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Recent Advances in Layered Metal-Oxide Cathodes for

1. Introduction
To meet future energy demands, currently, dominant lithium-ion batteries
(LIBs) must be supported by abundant and cost-effective alternative battery The ever-growing energy demand and
alarmingly increasing environmental pollu-
materials. Potassium-ion batteries (KIBs) are promising alternatives to LIBs
tion caused by the massive consumption of
because KIB materials are abundant and because KIBs exhibit intercalation fossil fuels have driven the research com-
chemistry like LIBs and comparable energy densities. In pursuit of superior munity to focus on developing sustainable
batteries, designing and developing highly efficient electrode materials are clean energy technologies.[1] Toward this
indispensable for meeting the requirements of large-scale energy storage goal, energy conversion and storage de-
applications. Despite using graphite anodes in KIBs instead of in sodium-ion vices are both equally important for over-
coming the global energy crisis.[2–5] Among
batteries (NIBs), developing suitable KIB cathodes is extremely challenging
various energy storage systems, lithium-
and has attracted considerable research attention. Among the various cathode ion batteries (LIBs) have been the predom-
materials, layered metal oxides have attracted considerable interest owing to inant power sources for consumer elec-
their tunable stoichiometry, high specific capacity, and structural stability. tronics and smart wearable devices ow-
Therefore, the recent progress in layered metal-oxide cathodes is ing to their high energy density, long cy-
cling life, and easy maintenance.[6,7] Re-
comprehensively reviewed for application to KIBs and the fundamental
cently, LIBs have been utilized in trans-
material design, classification, phase transitions, preparation techniques, and portation fields to power (hybrid) electric ve-
corresponding electrochemical performance of KIBs are presented. hicles, which minimize CO2 emissions and
Furthermore, the challenges and opportunities associated with developing noise pollution.[8] However, LIBs alone may
layered oxide cathode materials are presented for practical application to KIBs. not meet the future energy demands asso-
ciated with the rapid growth of the elec-
tric vehicle market and stationary storage
systems. Lithium is scarce and unevenly distributed in Earth’s
crust, which raises concerns about the soaring price of LIBs
and the sustainability of lithium for meeting future en-
ergy demands.[9,10] Therefore, developing economical, high-
M. G. T. Nathan, H. Yu, G.-T. Kim, J. Kim, J.-K. Kim performance post-LIBs is critical. Hence, sodium-ion batteries
Department of Energy Convergence Engineering (NIBs) and potassium-ion batteries (KIBs) are promising alter-
Cheongju University
Cheongju, Chungbuk 28503, Republic of Korea natives or complements to LIBs because sodium and potassium
E-mail: [email protected] are both abundant.[9,11,12] Interestingly, like LIBs, NIBs and KIBs
J.-H. Kim operate by a similar “rocking-chair” mechanism. Therefore, ex-
Department of Biomedical Laboratory Science tensive knowledge about LIBs enables the rapid development of
College of Health Science Cheongju University NIBs and KIBs. A schematic illustrating the KIB operating prin-
Cheongju, Chungbuk 28503, Republic of Korea
ciple is shown in Figure 1a. Clearly, K+ -ions shuttle between the
E-mail: [email protected]
cathode and anode during charging and discharging.[13,14]
J. S. Cho
Department of Engineering Chemistry Recently, KIBs have attracted considerable research interest
Chungbuk National University because they have some advantages over NIBs and exhibit
Chungbuk 28644, Republic of Korea some properties comparable to those of LIBs. For instance,
E-mail: [email protected] well-established LIB graphite anodes are easily transferrable
to KIBs because graphite can reversibly accommodate K+ -ions
The ORCID identification number(s) for the author(s) of this article forming intercalation compounds such as KC8 [15,16] in contrast
can be found under https://doi.org/10.1002/advs.202105882
to the formation of NC70 , which limits Na+ -ion intercalation into
© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.
This is an open access article under the terms of the Creative Commons
graphite.[17] The standard redox potentials of Li/Li+ , Na/Na+ , and
Attribution License, which permits use, distribution and reproduction in K/K+ are −3.04, −2.71, and −2.93 V versus a standard hydrogen
any medium, provided the original work is properly cited. electrode (SHE), respectively (Figure 1b). The standard redox
DOI: 10.1002/advs.202105882 potential of K/K+ is comparable to that of Li/Li+ in aqueous

