 (VO •• −VO2 ) through a repeated phase transi-
tion process (Figure 9D) and systematically investigated 4.3.2 Cation vacancy
the impacts of oxygen vacancy on Zn2+ intercalation in
VO2 . The obtained VO •• −VO2 exhibited a nanosheet mor- Cation vacancy refers to a cation missing from its lat-
phology with a thickness of ca. 5 nm (Figure 9E), and tice site, and this type of defect usually occurs in com-
the VO1.75 model was chosen for first-principles calcula- pounds where metals can exhibit a variable valency,
tions to study the impacts of VO •• on their electronic struc- such as Mn-based oxides. Chen’s group first developed
tures and zinc ion storage, primarily because of a similar a cation-deficient spinel ZnMn2 O4 cathode for ZIBs.[22]
VO •• concentration. Figure 9F and G shows the DOS and In a perfect spinel without cation deficiency, Zn2+ ions
band structure of the VO1.75 and VO2 structures. After the migrate from one tetrahedral site (4a) to another by
introduction of VO •• , VO1.75 exhibited a narrower bandgap passing through an unoccupied octahedral site (8c) and
and a lower diffusion energy barrier (0.24−0.71 eV) than thus experience a strong electrostatic repulsion from Mn
VO2 (0.78 eV) when zinc ions passed through the oxygen cations in a neighboring octahedral site (8d) (Figure 10A),
vacancy sites (Figure 9H). This would enable fast zinc ion which significantly hinders Zn2+ diffusion. For compar-
diffusion along the b tunnel in the host lattice. ison, the Mn-vacancy-rich structure allows for easy Zn-
The oxygen-vacancy strategies are the most commonly ion diffusion with a weakened electrostatic barrier, lead-
used method for structural engineering of cathode mate- ing to the high mobility of Zn2+ cations and consequently
rials, due to the easy formation of oxygen vacancy dur- fast reaction kinetics (Figure 10A). As a result, cation-
ing sample preparation. Various fabrication methods have defected ZnMn2 O4 exhibits a reversible specific capacity of
Review
F I G U R E 1 0 (A) Proposed Zn2+ diffusion pathway in ZMO spinel without and with Mn vacancies (reproduced with permission from
ref. [22]; copyright 2016, American Chemical Society). (B) HRTEM of the first fully charged state of MnO. The orange circles highlight the
missing Mn column position, indicating the formation of Mn cation defects. The right panels are the magnified images from the areas marked
by brown squares. Calculated DOS of (C) pristine MnO and (D) MnO with Mn defects. (E) Charge distribution of pristine MnO and MnO
with Mn defects, and the structures after Zn ion insertion. The green circle shows structural collapse (reproduced with permission from ref.
[104]; copyright 2020, Elsevier)
150 mAh/g at 50 mA/g and a high capacity-retention of and D), one can see that the formation of Mn defects in
94% after 500 cycles at a high current density of 500 mA/g. MnO increased the charge density around the Fermi level,
Additionally, Zhou et al. [104] developed an in situ elec- leading to enhanced electrical conductivity, as compared
trochemical approach to activate MnO by inducing Mn to pristine MnO. As shown in Figure 10E, the structure of
defects, which were formed through a charge process, and pristine MnO was greatly damaged upon Zn2+ insertion,
the introduction of Mn defects significantly enhanced the whereas no obvious structural change was observed with
electrochemical activity of MnO for aqueous ZIBs. High- Mn-defect MnO, as the Mn defects created large insertion
resolution transmission electron microscopy (HRTEM) channels and available active sites for Zn2+ ions, enabling
study (Figure 10B) showed a basic structure of MnO with fast reaction kinetics.
an interplanar spacing of 0.26 nm, corresponding to the In essence, cation vacancy can help improve ion diffu-
(111) plane of MnO. The magnified images (areas 1, 2, and 3) sion kinetics and increase electrochemical active sites for
clearly showed that the Mn columns in some areas became energy storage of the cathode materials. However, com-
weak or missing, indicating the formation of Mn defects pared to oxygen vacancy, cation-vacancy engineering has
(marked with dotted circles) in MnO. From the calculated been mostly confined to Mn-based oxides for ZIBs. Further
DOS of MnO with and without Mn defects (Figure 10C research is needed to extend the strategy to other cathode
Review
F I G U R E 1 1 (A, B) Low-magnification TEM images of the obtained HAVO hollow microspheres (reproduced with permission from ref.
[110]; copyright 2020, Elsevier). (C) TEM image of VO2 hollow spheres. (D) Percentages of capacitive and diffusion contributions of VO2 at
different scan rates. (E) Charge/discharge curves and the corresponding DZn 2+ values of the VO2 electrode in the sixth and seventh cycles
(reproduced with permission from ref. [111]; copyright 2019, Royal Society of Chemistry). (F) TEM image and selected area electron diffraction
patterns (inset) of VOOH. (G) Long-term cycling performance of Zn//ZVO battery at 10 A/g (reproduced with permission from ref. [112];
copyright 2019, American Association for the Advancement of Science)
