无机材料学报 ›› 2020, Vol. 35 ›› Issue (12): 1295-1306.DOI: 10.15541/jim20200134
所属专题： 能源材料论文精选(一)：锂离子电池(2020)； 【虚拟专辑】锂离子电池(2020~2021)
• 综述 • 下一篇
郑时有(
),董飞,庞越鹏,韩盼,杨俊和
收稿日期:2020-03-16
修回日期:2020-04-22
出版日期:2020-12-20
网络出版日期:2020-05-10
作者简介:郑时有(1974–), 男, 教授. E-mail: syzheng@usst.edu.cn
基金资助:
ZHENG Shiyou(),DONG Fei,PANG Yuepeng,HAN Pan,YANG Junhe
Received:2020-03-16
Revised:2020-04-22
Published:2020-12-20
Online:2020-05-10
About author:ZHENG Shiyou(1974–), male, professor. E-mail: syzheng@usst.edu.cn
Supported by:摘要：
负极材料是锂离子电池的重要组成部分, 目前商用锂离子电池的负极材料石墨的理论比容量仅为372 mAh/g, 严重制约了锂离子电池的进一步发展。在众多的锂离子电池负极材料新体系中, 金属氧化物具有理论比容量高、价格低廉、环境相容性好等优点, 受到广泛关注, 但是其存在导电性差、充放电体积变化大等缺点。研究发现, 纳米化可以在保持金属氧化物优点的同时克服其缺点, 因此成为金属氧化物基负极材料的研究热点。本文对近期纳米金属氧化物基锂离子电池负极材料研究的主要成果进行综述, 着重关注几种具有代表性的金属氧化物及其复合物的纳米结构设计与性能优化, 并为后续相关研究提出建议。
中图分类号:
郑时有, 董飞, 庞越鹏, 韩盼, 杨俊和. 纳米金属氧化物基锂离子电池负极材料研究进展[J]. 无机材料学报, 2020, 35(12): 1295-1306.
ZHENG Shiyou, DONG Fei, PANG Yuepeng, HAN Pan, YANG Junhe. Research Progress on Nanostructured Metal Oxides as Anode Materials for Li-ion Battery[J]. Journal of Inorganic Materials, 2020, 35(12): 1295-1306.
图1 (a, b)SnO2/C-NTs的SEM照片; (c)循环稳定性曲线以及(d)倍率性能曲线[23]
Fig. 1 (a, b) SEM images of SnO2/C-NTs; (c) Cycling performance at 500 mA/g, and (d) rate capabilities of SnO2-NTs and SnO2/C-NTs[23]
图2 (a)超细SnO2纳米颗粒固定在介孔碳的孔道中的合成原理示意图; SnO2/介孔碳复合电极材料的(b)循环稳定性曲线和(c)倍率性能曲线[31]
Fig. 2 (a) Illustration of the synthesis principles of ultrafine SnO2 NPs immobilized in the mesopore channels of mesoporous carbon; (b) Cycle performance at 200 mA/g between 0.005 and 3 V, and (c) rate performance of electrodes based on different SnO2 content[31]
图3 (a)CuO纳米棒阵列的SEM照片, 以及(b)在100 mA/g下的循环稳定性曲线[42]
Fig. 3 (a) SEM image, and (b) cycle performance at 100 mA/g of CuO NRAs[42]
图4 (a)空心CuO@NCS复合材料的合成示意图, (b)在100 mA/g下的循环稳定性曲线[46]
Fig. 4 (a) Schematic illustration of the synthesis of hollow CuO@NCS composites; (b) Cycle performance of CuO@NCS at 100 mA/g[46]
图5 (a)颗粒与片上以及(b~d)片与片上的Fe2O3-石墨烯复合材料的TEM照片[57]
Fig. 5 TEM images of (a) Fe2O3-graphene particle-on-sheet composite, and (b-d) Fe2O3-graphene sheet-on-sheet composite[57]
图6 Fe3O4@N-HPCNs的(a)合成过程示意图, (b)TEM照片, 以及(c)循环稳定性曲线[63]
Fig. 6 (a) Illustration for the synthetic procedure, (b) TEM image, and (c) rate capabilities of Fe3O4@N-HPCNs[63]
图7 (a)非晶多孔CoSnO3/Au复合纳米立方的结构示意图; 在(b) 0.2和(c) 5 A/g电流密度下的循环稳定性曲线[65]
Fig. 7 (a) Structure diagrams of the amorphous porous CoSnO3/Au composite nanocubes; Cycle performance of the amorphous porous CoSnO3/Au composite nanocubes at (b) 0.2 and (c) 5 A/g[65]
图8 尖晶石ZnxCo3-xO4空心多面体的(a)合成过程示意图, (b)TEM照片, 以及(c)倍率性能曲线[79]
Fig. 8 (a) Schematic illustration for the synthetic procedure, (b) TEM image, and (c) rate capabilities of spinel ZnxCo3-xO4 hollow polyhedron[79]