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Figure 1. a) Schematic illustration of working mechanism of KIB, b) standard redox potential of various metal anodes, and c) comparison of Shannon’s
ionic radius and Stokes radius in propylene carbonate of Li+ , Na+ and K+ .

electrolytes. Furthermore, the K/K+ redox couple exhibits even siderable interest in storing K+ ions in layered metal-oxide cath-
lower standard redox potentials than Li/Li+ in nonaqueous odes for application to KIBs because the cathodes exhibit high
electrolytes such as propylene carbonate (PC) (−0.09 V vs Li/Li+ ) capacity, large K+ -ion diffusion paths, and scalable synthesis. Re-
and a mixture consisting of ethylene carbonate and diethyl cently, various groups have published reviews of KIB electrode
carbonate (EC:DEC) (−0.12 V vs Li/Li+ ).[18,19] The low K/K+ materials and electrolytes.[9,14,18–21,23,34–38] From this perspective,
redox potential leads to a wider potential window for operating a comprehensive review of cathode material advantages and chal-
KIBs and will eventually achieve high-energy-density batteries. lenges is critical to further develop KIBs.
Alkali metal ion (e.g., Li+ , Na+ , and K+ ) transport properties Therefore, we report recent research progress on layered metal
influence the rate performance of this battery class. As shown in oxide cathodes for application to KIBs. First, we introduce the
Figure 1c, although K+ (1.38 Å) ions are larger than Na+ (1.02 Å) KIB charge storage mechanism and the advantages of KIBs over
and Li+ (0.76 Å) ones, K+ ions exhibit lower charge density and NIBs and LIBs. Then, the layered metal oxide structural classifi-
the lowest solvation and desolvation energies among the alkali cation and phase transitions are discussed. Recent works related
metal ions, which facilitates rapid desolvation at the electrode– to layered metal oxide cathodes for application to KIBs are sum-
electrolyte interface. Furthermore, because K+ -ions weakly marized based on the number of transition metals used by focus-
interact with solvent molecules, the smaller K+ -ion Stokes radius ing on the structural transformations and electrochemical perfor-
(Figure 1c) results in higher ionic conductivities and transfer- mances of half- and full-cell configurations. Finally, some strate-
ence numbers.[20,21] Another advantage of KIBs over LIBs is that gies are proposed to suppress irreversible phase transitions and
inexpensive aluminum current collectors can be used on both enhance the overall performance for future KIB development.
the cathode and anode sides because unlike lithium, potassium
does not alloy with aluminum—which reduces the KIB cost and 2. Structural Classification of Layered
weight.[22,23] Regarding safety, NIBs exhibit an Na+ -ion insertion Transition-Metal Oxides
potential of 0.05 V versus Na/Na+ for a hard carbon anode, which
is too close to the sodium metal plating potential, implying that Layered transition-metal oxides can be represented by the for-
dendrites will form in NIBs cycled at high current rates. In con- mula Ax MO2 (0 < x < 1), where A represents alkali metal ions
trast, KIBs exhibit an average K+ -ion intercalation potential of 0.2 (e.g., Li+ , Na+ , and K+ ), and M can be one or more transition-
V versus K/K+ for most carbon anodes, which is well above the metal ions in various oxidation states. Typically, layered Kx MO2
potassium metal plating potential, suggesting that KIBs are safer compounds are formed with alternately stacked edge-sharing
than NIBs.[24,25] However, although all these advantages make MO6 octahedral layers and K+ -ion layers. P2-, P3-, and O3-type
KIBs a promising alternative to LIBs, potassium metal must be layered Kx MO2 can be synthesized based on the surrounding K+ -
handled with the utmost care when fabricating half cells because ion environment and the number of unique oxide layer stacking
potassium metal is highly flammable. sequences.[39] P and O indicate whether K+ ions are in a pris-
The reversible intercalation of K+ ions into graphite anodes matic or an octahedral coordination environment, respectively.
has shifted the research focus to designing and exploring suitable Numbers 2 and 3 indicate the number of oxide layers in a single
cathode materials for practical application to KIBs. Obviously, unit cell. Figure 2 shows a schematic illustrating the O3, P3, and
the cathode is the key component determining the KIB elec- P2 crystal structures. In O3 crystals, all the K+ -ions occupy octa-
trochemical characteristics, energy density, and cost. Recently, hedral sites, and oxide layer stacking follows the AB–CA–BC pat-
extensive research efforts have led to the development of vari- tern. At high K+ concentrations (e.g., x = 1), strong electrostatic
ous cathode materials such as Prussian blue analogs,[26,27] lay- K+ –K+ repulsion destabilizes Kx MO2 layered compounds. O3-
ered metal oxides,[28,29] polyanionic frameworks,[30,31] and or- KCrO2 is the only electrochemically active Kx MO2 layered com-
ganic compounds.[32,33] The application of layered metal-oxide pound that forms O3 crystals.[40] In P3 crystals, oxide layer stack-
cathodes (such as LiCoO2 ) to commercial LIBs has attracted con- ing follows the AB–BC–CA pattern, and K+ ions are at prismatic

