钾离子电池过渡金属氧化物正极材料：研究进展与设计策略

doi:10.1016/j.actphy.2025.100217

摘要/Abstract

摘要：

钾离子电池由于其资源丰富且电化学特性与锂离子电池相似等优点在近年受到广泛关注。正极材料的设计优化是提升钾离子电池综合性能的关键。其中，过渡金属氧化物正极凭借其高理论容量、适宜的工作电压窗口、可调控的晶体结构等性质成为研究热点。然而，K⁺的大离子半径和过渡金属的姜-泰勒畸变易引发晶格结构失稳，导致不可逆相变、过渡金属溶出等问题，限制了正极材料的循环寿命与能量密度的提升。本综述系统介绍了钾离子电池过渡金属氧化物正极材料的评估体系和合成方法，并重点评述了近年来过渡金属氧化物正极材料针对上述核心挑战的研究进展。同时，结合过渡金属氧化物正极材料研究中元素掺杂、表面包覆以及多尺度合成等设计策略及其作用机理，剖析当前研究的关键瓶颈并对未来发展方向进行展望，为促进钾离子电池在大规模储能系统中的应用和其他二次电池技术的发展提供借鉴参考。

关键词: 钾离子电池, 正极, 过渡金属氧化物, 姜-泰勒效应, 相变

Abstract:

Potassium-ion batteries (PIBs) have emerged as promising candidates for large-scale energy storage systems, owing to the abundant potassium resources and electrochemical properties similar to those of lithium-ion systems. Cathode materials play a pivotal role in determining the overall performance of PIBs. Among them, transition metal oxides (TMOs) have attracted extensive research interest due to their high theoretical capacity, suitable operating voltage, and tunable crystal structures. However, the relatively large ionic radius of K⁺ often leads to significant volume variation and anisotropic strain during (de)intercalation, which induces irreversible phase transitions, severe lattice distortion, and structural collapse. In addition, the Jahn-Teller effect associated with transition-metal ions such as Mn³⁺ further aggravates local structural distortion and triggers transition metal dissolution, severely limiting the cycling stability and energy density of TMO cathodes. These issues underscore the importance of rational material design and interface regulation to achieve stable electrochemical performance. This review systematically summarizes the recent progress in TMO cathode materials for PIBs, encompassing evaluation metrics and synthesis methods. A variety of modification strategies, including elemental doping, surface coating, and multi-scale structural design, have been developed to modulate lattice parameters and defects, suppress phase transitions, and enhance ionic conductivity, operating voltage, structural stability, and cycling endurance. Among these approaches, P2/P3 biphasic integration and high-entropy doping, for example, have been shown to effectively inhibit Jahn-Teller distortion and volume change, thereby enabling long-term cyclability. In addition, the combination of in situ characterization and theoretical calculations has significantly deepened the understanding of K⁺ storage mechanisms and structure-performance relationships. Notwithstanding the substantial progress achieved, several critical challenges persist. These include capacity enhancement and structural stability optimization, cycle life improvement and the formulation of integrated strategies, cathode-electrolyte interphase engineering, the development of composite materials and hybrid systems, ensuring manufacturing consistency and scalability, advancing theoretical modeling and computational guidance, as well as leveraging artificial intelligence (AI)-assisted material design and prediction. Future efforts should focus on developing novel structural motifs, optimizing electrode/electrolyte interfaces, advancing sustainable manufacturing processes, and integrating AI-guided material design. This review provides a comprehensive overview of mechanistic strategies and recent progress, offering valuable insights for the rational design of high-performance PIBs suitable for practical applications in large-scale energy storage and next-generation energy storage applications.

Key words: Potassium-ion battery, Cathode, Transition metal oxide, Jahn-Teller effect, Phase transition

武利琛, 杨祎晗, 周江, 鲁兵安. 钾离子电池过渡金属氧化物正极材料：研究进展与设计策略[J]. 物理化学学报, 2026, 42(7), 100217. doi: 10.1016/j.actphy.2025.100217

Lichen Wu, Yihan Yang, Jiang Zhou, Bingan Lu. Transition metal oxide cathode materials for potassium-ion batteries: research progress and design strategies[J]. Acta Phys. -Chim. Sin. 2026, 42(7), 100217. doi: 10.1016/j.actphy.2025.100217

