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1.安徽工业大学 材料科学与工程学院 先进陶瓷研究中心,安徽马鞍山 243032
2.安徽工业大学,氢电高效转化与固态存储安徽省重点实验室,安徽马鞍山 243032
Received:27 April 2026,
Revised:2026-06-18,
Accepted:24 June 2026,
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PAN Meiyi, YIN Feilong, XU Shibiao, et al. La3+ Doped Spinel-Perovskite Dual-Phase High-Entropy Oxides for Lithium Storage Performance[J/OL]. CIESC Journal, 2026. DOI: 10.11949/0438-1157.20260598.
针对尖晶石型高熵氧化物(High entropy oxides
HEOs)负极材料的前期循环稳定性差及电子/离子传输动力学缓慢的问题。采用溶液燃烧法,在尖晶石型(Co
0.2
Cr
0.2
Fe
0.2
Mn
0.2
Ni
0.2
)
3
O
4
中掺杂大阳离子半径的La
3+
,构筑了一系列多孔网络结构的尖晶石-钙钛矿双相高熵氧化物(La
x
-Co
0.2
-Cr
0.2
-Fe
0.2
-Mn
0.2
-Ni
0.2
-O
x
=0.1、0.2、0.5和1.0)。结果表明,随着La
3+
掺杂量增加,试样中尖晶石相逐渐向钙钛矿相转变,钙钛矿相比例显著上升,当x=0.5(5MLa0.5,钙钛矿相约46%)时,电极表现出最优电化学性能。优化的5MLa0.5电极在0.2 A·g
-1
下循环340次后,可逆比容量达1251 mAh·g
-1
,均高于尖晶石型(Co
0.2
Cr
0.2
Fe
0.2
Mn
0.2
Ni
0.2
)
3
O
4
和钙钛矿型La(Co
0.2
Cr
0.2
Fe
0.2
Mn
0.2
Ni
0.2
)O
3
HEOs的理论比容量;在1 A·g
-1
下循环600次后,仍保持490 mAh·g
-1
的可逆比容量。电化学性能提升的原因主要归因于异质界面可以显著优化离子的吸附/脱附以及界面位置的电子密度,从而促进重复循环中的电荷转移以及电子/Li
+
扩散动力学,并增强了赝电容贡献。本研究通过La
3+
掺杂调控尖晶石-钙钛矿双相比例,是提升HEOs负极储锂性能并抑制前期容量衰减的有效策略。
To address the issues of poor initial cycling stability and sluggish electron/ion transport kinetics in spinel-type high-entropy oxides (HEOs) anode materials
a series of porous spinel–perovskite dual-phase HEOs (La
x
-Co
0.2
-Cr
0.2
-Fe
0.2
-Mn
0.2
-Ni
0.2
-O
x
=0.1
0.2
0.5 and 1.0) were constructed via a solution combustion method by introducing large-radius La
3+
into spinel-type (Co
0.2
Cr
0.2
Fe
0.2
Mn
0.2
Ni
0.2
)
3
O
4
. The results show that with increasing La
3+
content
the spinel phase gradually transforms into the perovskite phase
accompanied by a significant increase in the proportion of the perovskite phase. When
x
=0.5 (5MLa0.5
perovskite phase accounts for about 46%)
the electrode exhibits optimal electrochemical performance. After 340 cycles at 0.2 A·g
-1
the optimized 5MLa0.5 electrode delivers a reversible specific capacity of 1251 mAh·g
-1
which is higher than the theoretical specific capacities of both spinel-type (Co
0.2
Cr
0.2
Fe
0.2
Mn
0.2
Ni
0.2
)
3
O
4
and perovskite-type La(Co
0.2
Cr
0.2
Fe
0.2
Mn
0.2
Ni
0.2
)O
3
HEOs. It still maintains a reversible specific capacity of 490 mAh·g
-1
after 600 cycles at 1 A·g
-1
. The improvement in electrochemical performance is mainly attributed to the fact that heterogeneous interfaces can significantly optimize the adsorption/desorption of ions and the electron density at the interface
thereby facilitating charge transfer and the diffusion kinetics of electrons and Li
+
during repeated cycles
as well as enhancing the pseudocapacitance contribution. This study that tuning the spinel–perovskite dual-phase ratio via La
3+
doping is an effective strategy to improve the lithium storage performance of HEOs anodes and suppress early-stage capacity decay.
