掺杂技术在锰基层状富锂氧化物正极材料中应用进展

doi:10.19799/j.cnki.2095-4239.2022.0284

摘要/Abstract

摘要：

锂离子电池(LIBs)凭借能量密度高、能量转换效率高的优势，已成为当今最受欢迎的储能器件。嵌入型正极材料中，锰基层状富锂氧化物xLi₂MnO₃·(1-x)LiMO₂具有最高的放电比容量和高工作电压，但存在结构稳定性差等问题限制其应用在大规模储能领域。本文通过对近期相关文献的探讨，综述了提高富锂正极材料的结构稳定性和电化学性能的策略，回顾了晶格掺杂对锰基层状富锂氧化物正极材料的结构改性设计，分析了锂(Li)位、过渡金属(TM)位和氧(O)位的不同掺杂对其结构和性能的影响，着重介绍了单掺杂和双掺杂两种方法，总结了不同离子在不同位置单掺杂的电化学性能对比，阐述了掺杂后材料的结构变化和影响性能的机制。综合分析表明，晶格掺杂策略对提高循环性能、倍率性能、首次放电容量、首次库仑效率和缓解电压衰减等有显著影响，其中双掺杂的协同效应相比于单掺杂具有更高的结构稳定性和更优异的电化学性能。希望能为富锂相正极材料在下一代高能量密度锂离子电池储能领域的广泛应用提供参考。

关键词: 富锂正极, 离子掺杂, 单掺杂, 双掺杂

Abstract:

Because of their high energy density and high energy conversion efficiency, lithium-ion batteries (LIBs) have become the most popular energy storage device. Among the embedded cathode materials, Mn-based Li-rich oxide xLi₂MnO₃·(1-x)LiMO₂ has the highest discharge specific capacity and high working voltage; however, its poor structural stability limits its application in the field of large-scale energy storage. Based on a review of recent relevant literature, the purpose of this paper is to summarize strategies for improving the structural stability and electrochemical properties of lithium-rich cathode materials, review the structural modification design of manganese-based lithium-rich oxide cathode materials by lattice doping and analyze the effects of different doping lattice sites: lithium (Li), transition metal (TM), and oxygen (O) on their structures and properties, including single-doping and double-doping. We compare the electrochemical properties of single doping at various positions and describe structural changes in doped materials as well as the mechanism of affecting properties. According to the comprehensive analysis, the lattice-doping strategy has a significant impact on the improvement of cycle performance, rate capability, first discharge capacity, first coulomb efficiency, and voltage attenuation mitigation. Double doping has greater structural stability and better electrochemical properties than single doping. It is hoped that it will serve as an experimental foundation for the widespread use of Li-rich cathode materials in the energy storage field of next-generation high energy density LIBs.

Key words: Li-rich cathode, lattice doping, single-doping, double-doping

中图分类号:

TM 912

陈紫莹, 丁翔, 童庆松, 李俊延, 黄景瑜. 掺杂技术在锰基层状富锂氧化物正极材料中应用进展[J]. 储能科学与技术, 2022, 11(8): 2681-2690.

Ziying CHEN, Xiang DING, Qingsong TONG, Junyan LI, Jingyu HUANG. Application progress of doping technology in Mn-based lithium rich oxide cathode materials[J]. Energy Storage Science and Technology, 2022, 11(8): 2681-2690.

图/表 8

图1

图2

表1

富锂正极材料不同离子的单掺杂的电化学性能对比 (1 C=250 mAh/g)"