materials, and to exploit the synergistic interactions of var- 4.4.1 Hollow structure
ious types of defects for more complicated structural engi-
neering. Cathode materials with a hollow structure (i.e., a thin shell
and high active surface area) are anticipated to facilitate
ion transport between layers, improve ion adsorption, and
4.4 Micro/nanostructure design enhance surface redox reactions. Additionally, hollow
nanostructures offer a large void space, which signifi-
Design and construction of micro/nanostructures is cantly alleviates the volume change of cathodes during
another promising strategy to improve the electrochemi- charge/discharge. For instance, Wang et al.[110] prepared
cal performance of cathode materials, due to the enlarged H11 Al2 V6 O23.2 (HAVO) hollow spheres as cathode materi-
specific surface area, enhanced accessibility to electrolyte, als for ZIBs, which were composed of nanosheets with an
as well as increased active sites for ion absorption.[105,106] average thickness < 5 nm (Figure 11A) and found to serve
In fact, cathode materials with micro/nanospheres, as effective channels for ions transport and electrolyte
nanosheets, nanofibers, and nanotubes have been widely wetting (Figure 11B). In another study,[111] vanadium
used for ZIB applications,[107–109] demonstrating the signif- dioxide (VO2 ) hollow nanospheres were employed as
icance of micro/nanostructure design in the optimization cathode materials for ZIBs (Figure 11C), which delivered
of electrochemical performance for cathode materials. In a high reversible discharge capacity of 408 mAh/g at 0.1
this section, two types of micro/nanostructure designs A/g, an exceptional rate performance of 200 mAh/g at 20
(hollow and core-shell structures) of cathodes will be A/g, and long cyclic stability (with a low capacity-fading
examined to reveal the unique ion/charge transport rate of 0.0023% per cycle over 30,000 cycles). Moreover,
mechanisms in such structures. the bar chart in Figure 11D clearly shows the capacitive
Review
F I G U R E 1 2 (A) Scheme of the energy storage process in one-dimensional core-shell structures (reproduced with permission from ref.
[24]; copyright 2019, American Chemical Society). (B) TEM image and EDS elemental maps of Ti, N, V, and O of a single TiN@V2 O5 nanowire
core-shell nanocomposite. (C) Schematic illustration of a fiber-shaped all-solid-state TiN@V2 O5 NWA//Zn battery. (D) Long-term cycling
performance at 8.0 mA/cm2 . The inset displays the charge/discharge curves for the first and last 10 cycles (reproduced with permission from
ref. [113]; copyright 2019, Royal Society of Chemistry)
contributions in energy storage of such cathode materials transport pathways, and sufficient space to buffer the vol-
at different scan rates. With the sweep rate increased from ume changes during the intercalation/de-intercalation of
0.2 to 5.0 mV/s, the percentage of capacitive contribution Zn ions. Nevertheless, their low volumetric energy density
grew from 63.8% to 90.0%, suggesting that the surface is the main obstacle for practical applications. Thus, strik-
pseudocapacitance effect played a dominant role at high ing a balance between the rate/cycling performance and
rates, which was favored for high-rate performance. volumetric energy density is the key in battery research,
Figure 11E shows the charge/discharge curves and the where a good control of the hollow structure with a pre-
corresponding DZn 2+ values of the VO2 electrode in the cise shell thickness and well-defined morphology will be a
6th and 7th cycles. It can be seen that the DZn 2+ values focus in future research.
during the two insertion and extraction processes are
on the order of 10−8 to 10−10 cm2 /s, significantly higher 4.4.2 Core-shell structure
than those reported previously.[111] The excellent electro-
chemical performance was ascribed to the interior hollow Core-shell structures usually possess superb chemical
architecture that featured a large specific surface area, and physical properties, as compared to their single-
large internal cavity, permeable porous thin shells, and component counterparts, due to synergistic effects
hence numerous reactive sites for guest ion insertion. This between the different components. Zhang et al.[24] pre-
allowed facile infiltration of the electrolyte and facilitated pared fiber structures based on a metal oxide core and
rapid diffusion of Zn2+ . Zheng’s group[112] used VOOH a carbon shell. Specifically, Zn2 V2 O7 and V2 O5 were
hollow nanospheres (Figure 11F) as precursors to fabricate employed as the cores, which were then coated with a car-
porous Zn-vanadium oxide materials through electro- bon layer. As shown in Figure 12A, such one-dimensional
chemical cycling. The obtained Zn0.3 V2 O5 ⋅1.5H2 O (ZVO) core-shell structures provided bi-continuous conductive
cathode delivered a high specific capacity of 426 mAh/g at pathways and highly porous networks for supporting the
0.2 A/g and exhibited an unprecedented long-term cyclic in situ formed metal oxide nanoparticles, thus facilitating
stability with a capacity retention of 96% over 20,000 fast electron/ion transport and high mass loading. Yao
