Li x （Mg， Ni， Zn， Cu， Co） 1-x O高熵氧化物负极材料电化学储锂特性

doi:10.19799/j.cnki.2095-4239.2022.0738

储能科学与技术 ›› 2023, Vol. 12 ›› Issue (3): 743-753.doi: 10.19799/j.cnki.2095-4239.2022.0738

Li _x （Mg， Ni， Zn， Cu， Co） ₁_-_x O高熵氧化物负极材料电化学储锂特性

刘树港¹(), 蒙波², 李政隆³, 杨亚雄³(), 陈建¹

^1.西安工业大学材料与化工学院，陕西西安 710021
^2.中国航天科技集团有限公司第四研究院，陕西西安 710025
^3.西安工业大学新能源科学与技术研究院，陕西西安 710021

收稿日期:2022-12-09 修回日期:2022-12-16 出版日期:2023-03-05 发布日期:2023-01-18
通讯作者: 杨亚雄 E-mail:897260704@qq.com;yangyaxiong@xatu.edu.cn
作者简介:刘树港（1997—），男，硕士研究生，研究方向为锂离子电池负极材料，E-mail：897260704@qq.com；
基金资助:
国家自然科学基金青年项目(51901168);陕西省高校科协青年人才托举计划项目(20200428)

Electrochemical performance of chemical prelithiated Li _x （Mg, Ni, Zn, Cu, Co） ₁_-_x O high-entropy oxide as anode material for lithium ion battery

Shugang LIU¹(), Bo MENG², Zhenglong LI³, Yaxiong YANG³(), Jian CHEN¹

^1.The Materials Science and Chemical Engineering of Xi'an Technological University, Xi'an 710021, Shaanxi, China
^2.The Fourth Academy of CASC, Xi'an 710025, Shaanxi, China
^3.Institute of Science and Technology for New Energy of Xi'an Technological University, Xi'an 710021, Shaanxi, China

Received:2022-12-09 Revised:2022-12-16 Online:2023-03-05 Published:2023-01-18
Contact: Yaxiong YANG E-mail:897260704@qq.com;yangyaxiong@xatu.edu.cn

摘要/Abstract

摘要：

高熵氧化物是一种新型单相固溶体材料，作为转换反应类型的锂离子电池负极材料近年来受到了广泛关注。本工作通过氧化物与LiH固相加热反应合成了预锂化的单相Li _x (Mg，Ni，Zn，Cu，Co)_1-_x O(x=0，0.08，0.16，0.2)高熵氧化物负极材料，并研究了其电化学储锂特性。结果表明，低价态Li⁺在晶格中引入以及电荷补偿作用使得高熵氧化物中形成Co³⁺、Ni³⁺和氧空位，高价态Co³⁺和Ni³⁺的存在提高了转换反应的电子转移数；氧空位的形成提升了高熵氧化物的导电能力，有利于提高转换反应动力学；同时，非活性Mg²⁺充当缓冲基质保证了电化学过程中的结构稳定性。因此，预锂化的Li_0.16(Mg，Ni，Zn，Cu，Co)_0.84O高熵氧化物负极材料在100 mA/g的电流密度下表现出679 mAh/g的高可逆比容量，63.7%的首次库仑效率，较小的电极极化(充放电平台电压差为-0.9 V)，并且在1000 mA/g的高电流密度下，800次循环后可逆比容量仍保持在651 mAh/g，显示出优异的循环稳定性和倍率特性。

关键词: 锂离子电池, 负极材料, 高熵氧化物, 预锂化

Abstract:

High-entropy oxides, a new class of single-phase solid solution materials, have recently attracted significant attention as conversion-type anode material for lithium-ion batteries (LIBs). Prelithiated Li _x (Mg, Ni, Zn, Cu, Co)_1-_x O (x=0, 0.08, 0.16, 0.2) high-entropy oxide anode materials are synthesized by a chemical reaction of LiH with metal oxides, and the electrochemical performance of the prepared high-entropy oxides are investigated in this study. Introduction of low-valence Li⁺ in the lattice and charge compensation effect facilitate the formation of Co³⁺, Ni³⁺ and oxygen vacancies. Existence of high-valence Co³⁺ and Ni³⁺ increases the electron transfer number of the conversion reaction. The oxygen vacancies promote the electron/ion transportation of the oxide electrode and improve the conversion reaction kinetics. Meanwhile, the inactive Mg²⁺ makes the high entropy oxides maintain the stable rock salt structure upon lithiation/delithiation, which ensures the structural stability during the electrochemical process. As a result, a high reversible specific capacity (679 mAh/g at 100 mA/g), an improved first Coulomb efficiency (63.7%), a decreased polarization (voltage discrepancy between charge and discharge plateaus of -0.9 V), a good cycling stability and high rate capability (reversible specific capacity of 651 mAh/g after 800 cycles at 1000 mA/g) are achieved for prelithiated Li_0.16(Mg, Ni, Zn, Cu, Co)_0.84O high-entropy oxide anode material.

Key words: lithium-ion batteries, anode materials, high-entropy oxides, prelithiation

中图分类号:

TM 911.11

刘树港, 蒙波, 李政隆, 杨亚雄, 陈建. Li _x （Mg， Ni， Zn， Cu， Co） ₁_-_x O高熵氧化物负极材料电化学储锂特性[J]. 储能科学与技术, 2023, 12(3): 743-753.

Shugang LIU, Bo MENG, Zhenglong LI, Yaxiong YANG, Jian CHEN. Electrochemical performance of chemical prelithiated Li _x （Mg, Ni, Zn, Cu, Co） ₁_-_x O high-entropy oxide as anode material for lithium ion battery[J]. Energy Storage Science and Technology, 2023, 12(3): 743-753.