Anandkumar M , Trofimov E . Synthesis, properties, and applications of high-entropy oxide ceramics: Current progress and future perspectives [J ] . Journal of Alloys and Compounds , 2023 , 960 : 170690 .
Ma J X , Liu T Y , Ye W H , et al . High-entropy perovskite oxides for energy materials: a review [J ] . Journal of Energy Storage , 2024 , 90 : 111890 .
Ajayi S O , Dolla T H , Bello I T , et al . Recent developments strategies in high entropy modified lithium-rich layered oxides cathode for lithium-ion batteries [J ] . Inorganic Chemistry Communications , 2025 , 172 : 113721 .
王朋朋 , 贾洋刚 , 邵霞 , 等 . K + 掺杂尖晶石型(Co 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 高熵氧化物负极材料制备与储锂性能研究 [J ] . 化工学报 , 2022 , 73 ( 12 ): 5625 - 5637 .
Wang P P , Jia Y G , Shao X , et al . Preparation and lithium storage performance of K + -doped spinel (Co 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 high-entropy oxide anode materials [J ] . CIESC Journal , 2022 , 73 ( 12 ): 5625 - 5637 .
徐世彪 , 韦正兵 , 鲍梦凡 , 等 . Cu阳离子空位提升钙钛矿型高熵氧化物储锂性能 [J ] . 化工学报 , 2025 , 76 ( 12 ): 6718 - 6728 .
Xu S B , Wei Z B , Bao M F , et al . Cu cation vacancies enhance the lithium storage performance of perovskite-type high-entropy oxides [J ] . CIESC Journal , 2025 , 76 ( 12 ): 6718 - 6728 .
邵霞 , 贾洋刚 , 程婕 , 等 . 钙钛矿型La(Co 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 )O 3 高熵氧化物的制备及电化学性能 [J ] . 过程工程学报 , 2023 , 23 ( 5 ): 771 - 780 .
Shao X , Jia Y G , Cheng J , et al . Preparation and electrochemical properties of perovskite-type La(Co 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 )O 3 high-entropy oxide [J ] . The Chinese Journal of Process Engineering , 2023 , 23 ( 5 ): 771 - 780 .
Yang H M , He L X , Yang Z M , et al . Design optimization of spinel-rocksalt intergrown high entropy oxide structure for enhanced electrochemical properties [J ] . Journal of Alloys and Compounds , 2023 , 968 : 172135 .
Monsef R , Salavati-Niasari M , Masjedi-Arani M . Hydrothermal synthesis of spinel-perovskite Li-Mn-Fe-Si nanocomposites for electrochemical hydrogen storage [J ] . Inorganic Chemistry , 2022 , 61 ( 18 ): 6750 - 6763 .
Chen Y Z , Bovet N , Trier F , et al . A high-mobility two-dimensional electron gas at the spinel/perovskite interface of γ-Al 2 O 3 /SrTiO 3 [J ] . Nature Communications , 2013 , 4 : 1371 .
Sarkar A , Velasco L , Wang D , et al . High entropy oxides for reversible energy storage [J ] . Nature Communications , 2018 , 9 : 3400 .
Xiao B , Wu G , Wang T D , et al . High entropy oxides (FeNiCrMnX) 3 O 4 (X=Zn, Mg) as anode materials for lithium ion batteries [J ] . Ceramics International , 2021 , 47 ( 24 ): 33972 - 33977 .
Nguyen T X , Tsai C C , Patra J , et al . Co-free high entropy spinel oxide anode with controlled morphology and crystallinity for outstanding charge/discharge performance in Lithium-ion batteries [J ] . Chemical Engineering Journal , 2022 , 430 : 132658 .
贾洋刚 , 邵霞 , 程婕 , 等 . 赝电容控制型钙钛矿高熵氧化物La(Co 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 )O 3 负极材料的制备及储锂性能 [J ] . 高等学校化学学报 , 2022 , 43 ( 8 ): 163 - 173 .
Jia Y G , Shao X , Cheng J , et al . Preparat ion and lithium storage performance of pseudocapacitance-controlled chalcogenide high-entropy oxide La(Co 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 )O 3 anode materials [J ] . Chemical Journal of chinese universities , 2022 , 43 ( 8 ): 163 - 173 .
Li Y X , Qiu Y C , Yao G M , et al . Dual-phase (AlMgCoNiCuZn)O high-entropy oxide embedded in graphite nanosheets with superior lithium storage capability [J ] . Journal of Energy Storage , 2025 , 115 : 115993 .