合成方法	材料	首次放电比容量	循环性能	倍率性能	参考文献
共沉淀	Na@0.5LiMnO₃, 0.5LiNi_1/3Co_1/3Mn_1/3O₂	286，0.1 C	223，0.2 C，100圈	185，2 C	[4]
共沉淀	Na@Li_1.23Mn_0.54 Ni_0.1Co_0.13O₂	276，0.1 C	202，1 C，100圈	125，5 C	[18]
溶胶凝胶	1%Na@Li_1.2Mn_0.54 Ni_0.13Co_0.13O₂	227，0.1 C	85%，10 C，1000圈	112，10 C	[19]
溶胶凝胶	5% Cs@Li_1.23Mn_0.54 Ni_0.1Co_0.13O₂	280，0.1 C	195，0.5 C，100圈	116，10 C	[20]
水热	5%K@Li₂MoO₃	235，0.064 C	56%，0.064 C，100圈	83，2.56 C	[21]
水热	(900 ℃)K@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	315，0.08 C	267，1.6 C，110圈	—	[5]
共沉淀	K@LiNi_0.5Co_0.2Mn_0.3O₂	176.5，0.11 C	148，1.11 C，100圈	100，5.54 C	[22]
共沉淀	2.5%Rb@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	221.9，0.2 C	92.78%，0.2 C，100圈	117.6，2 C	[6]
—	2.5%Mg@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	250，0.08 C	195，0.08 C，100圈	120，4 C	[7]
溶胶凝胶	1%Mg@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	304	210，0.1 C，100圈	—	[23]
溶胶凝胶	2%Mg@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	275.8，0.16 C	254.9，0.16 C，50圈	127.5，4 C	[24]
溶胶凝胶	0.4%Ca@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	246，0.2 C	87%，0.2 C，100圈	133，4 C	[8]
溶剂热	3%Al@Li_1.5Mn_0.675Ni_0.1675Co_0.1675O₂	323.7，0.1 C	200，0.5 C，150圈	120，20 C	[25]
溶胶凝胶	2.5%Ti@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	320，0.24 C	229，0.24 C，300圈	136，6 C	[10]
共沉淀	8%Mg@Li_1.17Ni_0.25-_x Mn_0.58Mg _x O₂	201	95.1%，2 C，100圈	104.4，5 C	[26]
共沉淀	1%Mg@Li_1.2Ni_0.2Mn_0.6O₂	140.6，0.04 C	226.5，0.08 C，60圈	212.7，0.08 C	[27]
共沉淀	4%Mg@Li_1.2Ni_0.12Co_0.12Mn_0.56O₂	217.8，0.05 C	236.9，30圈	176.5，1.0 C	[28]
—	9%Mg@Li_1.2Ni_0.16Mn_0.56Co_0.08O₂	160，0.1 C	210，0.1 C，100圈	120，4 C	[29]
溶胶凝胶	4%Al@Li_1.14(Ni_0.136Co_0.136Mn_0.544)O₂	212，0.08 C	94.65%，100圈	—	[11]
共沉淀	Cr@Li(Li_0.2Mn_0.54Ni_0.13Co_0.13)O₂	219，0.05 C	170，0.2 C，133圈	—	[30]
高温固相	0.3%Cu@Li_1.05FePO₄	145	85%，40圈	75，3 C	[31]
共沉淀	Ga@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	259.8，0.05 C	229.4，0.1 C，100圈	155.7，5 C	[32]
共沉淀	2.5%Nb@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	282.6，0.05 C	83%，1 C，100圈	173.1，2 C	[33]
共沉淀	17.5%Se@Li_1.2Mn_0.56Ni_0.16Co_0.08O₂	265，0.08 C	93%，0.08 C，100圈	178，8 C	[34]
高温固相	Li_1.2Mn_0.568Ni_0.2Sn_0.032O₂	225，0.02 C	125，0.4 C，100圈	123，0.4 C	[9]
固相热解	2%V@Li_1.2Mn_0.52Co_0.08Ni_0.2O₂	253，0.1 C	152.2，1 C，50圈	99，5 C	[35]
热聚合	2%Mo@Li_1.2Ni_0.2Mn_0.6O₂	235，0.1	229，0.1 C，204圈	110，5 C	[36]
共沉淀	S@Li_1.2Mn_0.6Ni_0.2O₂	293.3，0.1 C	213.4，0.1 C，67圈	190，2 C	[37]
高温固相	0.6%B@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	293.9，0.4 C	228.55，0.4 C，100圈	—	[13]
高温固相	0.5%B@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	—	211，0.2 C，50圈	—	[38]
溶胶凝胶	B@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	—	190，0.2 C，100圈	—	[14]
共沉淀	2.5%F@Li_1.2Mn_0.54Co_0.13Ni_0.13O₂	200，0.2 C	87%，0.2 C，100圈	—	[12]
高温固相	2.5%F@Li(Li_1/6Ni_1/6Co_1/6Mn_1/2)O₂	275，0.1 C	198.75，1 C，40圈	—	[39]