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参考文献 40

1	麻亚挺, 黄健, 刘翔, 等. 微纳米空心结构金属氧化物作为锂离子电池负极材料的研究进展[J]. 储能科学与技术, 2017, 6(5): 871-888.
	MA Y T, HUANG J, LIU X, et al. Hollow micro/nanostructures metal oxide as advanced anodes for lithium-ion batteries[J]. Energy Storage Science and Technology, 2017, 6(5): 871-888.
2	佟永丽, 武祥. 金属有机框架衍生的Co₃O₄电极材料及其电化学性能[J]. 储能科学与技术, 2022, 11(3): 1035-1043.
	TONG Y L, WU X. Electrochemical performance of Co₃O₄electrode materials derived from Co metal-organic framework[J]. Energy Storage Science and Technology, 2022, 11(3): 1035-1043.
3	钮准, 张学燕, 冯佳伟, 等. FeSe₂-C三维导电复合材料的制备及其电化学性能[J]. 储能科学与技术, 2022, 11(11): 3470-3477.
	NIU Z, ZHANG X Y, FENG J W, et al. Preparation and electrochemical properties of FeSe₂-C three-dimensional conductive composites[J]. Energy Storage Science and Technology, 2022, 11(11): 3470-3477.
4	FAN L L, LI X F, SONG X S, et al. Promising dual-doped graphene aerogel/SnS₂ nanocrystal building high performance sodium ion batteries[J]. ACS Applied Materials & Interfaces, 2018, 10(3): 2637-2648.
5	YUAN S, DUAN X, LIU J Q, et al. Recent progress on transition metal oxides as advanced materials for energy conversion and storage[J]. Energy Storage Materials, 2021, 42: 317-369.
6	FANG S, BRESSER D, PASSERINI S. Transition metal oxide anodes for electrochemical energy storage in lithium‐and sodium-ion batteries[J]. Transition Metal Oxides for Electrochemical Energy Storage, 2022: 55-99.
7	LEI Z H, LEE J M, SINGH G, et al. Recent advances of layered-transition metal oxides for energy-related applications[J]. Energy Storage Materials, 2021, 36: 514-550.
8	WANG D, JIANG S D, DUAN C Q, et al. Spinel-structured high entropy oxide (FeCoNiCrMn)₃O₄ as anode towards superior lithium storage performance[J]. Journal of Alloys and Compounds, 2020, 844: doi: 10.1016/j.jallcom.2020.156158.
9	LIU J P, DONG L W, CHEN D J, et al. Metal oxides with distinctive valence states in an electron-rich matrix enable stable high-capacity anodes for Li ion batteries[J]. Small Methods, 2020, 4(2): doi: 10.1002/smtd.201900753.
10	尹坚, 董季玲, 丁皓, 等. 锂离子电池过渡金属氧化物负极材料研究进展[J]. 储能科学与技术, 2021, 10(3): 995-1001.
	YIN J, DONG J L, DING H, et al. Research progress of transition metal oxide anode materials for lithium-ion batteries[J]. Energy Storage Science and Technology, 2021, 10(3): 995-1001.
11	YUE L C, MA C Q, YAN S H, et al. Improving the intrinsic electronic conductivity of NiMoO₄ anodes by phosphorous doping for high lithium storage[J]. Nano Research, 2022, 15(1): 186-194.
12	NI S B, LIU J L, CHAO D L, et al. Vanadate-based materials for Li-ion batteries: The search for anodes for practical applications[J]. Advanced Energy Materials, 2019, 9(14): doi: 10.1002/aenm.201803324.
13	WAN B C, GUO J C, LAI W H, et al. Layered mesoporous CoO/reduced graphene oxide with strong interfacial coupling as a high-performance anode for lithium-ion batteries[J]. Journal of Alloys and Compounds, 2020, 843: doi: 10.1016/j.jallcom.2020.156050.
14	LI H, WU L J, ZHANG S G, et al. Facile synthesis of mesoporous one-dimensional Fe₂O₃ nanowires as anode for lithium ion batteries[J]. Journal of Alloys and Compounds, 2020, 832: doi: 10.1016/j.jallcom.2020.155008.
15	YANG X B, WANG H Q, SONG Y Y, et al. Low-temperature synthesis of a porous high-entropy transition-metal oxide as an anode for high-performance lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2022: 14(23): 26873-26881.
16	DING Y C, HU L H, HE D C, et al. Design of multishell microsphere of transition metal oxides/carbon composites for lithium ion battery[J]. Chemical Engineering Journal, 2020, 380: doi: 10.1016/j.cej.2019.122489.
17	SUN R, QIN Z X, LI Z Y, et al. Binary zinc-cobalt metal-organic framework derived mesoporous ZnCo₂O₄@NC polyhedron as a high-performance lithium-ion battery anode[J]. Dalton Transactions (Cambridge, England: 2003), 2020, 49(40): 14237-14242.
18	CHEN Z W, FEI S M, WU C H, et al. Integrated design of hierarchical CoSnO₃@NC@MnO@NC nanobox as anode material for enhanced lithium storage performance[J]. ACS Applied Materials & Interfaces, 2020, 12(17): 19768-19777.
19	LIANG W F, ZHONG L P, QUAN L J, et al. Sandwich-like MoO₃/ZnCo₂O₄ QDs@C@rGO/MoO₃ hybrid nanosheets as high-performance anode for lithium-ion batteries[J]. Ceramics International, 2021, 47(22): 32118-32129.
20	LIU J Z, WU J, ZHOU C C, et al. Single-phase ZnCo₂O₄ derived ZnO-CoO mesoporous microspheres encapsulated by nitrogen-doped carbon shell as anode for high-performance lithium-ion batteries[J]. Journal of Alloys and Compounds, 2020, 825: doi: 10.1016/j.jallcom.2020.153951.
