多级碳复合的大尺寸硅颗粒在锂离子电池负极中的性能

doi:10.19799/j.cnki.2095-4239.2022.0437

摘要/Abstract

摘要：

以光伏电池生产废料中的大尺寸硅颗粒(200～800 nm)为原料，水性聚氨酯(PU)和聚苯胺(PANI)作为碳源，通过液相包裹法和低温热解法制备了不同结构碳复合的硅碳负极材料(SPU与SPU#PANI)，分别研究了复合碳含量、微结构与元素掺杂对负极电化学性能的影响。SPU负极中碳复合量低，首次放电比容量高达2193.6 mAh/g，但循环稳定性差。经二级碳复合后的SPU#PANI导电性提高，在多孔碳微结构支撑作用下，不仅获得了较高的放电比容量(1488.8 mAh/g)，而且经100次循环后SPU#PANI放电比容量保持在756.8 mAh/g以上，表现出良好的倍率性能。研究结果表明，大尺寸硅颗粒表面复合了具备多孔结构的碳后，不仅为硅充放电过程中的膨胀提供了缓冲，也为锂离子传输提供通道，有效地提升了硅基负极的电化学性能和稳定性。本工作采用的多级碳低温热解复合方法，可为锂离子电池硅基负极产业化技术发展提供重要的借鉴。

关键词: 水性聚氨酯, 聚苯胺, 多级碳复合, 负极, 锂离子电池

Abstract:

Silicon-carbon composite materials within various carbon structures (SPU and SPU#PANI) were created using liquid phase wrapping and low-temperature pyrolysis, with large-size silicon particles (200—800 nm) from photovoltaic cell production waste as raw materials and water-based polyurethane (PU) and polyaniline (PANI) as carbon sources. The effects of carbon content, microstructure, and elemental doping on the electrochemical characteristics of SPU and SPU#PANI as anode materials for lithium-ion batteries were investigated. A low content of carbon composite in the SPU results in a high initial discharge capacity of up to 2193.6 mAh/g but poor charge and discharge cycle stability. However, the conductivity of SPU#PANI was increased after a secondary carbon composited. Additionally, it obtains a high discharge capacity (1488.8 mAh/g) as a result of the influence of porous carbon microstructure. The SPU#PANI's specific capacity was still over 756.8 mAh/g after 100 cycles, indicating good rate performance. The findings showed that the carbon with porous structure composite on the surface of large-size silicon particles serves not only a buffer for the expansion of the silicon in the process of charge and discharge but also a channel for lithium-ion transmission, significantly enhancing the electrochemical performance and stability of the silicon-based anode. The low-temperature pyrolysis technique used to composite multistage carbon on large-scale silicon particles provides a key reference for the industrialization technology development of silicon-based anode for lithium-ion batteries.

Key words: waterborne polyurethane, polyaniline, multistage carbon composite, anode, lithium ion battery

中图分类号:

O 646

郑瀚, 来沛霈, 田晓华, 孙卓, 张哲娟. 多级碳复合的大尺寸硅颗粒在锂离子电池负极中的性能[J]. 储能科学与技术, 2023, 12(1): 23-34.

Han ZHENG, Peipei LAI, Xiaohua TIAN, Zhuo SUN, Zhejuan ZHANG. Performance of large-scale silicon particles coated with multistage carbon as anode materials for lithium-ion batteries[J]. Energy Storage Science and Technology, 2023, 12(1): 23-34.

