锂离子电池正极材料研究进展

李仲明; 李斌; 冯东; 曾天标

doi:10.13801/j.cnki.fhclxb.20210708.002

锂离子电池正极材料研究进展

doi: 10.13801/j.cnki.fhclxb.20210708.002

李仲明^1,,
李斌^1,,
冯东^1, ,,
曾天标^2, ,

1.
昆明理工大学　化学工程学院，昆明 650500
2.
四川大学　高分子材料工程国家重点实验室，高分子研究所，成都 610065

基金项目: 国家自然科学基金(21666011)

详细信息

通讯作者:
冯东，讲师，研究方向为锂离子电池　E-mail：fdryan@kust.edu.cn

曾天标，讲师，研究方向为锂离子电池　E-mail：tianbiaozeng@126.com

中图分类号: TM911
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出版历程
- 收稿日期: 2021-04-14
- 修回日期: 2021-06-03
- 录用日期: 2021-06-30
- 网络出版日期: 2021-07-08
- 刊出日期: 2022-02-01

Research progress of cathode materials for lithium-ion battery

LI Zhongming^1
,,
LI Bin^1
,,
FENG Dong^{1
, ,},
ZENG Tianbiao^{2
, ,}

1.
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China
2.
State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu 610065, China

摘要

摘要: 锂离子电池(LIB)近年来受到了广泛的关注，与其他可充电电池相比，锂离子电池LIB具有更高的能量密度、功率和效率。正极作为LIB的关键部件，其特性会显著影响LIB的性能。本文分类综述了一些锂离子正极材料，包括一元、二元、三元金属锂氧化物和磷酸亚铁锂正极材料，并对其优缺点进行了介绍。此外，本文还对已商业化的正极材料物性数据和具有商业化应用前景的正极材料进行了系统评价。最后，总结了各类正极材料的优势和缺陷并讨论了未来的发展和挑战。
- 锂离子电池 /
- 正极材料 /
- 金属锂氧化物 /
- 磷酸亚铁锂 /
- 商业化价值
Abstract: Lithium-ion battery (LIB) has received considerable attention in recent years, mainly because LIB has higher energy density, power and efficiency compared with other rechargeable batteries. The cathode material plays an important role in determining the LIB performance (e.g, capacity, thermal stability, and potential) and is the main part of LIB system. This paper presents a systematic classification of LIB cathode materials, including mono-, binary-, and ternary-based lithium metal oxide and lithium iron phosphate cathode materials, and the advantages and disadvantages of these cathode materials are systematically reviewed. The physical properties of commercialized cathode materials are compared and evaluated for potential commercialization. Finally, the advantages and disadvantages of each cathode materials are summarized, and the challenges and prospects of cathode materials for the future application are discussed.
- lithium-ion battery /
- cathode material /
- lithium metal oxide /
- lithium ferrous phosphate /
- commercialization value

HTML全文

图 1 Li₂O/Co共包覆LiCoO₂ (CS-LiCoO₂)的充放电曲线(a)和LiCoO₂及CS-LiCoO₂的循环容量及库伦效率(b)^[16]

Figure 1. Discharge/charge curves of Li₂O/Co co-coated LiCoO₂ (CS-LiCoO₂) (a) and long-term cycle capacities/coulombic efficiencies of LiCoO₂ and CS-LiCoO₂(b)^[16]

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图 2 Li⁺脱出与插入位置(8a和16c)^[31] ((a)、(b))、LiMn₂O₄在1.4~4.4 V的CV曲线(c)、LiMn₂O₄在1.4~4.4 V的充放电曲线(d)、LiMn₂O₄在20 mA/g的循环容量曲线(e) ^[32]

Figure 2. Li⁺ delocalization and insertion positions (8a and 16c)^[31] ((a), (b)), CV curves of LiMn₂O₄ at 1.4 to 4.4 V (c),charge/discharge curves of LiMn₂O₄ at 1.4 to 4.4 V (d) and cycle capacity curves of LiMn₂O₄ at 20 mA/g (e) ^[32]

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图 3 不同温度烧结的LiNi_1/3Mn_1/3Co_1/3O₂在0.1 C的充放电循环性能 (a)、930℃烧结的LiNi_1/3Mn_1/3Co_1/3O₂的充放电曲线 (b)、930℃烧结的LiNi_1/3Mn_1/3Co_1/3O₂的CV曲线 (c)、LiNi_0.8Mn_0.1Co_0.1O₂在1 C的充放电循环性能 (d)、LiNi_0.8Mn_0.1Co_0.1O₂的充放电曲线 (e)、LiNi_0.8Mn_0.1Co_0.1O₂的CV曲线 (f)^[47-48]

