天然鳞片石墨球化尾料的高性能负极材料制备及储锂特性研究

doi:10.19799/j.cnki.2095-4239.2023.0274

摘要/Abstract

摘要：

以天然鳞片石墨球化尾料(球化微粉)为原料，将其纯化、与沥青混料、等静压压制成型、碳化、破碎及筛分处理，制备了可应用于锂离子电池的石墨负极材料(SG/C)。采用场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)、氮气吸附、激光粒度仪、X射线荧光光谱仪(XRF)及电化学方法等表征测试手段，研究了沥青加入量、碳化升温速率及碳化温度对SG/C材料的理化性能及电化学性能的影响。结果表明，在沥青添加量为10%、碳化升温速率为2 ℃/min、碳化温度为1000 ℃的优化处理条件下，所得SG/C-V2-1000材料表现出最优的电化学性能。其在0.1 C倍率下的首次可逆比容量为352.4 mAh/g，首次库仑效率为93.12%；在0.2 C倍率循环400圈后的容量保持率为79%，在0.5 C倍率下循环200圈后的容量保持率为85%。该研究对于实现天然鳞片石墨球化微粉的高值化利用提供了实验依据。

关键词: 锂离子电池, 天然鳞片石墨, 石墨负极材料, 球化微粉, 高值化利用

Abstract:

A graphite anode electrode material (SG/C) suitable for lithium-ion batteries was prepared using spheroidized tailings (spheroidized micropowder) of natural flake graphite as raw materials. They were purified, mixed with asphalt, isostatically pressed, carbonized, crushed, and underwent screening treatment. The effects of asphalt addition, carbonization heating rate, and carbonization temperature on the physicochemical and electrochemical properties of SG/C materials were studied using characterization methods such as field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), nitrogen adsorption isotherms, laser particle size analyzer, X-ray fluorescence spectrometer (XRF), and electrochemical methods. The results showed that under the optimized treatment conditions of 10% asphalt addition, 2 ℃/min carbonization heating rate, and 1000 ℃ carbonization temperature, the obtained SG/C-V2-1000 material exhibited the optimal electrochemical performance. Its first reversible specific capacity at 0.1 C magnification was 352.4 mAh/g, and its first Coulombic efficiency was 93.12%. The capacity retention rate after 400 cycles at a 0.2 C magnification was 79%, and after 200 cycles at a 0.5 C magnification, the capacity retention rate was 85%. This study provides the experimental basis for transforming spheroidized micropowders of natural flake graphite into high-value materials.

Key words: lithium-ion battery, natural flake graphite, graphite anode material, spheroidizing micro powder, spheroidized tailings, high-value utilization

中图分类号:

TM 242

周向阳, 胡颖杰, 梁家浩, 周其杰, 文康, 陈松, 杨娟, 唐晶晶. 天然鳞片石墨球化尾料的高性能负极材料制备及储锂特性研究[J]. 储能科学与技术, 2023, 12(9): 2767-2777.

Xiangyang ZHOU, Yingjie HU, Jiahao LIANG, Qijie ZHOU, Kang WEN, Song CHEN, Juan YANG, Jingjing TANG. Preparation and lithium storage characteristics of high-performance anode materials based on spheroidized tailings of natural flake graphite[J]. Energy Storage Science and Technology, 2023, 12(9): 2767-2777.