表1

图3

图4

图5

图 6

图7

参考文献 45

1	ZHENG J M, XIAO J, ZHANG J G. The roles of oxygen non-stoichiometry on the electrochemical properties of oxide-based cathode materials[J]. Nano Today, 2016, 11(5): 678-694.
2	NAYAK P K, ERICKSON E M, SCHIPPER F, et al. Review on challenges and recent advances in the electrochemical performance of high capacity Li- and Mn-rich cathode materials for Li-ion batteries[J]. Advanced Energy Materials, 2018, 8(8): doi: 10.1002/aenm.201702397.
3	李雨, 赵慧春, 白莹, 等. 高能量密度层状富锂锰基正极材料的改性研究进展[J]. 储能科学与技术, 2018, 7(3): 394-403.
	LI Y, ZHAO H C, BAI Y, et al. Progress in the modification of lithium-rich manganese-based layered cathode material[J]. Energy Storage Science and Technology, 2018, 7(3): 394-403.
4	QING R P, SHI J L, XIAO D D, et al. Enhancing the kinetics of Li-rich cathode materials through the pinning effects of gradient surface Na⁺ doping[J]. Advanced Energy Materials, 2016, 6(6): doi: 10.1002/aenm.201501914.
5	LI Q, LI G S, FU C C, et al. K(+)-doped Li(1.2)Mn(0.54)Co(0.13)Ni(0.13)O₂: A novel cathode material with an enhanced cycling stability for lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2014, 6(13): 10330-10341.
6	LI N, HE Y S, WANG X P, et al. Incorporation of rubidium cations into Li_1.2Mn_0.54Co_0.13Ni_0.13O₂ layered oxide cathodes for improved cycling stability[J]. Electrochimica Acta, 2017, 231: 363-370.
7	SALLARD S, SHEPTYAKOV D, VILLEVIEILLE C. Improved electrochemical performances of Li-rich nickel cobalt manganese oxide by partial substitution of Li⁺ by Mg²⁺[J]. Journal of Power Sources, 2017, 359: 27-36.
8	LAISA C P, RAMESHA R N, RAMESHA K. Enhanced electrochemical performance of lithium rich layered cathode materials by Ca²⁺ substitution[J]. Electrochimica Acta, 2017, 256: 10-18.
9	FENG X, GAO Y R, BEN L B, et al. Enhanced electrochemical performance of Ti-doped Li_1.2Mn_0.54Co_0.13Ni_0.13O₂ for lithium-ion batteries[J]. Journal of Power Sources, 2016, 317: 74-80.
10	YI T F, LI Y M, YANG S Y, et al. Improved cycling stability and fast charge-discharge performance of cobalt-free lithium-rich oxides by magnesium-doping[J]. ACS Applied Materials & Interfaces, 2016, 8(47): 32349-32359.
11	SONG B H, ZHOU C F, WANG H L, et al. Advances in sustain stable voltage of Cr-doped Li-rich layered cathodes for lithium ion batteries[J]. Journal of the Electrochemical Society, 2014, 161(10): A1723-A1730.
12	AN J, SHI L Y, CHEN G R, et al. Insights into the stable layered structure of a Li-rich cathode material for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2017, 5(37): 19738-19744.
13	SUN Z H, XU L Q, DONG C Q, et al. Enhanced cycling stability of boron-doped lithium-rich layered oxide cathode materials by suppressing transition metal migration[J]. Journal of Materials Chemistry A, 2019, 7(7): 3375-3383.
14	LI L, SONG B H, CHANG Y L, et al. Retarded phase transition by fluorine doping in Li-rich layered Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material[J]. Journal of Power Sources, 2015, 283: 162-170.
15	MING L, ZHANG B, CAO Y, et al. Effect of Nb and F co-doping on Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material for high-performance lithium-ion batteries[J]. Frontiers in Chemistry, 2018, 6: 76.