图/表 15

图1

图2

图3

图4

图5

图6

图7

图8

表1

图9

图10

图11

图12

图13

表2

参考文献 27

1	IKONEN T, NISSINEN T, POHJALAINEN E, et al. Electrochemically anodized porous silicon: Towards simple and affordable anode material for Li-ion batteries[J]. Scientific Reports, 2017, 7: 7880.
2	ZHANG Y, ZHANG X G, ZHANG H L, et al. Composite anode material of silicon/graphite/carbon nanotubes for Li-ion batteries[J]. Electrochimica Acta, 2006, 51(23): 4994-5000.
3	TARASCON J M, ARMAND M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001, 414(6861): 359-367.
4	DUNN B, KAMATH H, TARASCON J M. Electrical energy storage for the grid: A battery of choices[J]. Science, 2011, 334(6058): 928-935.
5	JIA H P, ZHENG J M, SONG J H, et al. A novel approach to synthesize micrometer-sized porous silicon as a high performance anode for lithium-ion batteries[J]. Nano Energy, 2018, 50: 589-597.
6	YU C L, TIAN X H, XIONG Z C, et al. High stability of sub-micro-sized silicon/carbon composites using recycling Silicon waste for lithium-ion battery anode[J]. Journal of Alloys and Compounds, 2021, 869: doi: 10.1016/j.jallcom.2021.159124.
7	HOELTGEN C, LEE J E, JANG B Y. Stepwise carbon growth on Si/SiO_x core-shell nanoparticles and its effects on the microstructures and electrochemical properties for high-performance lithium-ion battery's anode[J]. Electrochimica Acta, 2016, 222: 535-542.
8	CHO M K, YOU S J, WOO J G, et al. Anomalous Si-based composite anode design by densification and coating strategies for practical applications in Li-ion batteries[J]. Composites Part B: Engineering, 2021, 215: doi: 10.1016/j.compositesb.2021.108799.
9	PENG J, LUO J, LI W W, et al. Insight into the performance of the mesoporous structure SiO_x nanoparticles anchored on carbon fibers as anode material of lithium-ion batteries[J]. Journal of Electroanalytical Chemistry, 2021, 880: doi: 10.1016/j.jelechem. 2020.114798.
10	HSIEH C C, LIN Y G, CHIANG C L, et al. Carbon-coated porous Si/C composite anode materials via two-step etching/coating processes for lithium-ion batteries[J]. Ceramics International, 2020, 46(17): 26598-26607.
11	LV R T, CUI T X, JUN M S, et al. Open-ended, N-doped carbon nanotube-graphene hybrid nanostructures as high-performance catalyst support[J]. Advanced Functional Materials, 2011, 21(5): 999-1006.
12	ZAMFIR M R, NGUYEN H T, MOYEN E, et al. Silicon nanowires for Li-based battery anodes: A review[J].Journal of Materials Chemistry A, 2013, 1(34): doi: 10.1039/c3ta11714f.
13	FENG X J, CUI H M, MIAO R R, et al. Nano/micro-structured silicon@carbon composite with buffer void as anode material for lithium ion battery[J]. Ceramics International, 2016, 42(1): 589-597.
14	袁开军, 江治, 李疏芬, 周允基. 聚氨酯弹性体的热分解动力学研究[J]. 应用化学, 2005, 22(8): 861-864.
	YUAN K J, JIANG Z, LI S F, et al. Kinetics of thermal degradation of polyurethane elastomers[J]. Chinese Journal of Applied Chemistry, 2005, 22(8): 861-864.
15	BRANCA C, DI BLASI C, CASU A, et al. Reaction kinetics and morphological changes of a rigid polyurethane foam during combustion[J]. Thermochimica Acta, 2003, 399(1/2): 127-137.
16	WANG H, WANG L F, WANG L C, et al. Phosphorus particles embedded in reduced graphene oxide matrix to enhance capacity and rate capability for capacitive potassium-ion storage[J]. Chemistry-A European Journal, 2018, 24(52): 13897-13902.
17	JU Z C, LI P Z, MA G Y, et al. Few layer nitrogen-doped graphene with highly reversible potassium storage[J]. Energy Storage Materials, 2018, 11: 38-46.
18	LI Z L, ZHAO H L, LV P P, et al. Watermelon-like structured SiO_x-TiO₂@C nanocomposite as a high-performance lithium-ion battery anode[J]. Advanced Functional Materials, 2018, 28(31): doi: 10.1002/adfm.201605711.
19	WANG X R, LIU J Y, LIU Z W, et al. Identifying the key role of pyridinic-N-co bonding in synergistic electrocatalysis for reversible ORR/OER[J]. Advanced Materials, 2018, 30(23): doi: 10.1002/adma.201800005.
20	MADHAN KUMAR A, SURESH BABU R, OBOT I B, et al. Fabrication of nitrogen doped graphene oxide coatings: Experimental and theoretical approach for surface protection[J]. RSC Advances, 2015, 5(25): 19264-19272.
21	TAN Z Q, NI K, CHEN G X, et al. Incorporating pyrrolic and pyridinic nitrogen into a porous carbon made from C60 molecules to obtain superior energy storage[J]. Advanced Materials, 2017, 29(8): doi: 10.1002/adma.201603414.
22	HEUBNER C, SCHNEIDER M, MICHAELIS A. Diffusion-limited C-rate: A fundamental principle quantifying the intrinsic limits of Li-ion batteries[J]. Advanced Energy Materials, 2020, 10(2): doi: 10.1002/aenm.201902523.
23	ZHOU X Y, TANG J J, YANG J, et al. Silicon@carbon hollow core-shell heterostructures novel anode materials for lithium ion batteries[J]. Electrochimica Acta, 2013, 87: 663-668.
24	EIN-ELI Y. A new perspective on the formation and structure of the solid electrolyte interface at the graphite anode of Li-ion cells[J]. Electrochemical and Solid-State Letters, 1999, 2(5): doi: 10.1149/1.1390787.
25	XU C, WANG B Y, LUO H, et al. Embedding silicon in pinecone-derived porous carbon as a high-performance anode for lithium-ion batteries[J]. ChemElectroChem, 2020, 7(13): 2889-2895.
26	WANG J, POLLEUX J, LIM J, et al. Pseudocapacitive contributions to electrochemical energy storage in TiO₂ (anatase) nanoparticles[J]. The Journal of Physical Chemistry C, 2007, 111(40): 14925-14931.
27	SIMON P, GOGOTSI Y, DUNN B. Where do batteries end and supercapacitors begin? [J]. Science, 2014, 343(6176): 1210-1211.