| Materials structure | First cyclic capacity/(mAh?g-1) (Current density/(A?g-1)) | Coulombic efficiency | Cycling performance/ (mAh?g-1) (Current density/ (A?g-1), cycle number) | Rate performance/(mAh?g-1) (Current density/(A?g-1)) | Ref. |
|---|---|---|---|---|---|
| SnO2 NPs (5~20 nm) | 1310 (0.1) | 69% | 800 (0.1, 100) | 850 (1); 800 (2) | [ |
| SnO2/C-NT (15 nm) | 483 (0.5) | 51% | 596 (0.5, 200) | 683 (1); 550 (2) | [ |
| SnO2 nanosheets (7.4 nm) | 1338 (0.1) | 55% | 763 (0.1, 300) | 460 (1); 280 (2) | [ |
| SnO2 HS (50 nm) | 736 (0.1) | 47% | 540 (0.1, 50) | 550 (1); 422 (2) | [ |
| SnO2/C (50~100 nm) | 998 (0.1) | 69% | 750 (0.1, 100) | 413 (1); 325 (2) | [ |
| C-SnO2/CNT (7 nm) | 1373 (1) | 52% | 950 (1, 100) | 1100 (1); 950 (2) | [ |
| SnO2@G-SWCNT (7 nm) | 1007 (0.1) | 53% | 785 (0.1, 100) | 510 (1); 426 (2) | [ |
| SnO2@CMK-5 (4~5 nm) | 694 (0.2) | 71% | 1039 (0.1, 100) | 770 (1) | [ |
| SnO2/C (2.8 nm) | 899 (1.4) | 44% | 560 (1.4, 100) | 700 (1.4); 538 (2.8) | [ |
| CuO spheres (400 nm) | 590 (0.45) | 66% | 400 (0.45, 50) | - | [ |
| CuO octahedra (5 nm) | 506 (0.5) | 70% | 785 (0.5, 50) | 488 (1); 370 (2) | [ |
| CuO labyrinths (20 nm) | 645 (0.1) | 66% | 330 (1, 100) | 340 (1.3); 255 (3.4) | [ |
| CuO NRAs (2~3 μm) | 751 (0.1) | 56% | 671 (0.1, 150) | 367 (1); 300 (2) | [ |
| CuO spheres (10 nm) | 552 (0.67) | 55% | 750 (0.67, 350) | 650 (1.3); 600 (3.4) | [ |
| CuO/MWCNT (10 nm) | 462 (0.07) | 69% | 650 (0.07, 100) | 590 (1.3); 590 (2) | [ |
| Cu2O/CuO/rGO (500 nm) | 375 (0.3) | 75% | 570 (0.3, 100) | 350 (1.3); 250 (2.7) | [ |
| Cu@NCSs (45 nm) | 909 (0.5) | 62% | 602 (0.5, 200) | 760 (1); 570 (2) | [ |
| Graphene/Fe2O3 (40 nm) | 1074 (0.1) | 65% | 800 (0.1, 50) | - | [ |
| Fe2O3/CA (5~50 nm) | 836 (0.1) | 55% | 635 (0.1, 100) | 652 (0.4); 546 (0.8) | [ |
| RG-O/Fe2O3 (60 nm) | 1219 (0.1) | 72% | 1027 (0.1, 50) | 970 (0.4); 760 (0.8) | [ |
| Fe3O4@PCFs (10~60 nm) | 1014 (0.2) | 72% | 920 (0.2, 80) | 677 (1); 523 (2) | [ |
| Fe3O4/PPy (200 nm) | 493 (1) | 89% | 554 (1, 100) | 500 (1); 330 (2) | [ |
| Fe3O4-CNTs (50~100 nm) | 845 (0.05) | 77% | 702 (0.05, 50) | - | [ |
| Fe3O4@N-HPCNs (6 nm) | 521 (0.1) | 54% | 1240 (0.1, 100) | 700 (1); 600 (2) | [ |
| CoMoO4 NPs (2~10 nm) | 1051 (0.2) | 72% | 1185 (0.2, 100) | 900 (1); 850 (2) | [ |
| CoSnO3/Au cube (70 nm) | 1693 (0.2) | 68% | 1615 (0.2, 100) | 1425 (1); 1289 (2) | [ |
| NiFe2O4 NPs (20 nm) | 1177 (0.1) | 79% | 1390 (0.1, 20) | 823 (1); 725 (3) | [ |
| ZnxCo3-xO4 (10 nm) | 967 (0.1) | 76% | 990 (0.1, 50) | 1020 (0.9); 988 (2.7) | [ |
| NixCo3-xO4 (40 nm) | 1133 (0.1) | 70% | 1109 (0.1, 100) | 864 (1); 728 (2) | [ |
表1 不同金属氧化物负极材料的结构与综合电化学性能
Table 1 Structures and comprehensive electrochemical performances of different metal oxide anode materials