cycles at 10 A/g (Figure 11G). et al. [113] fabricated a TiN@V2 O5 core-shell heterostruc-
Hollow nanostructures demonstrate great potential for ture with V2 O5 nanosheets anchored on TiN nanowire
ZIB applications with abundant Zn ion storage sites, short arrays for ZIBs (Figure 12B). The TiN@V2 O5 cathode
Review
exhibited a remarkable Zn-ion storage performance, from +5 (or +4) to +3 during redox reactions, and the
with a high capacity of 1.45 mAh/cm2 (636.0 mAh/g) at electron transfer resulted in an increased capacity and
0.5 mA/cm2 and a high rate capability of 1.11 mAh/cm2 improved cyclic stability, as compared to V3 O7 or V2 O5
(486.8 mAh/g) at 10 mA/cm2 . The outstanding electro- alone. Qin et al. [119] designed V2 O5 /NaV6 O15 bi-phase
chemical performance was attributed to the introduction composites as ZIB cathodes and found that the plenti-
of TiN nanowire arrays as the 3D conductive skeleton, and ful phase boundaries in the composites generated sig-
secondary-growth substrate increased the mass loading of nificant crystal defects as well as active sites, which
the V2 O5 nanosheets and provided rapid transfer of ion were advantageous for Zn2+ storage and contributed to
and charge, further improving the capacity, rate perfor- the pseudocapacitive effect; in addition, the bi-phase of
mance, and cycling stability. Consequently, flexible wire V2 O5 /NaV6 O15 significantly enriched the redox reactions
ZIB was assembled through such TiN@V2 O5 core-shell to buffer the stress during Zn2+ insertion. As a result, the
fibers as cathode and Zn nanosheets grown on CNT fibers V2 O5 /NaV6 O15 composite exhibited excellent long-term
as anode (Figure 12C), and showed a high energy density cycling stability, with a high capacity of 164 mAh/g after
and excellent cyclic stability with a capacity retention of 2000 cycles at 5 A/g and 116.7 mAh/g after 4000 cycles at 10
over 90% after 3500 cycles (Figure 12D). A/g. Note that whereas an increasing number of active sites
Cathode materials with a core-shell hierarchical struc- were formed in such composite cathodes, the interfacial
ture are expected to exhibit outstanding electrochemical resistance was increased significantly, and the poor bond-
performance, due to the synergistic effect between the core ing between different active phases might lead to structural
and shell parts. However, it is difficult to precisely con- collapse during the cycling process, consequently defeat-
trol the structural parameters, such as the diameter, length, ing their primary purpose as high-performance cathodes.
and thickness of the core or shell. Moreover, the forma- Carbon structures have been widely utilized as sub-
tion mechanism remains largely elusive, and the fabrica- strates to prepare composite cathodes of ZIBs in combi-
tion technology has not yet matured, limiting their indus- nation with other active materials,[120,121] such that the
trial applications. Further research is urgently needed to aggregation of the active materials can be minimized on
address these issues. the surface. Additionally, continuous conductive networks
formed by carbon nanostructures can provide fast trans-
fer channels for ions/electrons, enhancing the conduc-
4.5 Composite construction tivity of the composite cathodes. Notably, carbon struc-
tures in some cases can act as a buffer layer to allevi-
In order to further improve the electrochemical perfor- ate the volumetric change of cathode materials during the
mance of cathode materials, composites with two or more charge/discharge process. For example, carbon nanotubes
components have been constructed by combining the (CNTs) have been employed to stitch zinc pyrovanadate
advantages of each component in the structure and exploit- (Zn3 (OH)2 V2 O7 ⋅2H2 O, CNT-stitched ZVO) nanosheets,
ing the synergistic effects between the different compo- forming high-performance wearable cathode materials
nents. Mai et al. [114] have discussed the heterostructure for ZIBs.[122] With the CNT-stitched 2D nanosheets
composite electrodes for ZIBs. From the viewpoint of struc- (Figure 13A), the open frameworks of ZVO provided a
tural optimization, reconstruction of the electrode struc- required spacing for reversible Zn2+ (de)intercalation, and
ture with the participation of functional materials is an the stitching CNTs offered the desperately needed elec-
effective method to improve the overall performance of trical conductivity and mechanical robustness across the
ZIBs. For example, Niu et al. [115] fabricated a freestanding ZVO 2D nanosheets. More importantly, the nanosheet
rGO/VO2 electrode through a freeze-drying method. The arrays possessed abundant two-dimensional ion channels
cross-linked porous interconnected channels constructed in the exposed b−c planes, which were crucial to pro-
by ultra-thin graphene films and nanostructured VO2 promote charge transfer and accelerate ion access at the elec-
vided a fast electron transfer for electrodes during the trode/electrolyte interface with a short Zn2+ and electron
charge/discharge process. In sharp contrast, in the bare transportation path, whereas the stitching CNTs provided