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Figure 2. Crystal structures of O3-, P3-, and P2-type layered metal oxides.

sites. P2 compounds are formed by AB–BA oxide layer stacking. ode, which encouraged researchers to develop different KIB elec-
In P2 crystals, K+ ions occupy distinct edge- or face-sharing pris- trode materials.[45] The number of K+ -ions in layered oxides plays
matic sites.[41] A prime symbol (ʹ) is used to specify the in-plane a crucial role in obtaining different structures, morphologies,
distortion of hexagonal crystal lattices such as monoclinic Pʹ3- and electrochemical performances. Liu et al. synthesized P2-
K0.8 CrO2 .[42] K0.3 MnO2 and P3-K0.45 MnO2 layered oxides by varying the K+ -
The reaction temperature is critical for obtaining different ion concentration under the same experimental conditions.[46]
crystals. Most P2 compounds stabilize at higher temperatures Reportedly, the higher-K+ P3-K0.45 MnO2 displayed smaller par-
than P3 ones. For instance, P3-Kx CoO2 and P2-Kx CoO2 are syn- ticles and slightly better cycling stability and rate performance
thesized at 400 ° C and 600 ° C, respectively.[43] The P3–P2 phase than P2-K0.3 MnO2 (Figure 3b). In a wider potential window of
transformation occurs by breaking M–O bonds at high temper- 1.5–4.0 V versus K/K+ , P3-K0.45 MnO2 delivered a specific capac-
atures. Layered compound electrochemical behaviors are influ- ity of 128.6 mAh g−1 at 20 mA g−1 and better rate performance
enced by both the initial pristine compound K+ -ion content and with a specific capacity of 51.2 mAh g−1 , even at a current density
structural stability. During K+ -ion extraction/insertion, O3 tran- of 200 mA g−1 .[46]
sitions to other phases because the MO2 -layer glides without Kim et al. investigated the P3-K0.5 MnO2 electrochemical
breaking any M–O bonds. When a trace of K+ -ions is extracted, performance and structural changes during reversible K+ -ion
layer gliding changes the O3 oxide stacking pattern to the P3 deintercalation/intercalation.[47] The in situ XRD patterns gener-
one, which may be because larger K+ -ions prefer to occupy ener- ated during charging/discharging and corresponding computa-
getically favorable prismatic sites rather than smaller octahedral tions elucidated the P3-K0.5 MnO2 K+ -ion storage mechanism and
ones.[40] Neither O3 nor P3 materials can electrochemically trans- how the K+ -content influenced the phase changes. As shown in
form into P2 ones because M–O bonds cannot break to form P2 the in situ XRD patterns (Figure 3c), P3-K0.5 MnO2 reversibly tran-
materials during charging and discharging. However, P2 mate- sitions among P3, O3, and X during K+ -ion extraction and rein-