16	LIU D M, FAN X J, LI Z H, et al. A cation/anion co-doped Li_1.12Na_0.08Ni_0.2Mn_0.6O_1.95F_0.05 cathode for lithium ion batteries[J]. Nano Energy, 2019, 58: 786-796.
17	LIM S N, SEO J Y, JUNG D S, et al. The crystal structure and electrochemical performance of Li_1.167Mn_0.548Ni_0.18Co_0.105O₂ composite cathodes doped and co-doped with Mg and F[J]. Journal of Electroanalytical Chemistry, 2015, 740: 88-94.
18	XUE Z C, QI X Y, LI L Y, et al. Sodium doping to enhance electrochemical performance of overlithiated oxide cathode materials for Li-ion batteries via Li/Na ion-exchange method[J]. ACS Applied Materials & Interfaces, 2018, 10(32): 27141-27149.
19	DING X, LI Y X, WANG S, et al. Towards improved structural stability and electrochemical properties of a Li-rich material by a strategy of double gradient surface modification[J]. Nano Energy, 2019, 61: 411-419.
20	DING X, LI Y X, DENG M M, et al. Cesium doping to improve the electrochemical performance of layered Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ cathode material[J]. Journal of Alloys and Compounds, 2019, 791: 100-108.
21	YU S S, PENG C, LI Z H, et al. K-doped Li-rich molybdenum-based oxide with improved electrochemical properties for lithium-ion batteries[J]. Arabian Journal for Science and Engineering, 2017, 42(10): 4291-4298.
22	YANG Z G, GUO X D, XIANG W, et al. K-doped layered LiNi_0.5Co_0.2Mn_0.3O₂ cathode material: Towards the superior rate capability and cycling performance[J]. Journal of Alloys and Compounds, 2017, 699: 358-365.
23	JIN X, XU Q J, LIU H M, et al. Excellent rate capability of Mg doped Li[Li_0.2Ni_0.13Co_0.13Mn_0.54]O₂ cathode material for lithium-ion battery[J]. Electrochimica Acta, 2014, 136: 19-26.
24	XU H J, DENG S N, CHEN G H. Improved electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ by Mg doping for lithium ion battery cathode material[J]. J Mater Chem A, 2014, 2(36): 15015-15021.
25	YAN W C, XIE Y, JIANG J C, et al. Enhanced rate performance of Al-doped Li-rich layered cathode material via nucleation and post-solvothermal method[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(4): 4625-4632.
26	WANG D, HUANG Y, HUO Z Q, et al. Synthesize and electrochemical characterization of Mg-doped Li-rich layered Li[Li_0.2Ni_0.2Mn_0.6]O₂ cathode material[J]. Electrochimica Acta, 2013, 107: 461-466.
27	XIANG Y H, LI J, WU X W, et al. Synthesis and electrochemical characterization of Mg-doped Li-rich Mn-based cathode material[J]. Ceramics International, 2016, 42(7): 8833-8838.
28	NAYAK P K, GRINBLAT J, LEVI E, et al. Understanding the influence of Mg doping for the stabilization of capacity and higher discharge voltage of Li-and Mn-rich cathodes for Li-ion batteries[J]. Physical Chemistry Chemical Physics, 2017, 19(8): 6142-6152.
29	GUO H C, XIA Y G, ZHAO H, et al. Stabilization effects of Al doping for enhanced cycling performances of Li-rich layered oxides[J]. Ceramics International, 2017, 43(16): 13845-13852.
30	LEE S B, CHO S H, HEO J B, et al. Copper-substituted, lithium rich iron phosphate as cathode material for lithium secondary batteries[J]. Journal of Alloys and Compounds, 2009, 488(1): 380-385.