VO2 cathode, electron transport was blocked by uncon- the desperately needed electrical conductivity across the
ducive binders. The functional structural components can ZVO nanosheets (inset to Figure 13A).[122] As a result,
be either active or non-active materials.[116,117] the fiber-shaped quasi-solid-state ZIB, assembled using
For composites that contain only electrochemically such cathodes, demonstrated an ultrahigh rate capabil-
active materials for Zn ion storage, every component ity, an impressive stack volumetric energy density of 71.6
contributes to energy storage. Yang et al. [118] prepared mWh/cm3 (Figure 13B), and outstanding cyclic stability.
a V3 O7 /V2 O5 composite as the cathode for ZIBs and Lu et al. [123] prepared MnO2 /graphene composite cath-
observed that the synergistic effects between V3 O7 and odes and observed significantly enhanced electrochemical
V2 O5 promoted the change of vanadium valence states properties. The graphene nanosheets-interconnected
Review
F I G U R E 1 3 (A) SEM image of 3D CNT-stitched ZVO NSs@OCNT fiberss. Inset shows the schematic illustration of electron transfer in
the CNT-stitched ZVO cathode. (B) Ragone plot to compare the energy storage performance of various devices (reproduced with permission
from ref. [122]; copyright 2020, American Chemical Society). (C) Schematic illustration of the fabrication of 3D spongy VO2 -rG. (D) Schematic
illustration of Zn ion/electron transfer in the architectural frame structure of VO2 -rG. (E) Long-term cycling of VO2 -rG at 10.0 A/g
(reproduced with permission from ref. [25]; copyright 2021, Elsevier)
MnO2 nanorods not only improved the conductivity of conductivity and energy density should be taken into con-
MnO2 but also endowed the electrode with the ability sideration in the design of carbon-based composite cath-
to accommodate the structural damage and dissolution odes. Additionally, the interfaces between different phases
of MnO2 during the charge/discharge process, leading in the composite structures would inevitably create barri-
to an enhanced rate and cyclic stability. Wang et al. [25] ers for ion/charge transfer, resulting in an increased inter-
prepared a multifaceted V2 O5 ⋅nH2 O-graphene composite facial resistance, which is a daunting challenge in the con-
(VOH-rG) through an in-situ self-transformation process struction of composite cathodes for ZIBs.
using three-dimensional spongy VO2 -graphene (VO2 -
rG) as the precursor (Figure 13C). Benefiting from the 4.6 Other strategies
highly conductive heterointerfaces, rich reaction sites,
and numerous ion diffusion channels of VO2 -rG, almost Surface coating of the cathode materials has also been used
100% VO2 nanobelts were converted into VOH during the as an effective way to improve the electrochemical perfor-
first charging with few side reactions, indicating highly mance of cathodes, where a uniform and stable protecting
efficient transformation kinetics. Additionally, numerous layer is constructed on the surface of the electrode mate-
graphene layers were anchored on the surface of the VO2 rial. Typically, conductive carbon has been widely used as
nanobelts to construct an architectural frame structure the coating layer to modify the cathode materials, due to
(Figure 13C), acting as “corbeled pillars,” which is favor- its high conductivity and easy processing. For example,
able for minimizing the self-stacking of VO2 nanobelts, Kim et al. [124] prepared carbon-coated α-MnO2 nanopar-
facilitating the diffusion of electrolyte, and enhancing the ticles (α-MnO2 @C) as cathodes of aqueous ZIBs. The car-
across-interlayer electron transfer (Figure 13D).[25] Conse- bon coating not only improved the electrical conductivity,
quently, the VOH-rG cathode exhibited a high capacity of but also significantly enhanced the specific capacity and
466 mAh/g at 0.1 A/g, an excellent rate performance (190 cycling performance of the α-MnO2 electrode. Meanwhile,
mAh/g even at 20 A/g), and cycling stability with 100% Xu et al. [125] prepared carbon-coated ZnNi0.5 Mn0.5 CoO4
capacity retention over 5000 cycles (Figure 13E). (ZnNi0.5 Mn0.5 CoO4 @C) as ZIB cathodes, where the car-
Carbon modification has been regarded as the most bon film served as a protective layer for the insertion and
widely used strategy in the structural engineering of cath- migration of electrons and ions, leading to improved struc-
ode materials for ZIBs. However, carbon materials alone tural stability of the cathode material and enhanced battery
possess negligible storage for Zn ions, and thus the intro- performance.
duction of carbon structures can satisfy the energy den- Table 1 summarizes the performances of a range of
sity of composite cathodes. Thus, the balance between the cathode materials modified through different strategies, in
Review
TA B L E 1 Summary of the electrochemical performance of typical ZIB cathodes modified through different strategies
Structural Cathode
Strategy engineering materials Capacity Cyclic stability Reference
Intercalation of pillars enlarge layer Znx MnO2 1.746 F/cm2 at 83.1% capacity [63]
spacing, 2 mA/cm2 retention (5,000