rials transition to O2 ones when the maximum K+ -ion concen- sertion. P3-K0.5 MnO2 delivered a specific capacity of 106 mAh
tration is extracted.[41,44] Therefore, owing to fewer phase transi- g−1 when cycled between 1.5 and 3.9 V versus K/K+ , and fur-
tions, P compounds are structurally more stable than O layered ther increasing the potential to 4.2 V resulted in considerable
compounds. stacking-fault-induced capacity fading when more K+ -ions were
extracted at high potentials; thus, the voltage range must be ap-
3. Layered Metal Oxide Cathodes for KIBs propriately tuned to optimize durable performance.[47] Structural
morphology and particle size also play important roles in im-
3.1. Single Metal Oxides proving electrochemical performance. For instance, Peng et al.
prepared P3-K0.5 MnO2 hollow submicrospheres (HSMSs) using
3.1.1. Manganese-Based Electrodes two-step self-templating.[48] When tested as a KIB cathode mate-
rial in the range 1.5–3.9 V versus K/K+ , the P3-K0.5 MnO2 HSMSs
Vaalma et al. demonstrated the first-ever nonaqueous KIB utiliz- demonstrated a capacity of 104 mAh g−1 at 10 mA g−1 and ex-
ing layered K0.3 MnO2 as cathode, which exhibited an initial dis- cellent capacity retention of 89.1% over 400 cycles at 200 mA
charge capacity of 70 mAh g−1 and a reasonable capacity retention g−1 . The enhanced electrochemical performance was ascribed to
of 57% over 685 cycles at 27.9 mA g−1 in the potential window the synergy between the particle size and the hollow spherical
1.5–3.5 V versus K/K+ (Figure 3a).[45] Nevertheless, K0.3 MnO2 morphology. The full cell assembled with a graphite anode and
exhibited considerable capacity fading under the higher cutoff the P3-K0.5 MnO2 HSMS cathode delivered an energy density of
condition (1.5–4.0 V) possibly because of irreversible phase tran- 100.7 Wh kg−1 at an average output of 2.09 V, which highlights
sitions at higher potentials. Furthermore, a KIB full cell was the HSMS feasibility for practical application to KIBs.[48]
constructed as a proof-of-concept model, with K0.3 MnO2 as the The major issues with manganese-based layered cathodes
cathode and a hard carbon/carbon black composite as the an- are Jahn–Teller (J–T) active Mn3+ ions and the associated

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Figure 3. a) Potential profiles of the 2nd and 50th cycle at 0.1 C in the voltage range 3.5–1.5 and 4.0–1.5 V. Reproduced with permission.[45] Copyright
2016, Electrochemical Society. b) Cycling performance of P2-K0.3 MnO2 and P3-K0.45 MnO2 at 20 mA g−1 . Reproduced with permission.[46] Copyright
2019, Elsevier. c) Structural changes of P3-K0.5 MnO2 during charge and discharge. Reproduced with permission.[47] Copyright 2017, Wiley.