Figure 3. Cycling performance at 0.1 C ofLiNi_1/3Mn_1/3Co_1/3O₂ synthesized in 850, 880, 900, and 930℃ (a), Discharge/charge curves of LiNi_1/3Mn_1/3Co_1/3O₂ synthesized in 930℃ (b), CV curves of LiNi_1/3Mn_1/3Co_1/3O₂ synthesized in 930℃(c), Cycling performances of LiNi_0.8Mn_0.1Co_0.1O₂ at 1 C (d), Discharge/charge curves of LiNi_0.8Mn_0.1Co_0.1O₂(e) and CV curves of LiNi_0.8Mn_0.1Co_0.1O₂(f)^[47-48]

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图 4 5wt%碳包覆、10wt%碳包覆、15wt%碳包覆的LiFePO₄/C的电化学性能：(a) 首次充电/放电曲线；(b)在0.2 C的循环性能；(c) 倍率放电性能^[57]

Figure 4. Electrochemical performances of LiFePO₄ coated with 5wt% carbon coated, 10wt% carbon, 15wt% carbon: (a) Initial charge/discharge curves; (b) Long-term cycling performance; (c) Rate ccyling performance^[57]

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图 5 V₂O₅/中空碳纤维阵列(V₂O₅@PRC)的CV曲线 (a)、V₂O₅@PRC的充放电曲线 (b)、V₂O₅@PRC及V₂O₅/中空碳纤维复合(V₂O₅/PRC)的倍率循环性能 (c)^[76]

Figure 5. CV curves of V₂O₅@PRC (a), discahrge/charge curves of V₂O₅@PRC (b) and rate cycling performance of V₂O₅@PRC and V₂O₅/PRC (c)^[76]

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图 6 不同碳含量包覆纳米氟化铁的储锂性能(FeF₃/C-0、FeF₃/C-2、FeF₃/C-3、FeF₃/C-4的碳含量分别为0wt%、2.1wt%、2.9wt%、3.9wt%)：(a) 充放电曲线；(b) 在0.84 C (600 mA/g) 的充放电循环曲线；(c) 倍率循环性能；(d) CV曲线^[93]

Figure 6. Lithium storage performances of carbon wrapped nano FeF₃(The carbon content in FeF₃/C-0, FeF₃/C-2, FeF₃/C-3, FeF₃/C-4 were 0wt%, 2.1wt%, 2.9wt%，3.9wt%, respectively): (a) Discharge/charge curves; (b) Cycling performance at 0.84 C (600 mA/g); (c) Rate cycling performance; (d) CV curves^[93]

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表 1 商业化锂离子电池正极材料的部分物性数据对比

Table 1. Performance data of commercial cathode materials

Cathode material	LiCoO₂	LiNiO₂	LiMnO₂	LiMn₂O₄	LiFePO₄	NCM	NCA
Cell types	α-NaFeO₂	α-NaFeO₂	α-NaFeO₂	Spinel	Peridot	α-NaFeO₂	α-NaFeO₂
Voltage platforms/V	Approx. 4.1	Approx. 3.8	Approx. 3.2	Approx. 4.1	Approx. 3.5	Approx. 3.8	Approx. 3.8
Theoretical specific capacity/ (mA·h·g⁻¹)	274	275	285	147	170	Approx. 270	275
Actual specific capacity/ (mA·h·g⁻¹)	Approx. 140	Approx. 180	Approx. 150	Approx. 130	Approx. 140	145-190	160-200
Compaction density/ (g·cm⁻³)	4.1-4.3	–	–	2.9-3.2	2.2-2.3	3.4-3.7	3.8
Conductivity/(S·cm⁻¹)	Approx. 10⁻³	Approx. 10⁻¹	–	Approx. 10⁻⁵	10⁻⁷−10⁻⁹	–	–
Li⁺ diffusion coefficient/ (cm²·s⁻¹)	10⁻⁹ -10⁻⁸	10⁻⁷	–	10⁻⁹ -10⁻¹¹	10⁻¹⁵	–	–
Thermal stability	Instability	Instability	–	Stability	Very stable	–	–
Cost	Very high	Moderate	–	Low	Minimum	–	–
Whether environmental protection	Toxic	Low toxicity	Basically non-toxic	Basically non-toxic	Basically non-toxic	Toxic	Toxic
Notes: NCM—LiNi_xMn_yCo₁₋_x−yO₂; “–”—Data not available.

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