stabilize cycles at
material 15 mA/cm2 )
structure, and Cu-V2 O5 (CuVO) 359 mAh/g at 1 180 mAh/g (10,000 [69]
reduce A/g cycles at 10 A/g)

electrostatic
Lix V2 O5 ⋅nH2 O 407.6 mAh/g at 192 mAh/g (1,000 [72]
interactions
1 A/g cycles at 10 A/g)
[21]
PANI-MnO2 298 mAh/g at 280 mAh/g (200
0.05 A/g cycles at 0.2 A/g)
[65]
PANI-V2 O5 353.6 mAh/g at 280 mAh/g (100
0.1 A/g cycles at 0.2 A/g)
[84]
381 mAh/g at 71% (900 cycles at 6
V2 O5 ⋅nH2 O/graphene 0.06 A/g A/g)
Heteroatom doping promote Ni-doped Mn2 O3 252 mAh/g at ≈85.6% capacity [23]
electronic re- 0.1 A/g retention (2,500

arrangement cycles at 1 A/g)
and enhance Mn-doped ZnO 268.1 mAh/g at 147 mAh/g (10,000 [91]
electrical 1 A/g cycles at 5 A/g)

conductivity [44]
ZnMn2 O4 /N- 221 mAh/g at 97.4% capacity
doped 0.1 A/g retention (2,500
graphene cycles at 1 A/g)
[97]
MnOx @N-C 305 mAh/g at 100 mAh/g (1,600
500 m A/g cycles at 2 Ag−1 )
[99]
Defect engineering modify the Od -MnO2 345 mAh/g at 80% capacity
electronic 0.2 A/g retention (2,000
properties cycles at 5 A/g)
VO •• −VO2 375 mAh/g at 175 mAh/g (2,000 [103]
0.1 A/g cycles at 5 A/g)