disproportionation reaction (2Mn3+ → Mn2+ + Mn4+ ), which ure 4b).[54] The AlF3 -coated K1.39 Mn3 O6 delivered a specific ca-
generate an asymmetric cathode structure and lead to Mn2+ -ion pacity of 110 mAh g−1 at 10 mA g−1 and outstanding cycling
dissolution into the electrolyte during cycling.[49–52] To circum- stability with a capacity retention of 94.9% over 100 cycles,
vent these issues and stabilize Mn-based cathode performance, which was far superior to the electrochemical performances of
different strategies have been employed. Notably, Lei et al. both the noncoated microspheres and the bulk counterpart (Fig-
reported the in situ formation of a dual interface on an Mn- ure 4c).[54] Therefore, surface modification is an efficient method
based P2-K0.67 MnO2 cathode consisting of an inactive K-poor of mitigating unwanted parasitic reactions and stabilizing cath-
spinel interlayer and a stable solid–electrolyte interface (SEI) ode interfaces.[54]
film (Figure 4a). The dual interface layers accommodated J-T
distortion, alleviated Mn dissolution, and improved the K+ -ion
diffusion kinetics, which resulted in good rate performance, a 3.1.2. Cobalt-Based Electrodes
small volumetric change of 9.9%, stable operation for 300 cycles,
and a capacity retention of 90.5% at 50 mA g−1 .[53] Although Delmas et al. synthesized and structurally char-
Zhao et al. coated the surface of K1.39 Mn3 O6 microspheres acterized Kx CoO2 crystals in 1975,[55] K+ -ion deintercala-
with AlF3 to enhance their electrochemical performance (Fig- tion/intercalation was not studied for Kx CoO2 compounds until

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Figure 4. a) Formation mechanism of the dual interphase layers composed of a SEI layer and spinel interlayer on P2-KMO during cycles. Reproduced
with permission.[53] Copyright 2019, Elsevier. b) Schematic illustration of the synthesis process of AlF3 @S-KMO. c) Cycling performance at 50 mA g−1
before and after refreshing the potassium metal anodes and electrolyte. Reproduced with permission.[54] Copyright 2019, Wiley.

2017 by Hironaka et al.[43] Because the synthesized P2-K0.41 CoO2 average output of 2.7 V versus K/K+ .[56] P2-K0.6 CoO2 maintained
and P3-K2/3 CoO2 were moisture sensitive, they had to be handled the P2 structure when the K+ -ion content was varied between
in an argon atmosphere. Both P2-K0.41 CoO2 and P3-K2/3 CoO2 de- 0.33 and 0.68, thereby implying a reversible topotactic reaction
livered similar specific capacities of ≈60 mAh g−1 in the poten- (Figure 5b); however, P2-K0.6 CoO2 exhibited poor cycling stabil-
tial window 2.0–3.9 V versus K/K+ . The multistep voltage pro- ity likely due to side reactions with the electrolyte.
file originated from strong K+ /vacancy ordering, which is sup- In another study, P2-K0.6 CoO2 (s-KCO) microspheres were
ported by the operando XRD results. Compared to O2-LiCoO2 , synthesized using self-templating.[57] The s-KCO electrode
P2-Na2/3 CoO2 and P2-K0.41 CoO2 both displayed a steep voltage demonstrated a high specific capacity of 82 mAh g−1 at 10 mA
drop (Figure 5a), which mainly depended on the ionic radius in- g−1 , high-rate capability, and excellent cycling stability with 87%
terslab distance and determined the alkali-metal ion battery work- capacity retention over 300 cycles at 40 mA g−1 (Figure 5c). The
ing voltage.[43] P2-K0.6 CoO2 synthesized with a higher K+ -ion con- hierarchical microsphere structure provided fast K+ -ion and elec-
tent delivered a specific capacity of 80 mAh g−1 at 2 mA g−1 and tron transport pathways and minimized the contact area between

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Figure 5. a) Voltage curves of A//AxCoO2 (A = Li, Na, and K). Reproduced with permission.[43] Copyright 2017, Royal Society of Chemistry. b) Typical
charge/discharge profile at a current rate of 2 mA g−1 and in situ XRD patterns of P2-K0.6 CoO2 . Reproduced with permission.[56] Copyright 2017, Wiley.
c) Rate capability of s-KCO and i-KCO at different current rates; Typical charge-discharge curves of s-KCO//K and hard carbon//K in a half-cell and
s-KCO//hard carbon full-cell configurations. Reproduced with permission.[57] Copyright 2018, American Chemical Society.