Wang M , Chen L , Liu M , et al . Enhanced electrochemical performance of La-doped Li-rich layered cathode material [J ] . Journal of Alloys and Compounds , 2020 , 848 : 156620 .
Petrovičovà B , Xu W L , Musolino M G , et al . High-entropy spinel oxides produced via sol-gel and electrospinning and their evaluation as anodes in Li-ion batteries [J ] . Applied Sciences , 2022 , 12 ( 12 ): 5965 .
Li S , Peng H R , Tong L K , et al . Development of a novel CNT-composited high entropy boride (MnFeCoNiZnAl) 1/6 B cathode material for ultra-stable and long-life sodium-ion batteries: DFT and experimental study [J ] . Acta Materialia , 2025 , 287 : 120813 .
Wang K , Hua W B , Huang X H , et al . Synergy of cations in high entropy oxide lithium ion battery anode [J ] . Nature Communications , 2023 , 14 : 1487 .
Nguyen T X , Patra J , Tsai C C , et al . Secondary-phase-induced charge–discharge performance enhancement of co-free high entropy spinel oxide electrodes for Li-ion batteries [J ] . Advanced Functional Materials , 2023 , 33 ( 30 ): 2300509 .
Liu X F , Ding L X , Li K Z , et al . The role of oxygen defects in high entropy perovskite for lithium ion batteries [J ] . Acta Materialia , 2025 , 287 : 120812 .
马连波 , 郑雨爽 , 李莉媛 . 锌碘电池中碘载体材料的研究进展 [J ] . 安徽工业大学学报(自然科学版) , 2024 , 41 ( 2 ): 118 - 134 .
Ma L B , Zheng Y S , Li L Y . Research progress on iodine host materials for zinc‒iodine batteries [J ] . Journal of Anhui University of Technology (Natural Science) , 2024 , 41 ( 2 ): 118 - 134 .
Yang H M , He L X , Chen Q C , et al . Phase-selective defects engineering in dual-phase high entropy oxide for Li-ion storage [J ] . Chemical Engineering Journal , 2024 , 488 : 151113 .
Duan C Q , Tian K H , Li X L , et al . New spinel high-entropy oxides (FeCoNiCrMnXLi) 3 O 4 (X = Cu, Mg, Zn) as the anode material for lithium-ion batteries [J ] . Ceramics International , 2021 , 47 ( 22 ): 32025 - 32032 .
Liang Y H , Feng R H , Jin C Q , et al . Preparation and electrochemical properties of high-entropy oxide Li x (CrMnCoNiZn) 3- x O 4 [J ] . Materials Today Communications , 2025 , 47 : 113111 .
Tian K H , Duan C Q , Ma Q , et al . High-entropy chemistry stabilizing spinel oxide (CoNiZnXMnLi) 3 O 4 (X = Fe, Cr) for high-performance anode of Li-ion batteries [J ] . Rare Metals , 2022 , 41 ( 4 ): 1265 - 1275 .
Kim H , Choi W , Yoon J , et al . Exploring anomalous charge storage in anode materials for next-generation Li rechargeable batteries [J ] . Chemical Reviews , 2020 , 120 ( 14 ): 6934 - 6976 .
Augustyn V , Simon P , Dunn B . Pseudocapacitive oxide materials for high-rate electrochemical energy storage [J ] . Energy & Environmental Science , 2014 , 7 ( 5 ): 1597 - 1614 .
He Q Y , Li J T , Liu W , et al . High entropy oxides for electrochemical energy storage and conversion: a critical review [J ] . Journal of Power Sources , 2024 , 619 : 235207 .
Wang X L , Liu J , Hu Y F , et al . Oxygen vacancy-expedited ion diffusivity in transition-metal oxides for high-performance lithium-ion batteries [J ] . Science China Materials , 2022 , 65 ( 6 ): 1421 - 1430 .
Chen S J , Bao M F , Jia Y G , et al . Lattice distortion induced rock salt high-entropy oxide for high-rate lithium-ion storage [J ] . Journal of Alloys and Compounds , 2024 , 990 : 174480 .
Bao M F , Wei Z B , Xu S B , et al . Temperature-mediated crystallinity engineering in spinel high-entropy oxide anode enable high-rate pseudocapacitive lithium-ion storage [J ] . Journal of Power Sources , 2026 , 661 : 238632 .
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