31	YU T H, LI J L, XU G F, et al. Improved cycle performance of Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ by Ga doping for lithium ion battery cathode material[J]. Solid State Ionics, 2017, 301: 64-71.
32	HU X, GUO H J, PENG W J, et al. Effects of Nb doping on the performance of 0.5Li₂MnO₃ ·0.5LiNi_1/3Co_1/3Mn_1/3O₂ cathode material for lithium-ion batteries[J]. Journal of Electroanalytical Chemistry, 2018, 822: 57-65.
33	MA Q X, LI R H, ZHENG R J, et al. Improving rate capability and decelerating voltage decay of Li-rich layered oxide cathodes via selenium doping to stabilize oxygen[J]. Journal of Power Sources, 2016, 331: 112-121.
34	WANG Y Q, YANG Z Z, QIAN Y M, et al. New insights into improving rate performance of lithium-rich cathode material[J]. Advanced Materials, 2015, 27(26): 3915-3920.
35	LU C, YANG S Q, WU H, et al. Enhanced electrochemical performance of Li-rich Li_1.2Mn_0.52Co_0.08Ni_0.2O₂ cathode materials for Li-ion batteries by vanadium doping[J]. Electrochimica Acta, 2016, 209: 448-455.
36	ZANG Y, DING C X, WANG X C, et al. Molybdenum-doped lithium-rich layered-structured cathode material Li_1.2Ni_0.2Mn_0.6O₂ with high specific capacity and improved rate performance[J]. Electrochimica Acta, 2015, 168: 234-239.
37	LIU J T, WANG S B, DING Z P, et al. The effect of boron doping on structure and electrochemical performance of lithium-rich layered oxide materials[J]. ACS Applied Materials & Interfaces, 2016, 8(28): 18008-18017.
38	PAN L C, XIA Y G, QIU B, et al. Structure and electrochemistry of B doped Li(Li_0.2Ni_0.13Co_0.13Mn_0.54)_1- xBxO₂ as cathode materials for lithium-ion batteries[J]. Journal of Power Sources, 2016, 327: 273-280.
39	SONG J H, KAPYLOU A, CHOI H S, et al. Suppression of irreversible capacity loss in Li-rich layered oxide by fluorine doping[J]. Journal of Power Sources, 2016, 313: 65-72.
40	LIU Y, DE NING, ZHENG L R, et al. Improving the electrochemical performances of Li-rich Li_1.20Ni_0.13Co_0.13Mn_0.54O₂ through a cooperative doping of Na⁺ and PO₄ ^3- with Na₃PO₄[J]. Journal of Power Sources, 2018, 375: 1-10.
41	CHEN G R, AN J, MENG Y M, et al. Cation and anion Co-doping synergy to improve structural stability of Li- and Mn-rich layered cathode materials for lithium-ion batteries[J]. Nano Energy, 2019, 57: 157-165.
42	LIU Q, SU X, LEI D, et al. Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping[J]. Nature Energy, 2018, 3(11): 936-943.
43	PENG Z D, MU K C, CAO Y B, et al. Enhanced electrochemical performance of layered Li-rich cathode materials for lithium ion batteries via aluminum and boron dual-doping[J]. Ceramics International, 2019, 45(4): 4184-4192.
44	LIANG Y W, LI S Y, XIE J, et al. Synthesis and electrochemical characterization of Mg-Al co-doped Li-rich Mn-based cathode materials[J]. New Journal of Chemistry, 2019, 43(30): 12004-12012.
45	LIU Y Y, LI R R, LI J L, et al. A high-performance Ce and Sn co-doped cathode material with enhanced cycle performance and suppressed voltage decay for lithium ion batteries[J]. Ceramics International, 2019, 45(16): 20780-20787.