the electroactive materials and the electrolyte, thus reducing un- is attributed to strong K+ –K+ interactions. Moreover, the incom-
desirable side reactions and enhancing K+ -ion storage in P2- plete recovery of K+ ions—even at the end of discharging—shows
K0.6 CoO2 . Furthermore, the s-KCO//hard carbon full cell exhib- that the Oʹ3 structure is not converted into the O3 one, which
ited a high capacity of 71 mAh g−1 at 30 mA g−1 and excellent is likely owing to the sluggish K+ -ion kinetics when x ≈ 1 in
capacity retention (>80%) after 100 cycles.[57] Kx CrO2 . The full cell constructed using the O3-KCrO2 cathode
and a graphite anode exhibited a capacity of ≈82 mAh g−1 at 5 mA
g−1 .[40] This work provides insight into the design of stoichio-
3.1.3. Chromium-Based Electrodes metrically layered compounds for application to KIBs. Naveen
et al. synthesized layered O3-KCrS2 with a stoichiometric amount
Most layered K+ -ion compounds prepared are having lower K+ of K+ . O3-KCrS2 exhibited high electrochemical reversibility be-
concentrations than sodium and lithium analogs[43,58–60] because tween P3-K0.39 CrS2 and O3-K0.80 CrS2 because the material mostly
strong K+ –K+ repulsion cannot accommodate all the K+ ions retains the P3 structure
in the K+ -ion layer, thus generating K+ -deficient compounds during K+ deintercalation/intercalation, thereby enabling fast
+
(Kx MO2 ; x ≤ 0.7). Computational studies have indicated that only K -ion diffusion through larger prismatic sites. The O3-KCrS2
KScO2 and KCrO2 are thermodynamically stable layered com- cathode delivered a specific capacity of 71 mAh g−1 and excel-
pounds (Figure 6a). Kim et al. prepared stoichiometrically layered lent cycling stability with ≈90% capacity retention over 1000 cy-
O3-KCrO2 and investigated its electrochemical performance as a cles owing to the soft sulfide framework, which buffered the K+ -
KIB cathode.[40] The layered KCrO2 was stabilized owing to the deinsertion/insertion-induced stress.[61]
unusual Cr3+ -ligand-field preference for octahedral sites, which Hwang et al. prepared another Cr-based cathode, P3-K0.69 CrO2 ,
compensated for the K+ –K+ -repulsion-induced energy penalty. from O3-NaCrO2 through electrochemical ion exchange, which
O3-KCrO2 delivered a discharge capacity of 92 mAh g−1 at 5 mA is an efficient process when synthesizing layered compounds
g−1 and exhibited a multistep voltage profile (Figure 6b). During is difficult using the conventional solid-state method.[62–65] The
charging, the O3-KCrO2 cathode reversibly transitioned among P3-K0.69 CrO2 cathode exhibited a discharge capacity of 100 mAh
O3–Oʹ3–Pʹ3–P3–Pʹ3–P3–O3 (Figure 6c). These phase transitions g−1 at 10 mA g−1 in the range 1.5–3.8 V versus K/K+ . Although
are more complex than those observed for O3-NaCrO2 , which this cathode exhibited staircase-like voltage profiles, it reversibly

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Figure 6. a) Thermodynamic stability of layered KMO2 compounds. b) Typical voltage-capacity curves at a current rate of 5 mA g−1 and c) in situ XRD
patterns of O3-KCrO2 . Reproduced with permission.[40] Copyright 2018, American Chemical Society.