[104]
Mn-defective 300 mAh/g at 116 mAh/g (1,500
MnO 0.1 A/g cycles at 1 A/g)
[110]
Micro/nanostructure enlarge specific H11 Al2 V6 O23.2 288.4 mAh/g at 88.6% capacity
design surface area, hollow spheres 0.1 A/g retention (7,000
enhance cycles at 5 A/g)
accessibility to VO2 hollow 408 mAh/g at 116 mAh/g (20,000 [111]
electrolyte, spheres 0.1 A/g cycles at 15 A/g)

and increase [113]
TiN@V2 O5 636 mAh/g at 90.6% retention
the number of
core-shell 0.5 mA/cm2 (3,500 cycles at
active sites
8 mA/cm2 )
[118]
Composite construction combine the V3 O7 /V2 O5 306 mAh/g at 17.4% fading (6,500
advantages 0.5 A/g at 5 A/g)
and MnO2 /graphene 301 mAh/g at 64.1% retention [123]
synergistic 0.5 A/g (300 cycle at

effects 20 mA/cm2 )
between the
V2 O5 ⋅nH2 O- 466 mAh/g at 100% retention [25]
different
graphene 0.1 A/g (5,000 cycle at 10
components
A/g)
Review
terms of the modification strategy, structural engineering, realized through pre-intercalation (interlayer modula-
capacity, and cyclic stability. It is obvious that the elec- tion), substitution, or defect engineering.[59] The mech-
trochemical performance of the cathode materials can be anistic insights of the reaction kinetics in cathode mate-
effectively improved through these different strategies. rials will be critical for the rational design of high-
performance cathode materials of ZIBs. This should be
a focus in future research.
5 CONCLUSION AND OUTLOOK 3. Properties of cathode/electrolyte interface. As an essen-
tial part of ZIBs, the electrolyte is a bridge that effec-
ZIBs have been attracting ever-increasing attention, due tively connects the cathode and anode materials dur-
to the low cost, environmental benignity, high safety, and ing the charge/discharge process. Currently, studies
high energy density. Despite substantial progress in recent have mostly focused on the selection of a specific
years, to render ZIBs competitive to LIBs in energy stor- electrolyte for ZIBs, while the impacts of the cath-
age, rational design of the cathode materials is of great sig- ode/electrolyte interface on the capacity performance
nificance to further improve the ZIB performance. Toward as well as the compatibility between the cathode mate-
this end, a range of critical roadblocks needs to be tack- rials and electrolyte have remained largely unexplored.
led, such as dissolution and structural collapse of cath- Advanced characterization tools need to be developed
ode materials during cycling, generation of by-products, and employed to unravel the microstructure and struc-
formation of zinc dendrite, corrosion of zinc anode, and tural evolution of the cathode/electrolyte interface dur-
hydrogen evolution. In this review, the recent cathode- ing the charge/discharge process. Furthermore, coating
based strategies are summarized to address the issues of modification on the cathode surface is beneficial to opti-
active materials dissolution, degradation of electrochemi- mizing the cathode/electrolyte interfacial properties.
cal performance, and structural collapse during cycling. To 4. High mass loading of active materials on cathodes.
further enhance the electrochemical performance of ZIBs, To achieve a high energy density of ZIBs, high mass-
addiitonal research is needed, in particular, in the follow- loading cathode materials are needed in battery design.
ing key areas. However, with an increased loading of the active mate-
rials in cathodes, inevitable issues emerge, such as pow-
1. Multi-strategies for cathode material engineering. Cur- der aggregation, low usage efficiency of active mate-
rent research has mostly focused on a single strategy rials, and cracking and pulverization, which severely
to improve the performance of the cathode materi- deteriorate the electrochemical performance of the
als, and the enhancement is limited (Table 1). Thus, cathode materials. Therefore, effective binders are crit-