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2025.100217

https://www.whxb.pku.edu.cn/CN/Y2026/V42/I7/100217

图/表 17

图1

图2

表1

图3

图4

图5

图6

图7

图8

表2

doping elements	Valence state	Doping site	Electrochemical activity	Advantages
Co	+3	TM	Yes	Suppress the Jahn-Teller effect, enhance the K⁺ migration ability and cycling stability, and elevate the voltage
Ni	+2	TM	Yes	Stabilize the structure by suppressing the Jahn-Teller effect, increase the interlayer spacing, and facilitate multi-electron reactions
Fe	+3	TM	Yes	Generate a more stable atomic configuration, suppress the Jahn-Teller effect, enhance the K⁺ migration ability, and elevate the voltage
Li	+1	TM	No	Inhibit K⁺/vacancy ordering, homogenize Mn–O bond lengths, and enhance phase transition reversibility
Rb	+1	K	No	Expand the interlayer spacing, maintain the symmetry of the MnO₆ structure
Cu	+2	TM	No	Elevate the Mn valence state, suppress the Jahn-Teller effect, and improve air stability
Mg	+2	TM/K	No	Suppress the Jahn-Teller effect, increase the interlayer distance, facilitate the migration of K⁺, and inhibit phase transitions
Zn	+2	TM	No	Reduce the electrostatic repulsion of O²⁻ and suppress the Jahn-Teller distortion
Al	+3	TM	No	Suppress the Jahn-Teller effect and mitigate the dissolution of Mn
Cr	+3	TM	No	Forming O vacancies, and facilitate the migration of K⁺
B	+3	Gap	No	Expand the interlayer spacing, and suppress the loss of lattice oxygen
Ti	+4	TM	No	Increase the covalency of the Mn–O bond, suppress the Jahn-Teller effect, and inhibit phase transition
Nb	+5	TM	No	Expand the interlayer spacing, activate lattice oxygen, and inhibit phase transition
P	+6	Gap	No	Expand the interlayer spacing, stabilize the MnO₆ octahedral structure, and suppress the Jahn-Teller effect
W	+6	TM	No	Enhance the Mn–O–W covalent bond, inhibit the dissolution of manganese, expand the interlayer spacing, and suppress the phase transition
Mo	+6	TM	No	Enhance structural stability, suppress the Jahn-Teller effect, and improve the migration ability of K⁺
F	−1	O	No	Expand the interlayer spacing, and suppress the loss of lattice oxygen
N	−3	O	No	Expand the interlayer spacing, enhance the migration ability of K⁺, and improve the electronic conductivity