transitioned between P3 and P″3 and exhibited outstanding long- ure 7a).[71] The K0.5 V2 O5 cathode delivered a specific capacity of
term cyclability at 100 mA g−1 with 65% capacity retention over 90 mAh g−1 at 10 mA g−1 in the range 1.5–3.8 V versus K/K+ . To
1000 cycles.[66] Further studies are required to optimize the elec- prepare a full cell using carbon-based anodes, a suitable cathode
trolyte and reduce the slow ion exchange to improve the potential must exhibit numerous extractable K+ ions because the cathode
for practical applications. Naveen et al. developed a facile method serves as a reservoir for reversible K+ ions. Although only a trace
of synthesizing Pʹ3-K0.8CrO2 .[42] The Pʹ3-K0.8 CrO2 cathode dis- of K+ ions was extracted from K0.5 V2 O5 during the initial charg-
played different O3-KCrO2 phase transitions, resulting in differ- ing (Figure 7b), this problem was solved by prepotassiation.[71]
ent electrochemical performances. The absence of the O3 phase Clites et al. prepared K+ -preintercalated bilayered Kx V2 O5 ·nH2 O
and persistence of the Pʹ3 ones in most redox states contributed by the sol–gel method.[72] During synthesis, K+ ions and water
to limited volumetric changes (ΔV = 1.08%) and rapid K+ -ion molecules are trapped between growing vanadium oxide bilayers
diffusion, which eventually resulted in improved cyclability and to form 𝛿-Kx V2 O5 ·nH2 O (Figure 7d). The 𝛿-Kx V2 O5 ·nH2 O cath-
99% capacity retention at 218 mA g−1 after 300 cycles.[42] ode demonstrated a high initial capacity of 226 mAh g−1 at 20 mA
g−1 . K+ -ion extraction and insertion were accompanied by a re-
versible change between V5+ and V3+ involving two electrons.
3.1.4. Vanadium-Based Electrodes The enhanced 𝛿-Kx V2 O5 ·nH2 O performance is attributed to well-
defined sites for electrochemically cycled K+ ions and the large in-
Vanadium oxides have been investigated as cathode and an- terlayer spacing achieved through chemical preintercalation.[72]
ode materials for application to rechargeable batteries owing Yang et al. hydrothermally synthesized K2 V3 O8 , and the
to their versatile structures, multiple vanadium valence states, cathode delivered a discharge capacity of 107.8 mAh g−1 at
high specific capacities, and high electrochemical reactivity.[67–70] 10 mA g−1 .[73] The use of a highly concentrated electrolyte [7 m
K0.5 V2 O5 exhibits a layered structure formed by edge-sharing oc- potassium bis(fluorosulfonyl)imide (KFSI) dissolved in EC:DEC]
tahedral VO6 and K+ ions sandwiched between the layers (Fig- supported K2 V3 O8 cycling in a wide potential range 4.5–1.5 V

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Figure 7. a) Crystal structure of K0.5 V2 O5, b) galvanostatic charge/discharge voltage profiles, c) rate capability of K0.5 V2 O5 . Reproduced with
permission.[71] Copyright 2018, Wiley. d) Schematic illustration of chemical pre-intercalation synthesis approach. Reproduced with permission.[72] Copy-
right 2018, American Chemical Society. e) Ex situ XRD patterns of the K2 V3 O8 electrode at various charge/discharge states at 10 mA g−1 . Reproduced
with permission.[73] Copyright 2019, Royal Society of Chemistry.

versus K/K+ , and the cathode discharged an average of 2.7 V. pared with high initial K+ -ion contents, Zhang et al. synthesized
However, the cathode exhibited poor cycling stability with only K0.83 V2 O5 .[74] The cathode delivered an initial charge capacity of
73% capacity retention after 50 cycles. Ex situ XRD (Figure 7e) 86 mAh g−1 and a reversible capacity of 90 mAh g−1 at 10 mA
revealed that the capacity degraded because K2 V3 O8 undergoes g−1 . Furthermore, it exhibited cycling stability with 86% capacity
nontopotactic K+ -ion extraction/insertion and reversibly changes retention over 200 cycles. The full cell fabricated using the
between K2 V3 O8 and K2 V3 O8 accompanied by huge volumetric K0.83 V2 O5 cathode and a graphite anode demonstrated an energy
changes (ΔV ≈ 23.4%), which caused the electrode materials to density of 136 Wh kg−1 with an average output of 2.4 V. This
mechanically fail.[73] In the context of layered compounds pre- study provides some insights for designing high-K+ -content

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