| Materials structure | First cyclic capacity/(mAh?g-1) (Current density/(A?g-1)) | Coulombic efficiency | Cycling performance/ (mAh?g-1) (Current density/ (A?g-1), cycle number) | Rate performance/(mAh?g-1) (Current density/(A?g-1)) | Ref. |
|---|---|---|---|---|---|
| SnO2 NPs (5~20 nm) | 1310 (0.1) | 69% | 800 (0.1, 100) | 850 (1); 800 (2) | [ |
| SnO2/C-NT (15 nm) | 483 (0.5) | 51% | 596 (0.5, 200) | 683 (1); 550 (2) | [ |
| SnO2 nanosheets (7.4 nm) | 1338 (0.1) | 55% | 763 (0.1, 300) | 460 (1); 280 (2) | [ |
| SnO2 HS (50 nm) | 736 (0.1) | 47% | 540 (0.1, 50) | 550 (1); 422 (2) | [ |
| SnO2/C (50~100 nm) | 998 (0.1) | 69% | 750 (0.1, 100) | 413 (1); 325 (2) | [ |
| C-SnO2/CNT (7 nm) | 1373 (1) | 52% | 950 (1, 100) | 1100 (1); 950 (2) | [ |
| SnO2@G-SWCNT (7 nm) | 1007 (0.1) | 53% | 785 (0.1, 100) | 510 (1); 426 (2) | [ |
| SnO2@CMK-5 (4~5 nm) | 694 (0.2) | 71% | 1039 (0.1, 100) | 770 (1) | [ |
| SnO2/C (2.8 nm) | 899 (1.4) | 44% | 560 (1.4, 100) | 700 (1.4); 538 (2.8) | [ |
| CuO spheres (400 nm) | 590 (0.45) | 66% | 400 (0.45, 50) | - | [ |
| CuO octahedra (5 nm) | 506 (0.5) | 70% | 785 (0.5, 50) | 488 (1); 370 (2) | [ |
| CuO labyrinths (20 nm) | 645 (0.1) | 66% | 330 (1, 100) | 340 (1.3); 255 (3.4) | [ |
| CuO NRAs (2~3 μm) | 751 (0.1) | 56% | 671 (0.1, 150) | 367 (1); 300 (2) | [ |
| CuO spheres (10 nm) | 552 (0.67) | 55% | 750 (0.67, 350) | 650 (1.3); 600 (3.4) | [ |
| CuO/MWCNT (10 nm) | 462 (0.07) | 69% | 650 (0.07, 100) | 590 (1.3); 590 (2) | [ |
| Cu2O/CuO/rGO (500 nm) | 375 (0.3) | 75% | 570 (0.3, 100) | 350 (1.3); 250 (2.7) | [ |
| Cu@NCSs (45 nm) | 909 (0.5) | 62% | 602 (0.5, 200) | 760 (1); 570 (2) | [ |
| Graphene/Fe2O3 (40 nm) | 1074 (0.1) | 65% | 800 (0.1, 50) | - | [ |
| Fe2O3/CA (5~50 nm) | 836 (0.1) | 55% | 635 (0.1, 100) | 652 (0.4); 546 (0.8) | [ |
| RG-O/Fe2O3 (60 nm) | 1219 (0.1) | 72% | 1027 (0.1, 50) | 970 (0.4); 760 (0.8) | [ |
| Fe3O4@PCFs (10~60 nm) | 1014 (0.2) | 72% | 920 (0.2, 80) | 677 (1); 523 (2) | [ |
| Fe3O4/PPy (200 nm) | 493 (1) | 89% | 554 (1, 100) | 500 (1); 330 (2) | [ |
| Fe3O4-CNTs (50~100 nm) | 845 (0.05) | 77% | 702 (0.05, 50) | - | [ |
| Fe3O4@N-HPCNs (6 nm) | 521 (0.1) | 54% | 1240 (0.1, 100) | 700 (1); 600 (2) | [ |
| CoMoO4 NPs (2~10 nm) | 1051 (0.2) | 72% | 1185 (0.2, 100) | 900 (1); 850 (2) | [ |
| CoSnO3/Au cube (70 nm) | 1693 (0.2) | 68% | 1615 (0.2, 100) | 1425 (1); 1289 (2) | [ |
| NiFe2O4 NPs (20 nm) | 1177 (0.1) | 79% | 1390 (0.1, 20) | 823 (1); 725 (3) | [ |
| ZnxCo3-xO4 (10 nm) | 967 (0.1) | 76% | 990 (0.1, 50) | 1020 (0.9); 988 (2.7) | [ |
| NixCo3-xO4 (40 nm) | 1133 (0.1) | 70% | 1109 (0.1, 100) | 864 (1); 728 (2) | [ |
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