21	WANG Q S, SARKAR A, WANG D, et al. Multi-anionic and-cationic compounds: New high entropy materials for advanced Li-ion batteries[J]. Energy & Environmental Science, 2019, 12(8): 2433-2442.
22	SARKAR A, VELASCO L, WANG D, et al. High entropy oxides for reversible energy storage[J]. Nature Communications, 2018, 9(1): 1-9.
23	ROST C M, RAK Z, BRENNER D W, et al. Local structure of the Mgx Nix Cox Cux Znx O(x=0.2) entropy-stabilized oxide: An EXAFS study[J]. Journal of the American Ceramic Society, 2017, 100(6): 2732-2738.
24	BÉRARDAN D, FRANGER S, DRAGOE D, et al. Colossal dielectric constant in high entropy oxides[J]. Physica Status Solidi (RRL)-Rapid Research Letters, 2016, 10(4): 328-333.
25	BÉRARDAN D, FRANGER S, MEENA A K, et al. Room temperature lithium superionic conductivity in high entropy oxides[J]. Journal of Materials Chemistry A, 2016, 4(24): 9536-9541.
26	GRZESIK Z, SMOŁA G, MISZCZAK M, et al. Defect structure and transport properties of (Co, Cr, Fe, Mn, Ni)₃O₄ spinel-structured high entropy oxide[J]. Journal of the European Ceramic Society, 2020, 40(3): 835-839.
27	SARKAR A, WANG Q S, SCHIELE A, et al. High-entropy oxides: Fundamental aspects and electrochemical properties[J]. Advanced Materials (Deerfield Beach, Fla), 2019, 31(26): doi: 10.1002/adma.201806236.
28	GHIGNA P, AIROLDI L, FRACCHIA M, et al. Lithiation mechanism in high-entropy oxides as anode materials for Li-ion batteries: An operando XAS study[J]. ACS Applied Materials & Interfaces, 2020, 12(45): 50344-50354.
29	KHERADMANDFARD M, MINOUEI H, TSVETKOV N, et al. Ultrafast green microwave-assisted synthesis of high-entropy oxide nanoparticles for Li-ion battery applications[J]. Materials Chemistry and Physics, 2021, 262: doi: 10.1016/j.matchemphys. 2021.124265.
30	CHEN T Y, WANG S Y, KUO C H, et al. In operando synchrotron X-ray studies of a novel spinel (Ni_0.2Co_0.2Mn_0.2Fe_0.2Ti_0.2)₃O₄ high-entropy oxide for energy storage applications[J]. Journal of Materials Chemistry A, 2020, 8(41): 21756-21770.
31	MIN X Q, XU G J, XIE B, et al. Challenges of prelithiation strategies for next generation high energy lithium-ion batteries[J]. Energy Storage Materials, 2022, 47: 297-318.
32	SUN J R, HUANG L, XU G J, et al. Mechanistic insight into the impact of pre-lithiation on the cycling stability of lithium-ion battery[J]. Materials Today, 2022, 58: 110-118.
33	CHUNG D J, YOUN D, KIM S, et al. Dehydrogenation-driven Li metal-free prelithiation for high initial efficiency SiO-based lithium storage materials[J]. Nano Energy, 2021, 89: doi: 10.1016/j.nanoen.2021.106378.
34	CHOI J, JEONG H, JANG J, et al. Weakly solvating solution enables chemical prelithiation of graphite-SiOx anodes for high-energy Li-ion batteries[J]. Journal of the American Chemical Society, 2021, 143(24): 9169-9176.
35	YANG Y X, QU X L, ZHANG X, et al. Higher than 90% initial coulombic efficiency with staghorn-coral-like 3D porous LiFeO_2- x as anode materials for Li-ion batteries[J]. Advanced Materials (Deerfield Beach, Fla), 2020, 32(22): doi: 10.1002/adma.201908285.
36	XIE W L, YANG Z Q, CHUN H. Catalytic properties of lithium-doped ZnO catalysts used for biodiesel preparations[J]. Industrial & Engineering Chemistry Research, 2007, 46(24): 7942-7949.
37	USHARANI N J, SHRINGI R, SANGHAVI H, et al. Role of size, alio-/ multi-valency and non-stoichiometry in the synthesis of phase-pure high entropy oxide (Co, Cu, Mg, Na, Ni, Zn)O[J]. Dalton Transactions (Cambridge, England: 2003), 2020, 49(21): 7123-7132.
38	QIU N, CHEN H, YANG Z M, et al. A high entropy oxide (Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2O) with superior lithium storage performance[J]. Journal of Alloys and Compounds, 2019, 777: 767-774.
39	ZHANG J, JIANG H, ZENG Y B, et al. Oxygen-defective Co₃O₄ for pseudo-capacitive lithium storage[J]. Journal of Power Sources, 2019, 439: doi: 10.1016/j.jpowsour.2019.227026.
40	YUAN D, DOU Y H, XU L, et al. Atomically thin mesoporous NiCo₂O₄ grown on holey graphene for enhanced pseudocapacitive energy storage[J]. Journal of Materials Chemistry A, 2020, 8(27): 13443-13451.

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Li _x （Mg， Ni， Zn， Cu， Co） ₁_-_x O高熵氧化物负极材料电化学储锂特性

Electrochemical performance of chemical prelithiated Li _x （Mg, Ni, Zn, Cu, Co） ₁_-_x O high-entropy oxide as anode material for lithium ion battery

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