表2

图9

图10

图11

图12

表3

Cathodes	Voltage window (V)	Discharge capacity (mAh g⁻¹)/Current density (mA g⁻¹)	Capacity retention/ Cycles/Current density (mA g⁻¹)	References
P2-K_0.21MnO₂	1.5–3.9	99.3/20	49.8%/100/20	[45]
P2-K_1/3Co_1/3Mn_2/3O₂	1.5–4.2	98/15	74%/100/15	[46]
P2/P3-K_0.7Mn_0.67Ni_0.33O₂	1.5–4.0	116.3/10	83.1%/600/100	[47]
P3-K_0.5Mn_0.8Co_0.1Ni_0.1O₂	1.5–4.0	94.5/20	62%/300/100	[48]
P3-K_0.45Ni_0.1Fe_0.1Mn_0.8O₂	1.5–3.9	91/20	67%/100/20	[49]
P3-K_0.67Li_0.07Mn_0.93O₂	1.5–4.0	84.3/10	81.3%/100/50	[50]
P2-K_0.56Na_0.11Li_0.12Ni_0.22Mn_0.66O₂	1.5–4.6	90.2/30	91.5%/300/75	[51]
P3-K_0.45Rb_0.05Mn_0.85Mg_0.15O₂	1.5–3.9	108/20	98.2%/200/200	[52]
P3-K_0.5Mn_0.7Fe_0.2Cu_0.1O₂	1.5–4.2	91/50	62.3%/100/100	[53]
P3-K_0.5Mg_0.15[Mn_0.8Mg_0.05]O₂	1.4–4.0	102/10	48.2%/400/100	[54]
P3-K_0.5MnO₂-Zn-30C	1.5–4.2	127/50	70.2%/50/50	[55]
P3-K_0.45Mn_0.9Al_0.1O₂	1.5–3.9	152/20	67%/1000/500	[56]
P3-K_0.5Mn_0.95Cr_0.05O₂	1.5–4.0	90/50	70%/300/500	[57]
P3-K_0.5Mn_0.92Ti_0.08O₂	1.5–3.9	126.9/20	53.7%/100/20	[58]
P2-K_0.67Mn_0.75Ni_0.23Nb_0.02O₂	1.7–4.0	134.8/10	82.6%/300/200	[59]
P2-K_0.6MnP_0.02O₂	1.5–3.9	102.8/50	59.5%/500/500	[60]
P3-K_0.5Mn_0.95W_0.05O₂	1.5–4.0	94.2/100	90.5%/1000/200	[61]
P3-K_0.5Mn_0.95Mo_0.05O₂	1.5–4.0	100.6/20	75%/500/200	[62]
P2-K_2/3Mn_7/9Ni_1/9Ti_1/9O_17/9F_1/9	1.5–4.2	132.5/10	91%/50/100	[63]
K_0.45Li_0.045Mn_0.8Co_0.1Fe_0.05Ni_0.05O_1.95F_0.05	1.5–3.9	123.7/50	74%/500/1000	[64]
P′2-K_0.5Mn_0.85Mg_0.1Ti_0.05B_0.02F_0.1O_1.9	1.5–4.3	147/50	98%/2200/500	[65]
P3-K_0.5Mn_0.67Fe_0.33O_1.95N_0.05	1.5–4.0	104.2/20	74.4%/300/100	[66]
P3-K_0.7Fe_0.05Co_0.1Mn_0.75Ni_0.05V_0.05O₂	1.5–3.9	106.2/50	70.3%/500/1000	[67]
P3-K_0.45Mn_0.6Co_0.1Mg_0.1Cu_0.1Ti_0.1O₂	1.5–4.0	98.8/20	83.3%/500/100	[68]
P3-K_0.45Mn_0.60Ni_0.075Fe_0.075Co_0.075Ti_0.10Cu_0.05Mg_0.025O₂	1.5–4.2	106.8/10	60.4%/200/100	[69]
K-birnessite K_0.21MnO₂·0.31H₂O	1.5–4.0	86.3/40	80.1%/50/40	[70]
K-birnessite K_0.28MnO₂·0.29H₂O	1.5–3.9	137.9/20	81%/300/1000	[71]
P3-K_0.6MnO_1.97F_0.03@KF	1.5–3.9	110/10	77.3%/100/100	[72]
P2-K_0.5Ni_0.1Mn_0.9O₂@FePO₄	1.5–3.9	134.7/50	66%/2500/500	[73]
P3-K_0.5MnO₂@KTaO₃	1.5–3.9	100/50	98.8%/200/300	[74]
P2-K_0.6CoO₂	1.7–4.0	87.2/20	86.9%/1000/40	[75]
P3-K_0.70[Cr_0.86Sb_0.14]O₂	1.5–4.1	126.1/15	92.4%/200/150	[76]
P3-K_0.71[Cr_0.75Ti_0.25]O₂	1.5–4.0	150/16	73%/300/158	[77]
α-V₂O₅	1.5–4.0	120/25	66.7%/200/25	[78]
γ′-V₂O₅	2.4–4.4	70/7.5	78%/100/15	[79]
K_0.486V₂O₅/PAN	1.5–3.8	81.87/20	57%/500/200	[80]
V₁₀O₂₄·2.81H₂O	2.0–4.0	110/10	99.2%/700/500	[81]
K_0.34Sr_0.03V₂O₅	1.5–4.2	113/20	67%/100/100	[82]
K_0.12(NH₄)_0.31V₂O₅	1.5–3.8	118.2/50	69.3%/2000/500	[83]
Amorphous VO₂	1.0–4.0	111/20	80%/8500/500	[84]
K_0.8Mn_0.8Ti_1.2O₄	1.5–4.2	77.8/20	65.7%/300/100	[85]
K_0.17TiO₂	1.0–4.2	79/15.5	98%/1000/1550	[86]
KFeO₂	2.5–3.7	44.3/10	44.5%/30/10	[87]
KFeO₂/KFe₅O₈	1.5–4.0	51.7/20	59%/30/20	[88]

表3

图13

图14

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Synthesis methods	Cost	Purity	Morphology	Milling/Calcination	Advantages	Disadvantages
Solid-state method	Low	Poor	Poor	Required	The route is simple and amenable to mass production	The purity and morphology of the materials are difficult to control
Hydrothermal synthesis	Medium	Moderate	Good	Not required	No milling required and low preparation temperature	The reaction products are not easy to separate
Co-precipitation method	Medium	Moderate	Moderate	Required	Uniform particle size and good morphology	The precipitating agent, rotational speed, and pH value are hard to determine
Sol-gel method	High	Good	Moderate	Required	The precursors are well mixed and the sample purity is high	The cost is high, and pH value and precursors have a significant impact

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