future research should be conducted whereby multi- ically needed to homogenize and strongly adhere the
ple strategies are combined to enhance the performance powders of active materials, as well as facile methods
of cathode materials through the realization of syner- to coat high massing-loading active materials onto the
gistic effects. Within this context, facile, cost-effective, current collectors.
and simple fabrication processes are needed to achieve 5. Smart and miniature devices. With the increasing
multi-modification of the cathode materials. demand for miniature electronics, energy storage
2. Reaction kinetics in cathode materials. Since the elec- devices need to be smarter, smaller, more flexible,
trochemical properties of cathode materials are signifi- and more portable. Thus, extensive efforts should be
cantly affected by the reaction kinetics, attention should devoted to the design of cathode materials with high
be focused on enhancing the Zn ion transport kinet- flexibility, high wearability, and lightweight to meet the
ics in the cathode materials. The ionic diffusion coef- ever-increasing demand for functional ZIBs. Moreover,
ficients, pseudocapacitive behaviors, Zn-ion migration free-standing cathode materials without any binder can
paths, and energy barriers should be taken into consid- improve the structural stability and reduce the interface
eration in the design of cathode materials. For example, resistance of electrodes, a unique feature for the appli-
the large contribution of pseudocapacitance in cathode cation in smart ZIB devices.
materials will lead to a high rate capability and long 6. Development of advanced in-situ characterization and
cycle life, which can be achieved through the construc- simulation methods. In situ characterization methods
tion of nanosized cathode materials with controllable can clearly probe the dynamic process of Zn ion diffu-
pores and large specific surface area. Moreover, for the sion into/from cathode materials, and shed light on the
cathode materials based on ion (de)intercalation mech- energy storage mechanism of ZIBs. Moreover, DFT sim-
anism, the key point to improve the electrochemical ulation methods can greatly contribute to a deep under-
performance is to provide sufficient diffusion space and standing of the intrinsic properties of cathode materi-
meanwhile maintain a stable structure, which can be als as well as the energy storage mechanism, which are
Review
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How to cite this article: He P, Chen S. Cathode
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strategies to improve the performance of zinc-ion
815. batteries. Electrochem Sci Adv. 2022, 2, e2100090.
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2021, 50, 5795.

Cathode Strategies To Improve The Performance of Z

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1 of 24 Electrochemical Science Advances doi.org/10.1002/elsa.202100090

Received: 19 May 2021

Cathode strategies to improve the performance of zinc-ion

Pingge He Shaowei Chen

Department of Chemistry and

1 INTRODUCTION ern era.[8] Among them, zinc-ion batteries (ZIBs) have

Electrochem. Sci. Adv. 2022;2:e2100090. wileyonlinelibrary.com/journal/elsa 1 of 24

batteries. Various types of materials have been used as

3.1 Zn2+ intercalation/de-intercalation 1∕2𝑍𝑛2+ + 𝑂𝐻 − + 1∕6𝑍𝑛𝑆𝑂4 + 𝑥∕6𝐻2 𝑂

3.3 H+ /H2 O and Zn2+ co-insertion 4 STRATEGIES TO IMPROVE THE

spacing, 2 mA/cm2 retention (5,000

reduce A/g cycles at 10 A/g)

electronic re- 0.1 A/g retention (2,500

electrical 1 A/g cycles at 5 A/g)

0.1 A/g cycles at 5 A/g)

electrolyte, spheres 0.1 A/g cycles at 15 A/g)

synergistic 0.5 A/g (300 cycle at

104. C. Zhu, G. Fang, S. Liang, Z. Chen, Z. Wang, J. Ma, H. Wang, B. AU T H O R B I O G R A P H I E S

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