样品名	循环首次			循环100次
样品名	充电/(mAh/g)	放电/(mAh/g)	效率/%	充电/(mAh/g)	放电/(mAh/g)	效率/%	容量保持率/%
SPU-4	1454.8	1885.7	77.15	609.2	614	99.23	38.82
SPU-8	1839.2	2193.6	83.84	615.7	620	99.31	30.74
SPU-24	608	772.2	78.73	564.8	570.3	99.04	80.14
SPU#PANI-1	939.7	1291.4	77.26	702.8	738.7	99.3	59.09
SPU#PANI-2	1011.3	1177.8	85.87	669.8	675.8	99.11	61.55
SPU#PANI-3	1011.8	1162.6	87.03	747.7	756.3	98.87	64.32

电极	R_S/Ω	R_ct/Ω
SPU-8	2.177	1056
SPU#PANI-1	4.337	1216
SPU#PANI-2	3.467	968.4
SPU#PANI-3	2.429	678.5

[1]	韩江浩, 王晓丹, 李奇松, 李慧芳, 王睿, 许刚. 锂离子电池加速循环测试研究[J]. 储能科学与技术, 2023, 12(1): 255-262.
[2]	潘岳, 韩雪冰, 欧阳明高, 任华华, 刘巍, 闫月君. 锂离子电池内短路检测算法及其在实际数据中的应用[J]. 储能科学与技术, 2023, 12(1): 198-208.
[3]	张文舒, 胡方圆, 黄昊, 王旭东, 姚曼. 基于Ti基MXene的储钠负极及其性能调控机制[J]. 储能科学与技术, 2023, 12(1): 35-41.
[4]	何骁龙, 石晓龙, 王子阳, 韩路豪, 姚斌. 过充、过热及其共同作用下车用三元锂离子电池热失控特性[J]. 储能科学与技术, 2023, 12(1): 218-226.
[5]	邓林旺, 冯天宇, 舒时伟, 郭彬, 张子峰. 锂离子电池无损析锂检测研究进展[J]. 储能科学与技术, 2023, 12(1): 263-277.
[6]	田孟羽, 武怿达, 郝峻丰, 朱璟, 岑官骏, 乔荣涵, 申晓宇, 季洪祥, 金周, 詹元杰, 闫勇, 贲留斌, 俞海龙, 刘燕燕, 黄学杰. 锂电池百篇论文点评（2022.10.01—2022.11.30）[J]. 储能科学与技术, 2023, 12(1): 1-15.
[7]	朱璟, 武怿达, 郝峻丰, 岑官骏, 乔荣涵, 申晓宇, 田孟羽, 季洪祥, 金周, 詹元杰, 闫勇, 贲留斌, 俞海龙, 刘燕燕, 黄学杰. 锂电池百篇论文点评（2022.6.1—2022.7.31）[J]. 储能科学与技术, 2022, 11(9): 3035-3050.
[8]	张俊, 李琦, 陶莹, 杨全红. 钠离子电池筛分型碳：缘起与进展[J]. 储能科学与技术, 2022, 11(9): 2825-2833.
[9]	贡淑雅, 王跃, 李萌, 邱景义, 王洪, 文越华, 徐斌. 锂离子电池负极材料TiNb₂O₇ 的研究进展[J]. 储能科学与技术, 2022, 11(9): 2921-2932.
[10]	沈馨, 张睿, 赵辰孜, 武鹏, 张羽彤, 张俊东, 范丽珍, 刘全兵, 陈爱兵, 张强. 金属锂电池中力-电化学机制研究进展[J]. 储能科学与技术, 2022, 11(9): 2781-2797.
[11]	张群斌, 董陶, 李晶晶, 刘艳侠, 张海涛. 废旧电池电解液回收及高值化利用研发进展[J]. 储能科学与技术, 2022, 11(9): 2798-2810.
[12]	邓林旺, 冯天宇, 舒时伟, 张子峰, 郭彬. 锂离子电池快充策略技术研究进展[J]. 储能科学与技术, 2022, 11(9): 2879-2890.
[13]	栗志展, 秦金磊, 梁嘉宁, 李峥嵘, 王瑞, 王得丽. 高镍三元层状锂离子电池正极材料：研究进展、挑战及改善策略[J]. 储能科学与技术, 2022, 11(9): 2900-2920.
[14]	牛少军, 吴凯, 朱国斌, 王艳, 曲群婷, 郑洪河. 锂离子电池硅基负极循环过程中的膨胀应力[J]. 储能科学与技术, 2022, 11(9): 2989-2994.
[15]	陈晓宇, 耿萌萌, 王乾坤, 沈佳妮, 贺益君, 马紫峰. 基于电化学阻抗特征选择和高斯过程回归的锂离子电池健康状态估计方法[J]. 储能科学与技术, 2022, 11(9): 2995-3002.