图/表 19

表1

表2

图1

表3

图2

表4

表5

图3

图4

图5

表6

图6

表7

图7

表8

图8

表9

图9

图10

参考文献 25

1	WU Y P, RAHM E, HOLZE R. Carbon anode materials for lithium ion batteries[J]. Journal of Power Sources, 2003, 114(2): 228-236.
2	陆浩, 刘柏男, 禇赓, 等. 锂离子电池负极材料产业化技术进展[J]. 储能科学与技术, 2016, 5(2): 109-119.
	LU H, LIU B N, CHU G, et al. Technology review of anode materials for lithium ion batteries[J]. Energy Storage Science and Technology, 2016, 5(2): 109-119.
3	FU L J, LIU H, LI C, et al. Surface modifications of electrode materials for lithium ion batteries[J]. Solid State Sciences, 2006, 8(2): 113-128.
4	MUNDSZINGER M, FARSI S, RAPP M, et al. Morphology and texture of spheroidized natural and synthetic graphites[J]. Carbon, 2017, 111: 764-773.
5	刘业翔, 周向阳, 李劼, 等. 天然石墨中的嵌/脱锂离子过程[J]. 中国有色金属学报, 2002, 12(6): 1257-1262.
	LIU Y X, ZHOU X Y, LI J, et al. Li⁺ intercalation/deintercalation process in natural graphite[J]. The Chinese Journal of Nonferrous Metals, 2002, 12(6): 1257-1262.
6	WANG C S, WU G T, LI W Z. Lithium insertion in ball-milled graphite[J]. Journal of Power Sources, 1998, 76(1): 1-10.
7	LU M, TIAN Y Y, YANG Y. A comparison of electrochemical performance of natural graphite sulfurized by ball-milling and heat-treating as an anode for lithium ion batteries[J]. Electrochimica Acta, 2009, 54(27): 6792-6796.
8	ZHOU X W, YANG Y, MA J T, et al. Effects of purification on the properties and microstructures of natural flake and artificial graphite powders[J]. Nuclear Engineering and Design, 2020, 360: 110527.
9	李金懋, 宋春莲, 俞哲, 等. 晶质石墨纯化技术研究现状与展望[J]. 炭素技术, 2021, 40(6): 15-19.
	LI J M, SONG C L, YU Z, et al. Status and prospect for purification technology of crystalline graphite[J]. Carbon Techniques, 2021, 40(6): 15-19.
10	KIM B R, KIM J H, IM J S. Effect and mechanism of pitch coating on the rate performance improvement of lithium-ion batteries[J]. Materials, 2022, 15(13): 4713.
11	IM U S, HWANG J U, YUN J H, et al. The effect of mild activation on the electrochemical performance of pitch-coated graphite for the lithium-ion battery anode material[J]. Materials Letters, 2020, 278: 128421.
12	冯国飞, 武建国, 刘伟, 等. 沥青包覆人造石墨炭化处理工艺[J]. 储能科学与技术, 2019, 8(3): 580-582.
	FENG G F, WU J G, LIU W, et al. Carbonization process of artificial graphite coated with asphalt[J]. Energy Storage Science and Technology, 2019, 8(3): 580-582.
13	XING B L, ZHANG C T, CAO Y J, et al. Preparation of synthetic graphite from bituminous coal as anode materials for high performance lithium-ion batteries[J]. Fuel Processing Technology, 2018, 172: 162-171.
14	HAN Y J, HWANG J U, KIM K S, et al. Optimization of the preparation conditions for pitch based anode to enhance the electrochemical properties of LIBs[J]. Journal of Industrial and Engineering Chemistry, 2019, 73: 241-247.
15	OHZEKI K, SAITO Y, GOLMAN B, et al. Shape modification of graphite particles by rotational impact blending[J]. Carbon, 2005, 43(8): 1673-1679.
16	OHZEKI K, SEINO K, KUMAGAI T, et al. Characterization of packing structure of tape cast with non-spherical natural graphite particles[J]. Carbon, 2006, 44(3): 578-586.
17	HENG S A, SHAN X J, WANG W, et al. Controllable solid electrolyte interphase precursor for stabilizing natural graphite anode in lithium ion batteries[J]. Carbon, 2020, 159: 390-400.
18	齐仲辉, 徐有红, 刘洪波, 等. 整形和表面改性对人造石墨负极材料性能的影响[J]. 炭素技术, 2012, 31(1): 1-5.
	QI Z H, XU Y H, LIU H B, et al. The influences of shaping and surface modification on the performance of artifical graphite anode materials[J]. Carbon Techniques, 2012, 31(1): 1-5.
19	王靖, 高惠民, 焦玄, 等. 吉林某隐晶质石墨球形化整形及提纯试验研究[J]. 硅酸盐通报, 2018, 37(10): 3244-3247, 3255.
	WANG J, GAO H M, JIAO X, et al. Spheroidization and purification on aphanitic graphite in Jilin[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(10): 3244-3247, 3255.
20	杨旭, 谷小虎, 王育红, 等. 锂离子电池负极材料石墨碎除杂整形研究[J]. 炭素技术, 2013, 32(3): 35-37.
	YANG X, GU X H, WANG Y H, et al. Research on removing impurities and shaping of graphite scraps for lithium ion battery anode materials[J]. Carbon Techniques, 2013, 32(3): 35-37.
21	PARK Y S, LEE T W, SHIN M S, et al. Modification for improving the electrochemical performance of spherically-shaped natural graphite as anode material for lithium-ion batteries[J]. Journal of the Electrochemical Society, 2016, 163(14): A3078-A3086.
22	YOSHIO M, WANG H Y, FUKUDA K, et al. Improvement of natural graphite as a lithium-ion battery anode material, from raw flake to carbon-coated sphere[J]. Journal of Materials Chemistry, 2004, 14(11): 1754-1758.
23	SHI P, ZHANG X Q, SHEN X, et al. A review of composite lithium metal anode for practical applications[J]. Advanced Materials Technologies, 2020, 5(1): 1900806.
24	何鹏, 张国旺, 肖骁, 等. 天然石墨球形化设备应用现状与展望[J]. 中国非金属矿工业导刊, 2020(4): 6-9.
	HE P, ZHANG G W, XIAO X, et al. Application and prospect of natural graphite spheroidization equipment[J]. China Non-Metallic Minerals Industry, 2020(4): 6-9.
25	杨玉芬, 陈湘彪, 盖国胜, 等. 天然石墨球形化工艺研究[J]. 过程工程学报, 2004, 4(S1): 309-313.
	YANG Y F, CHEN X B, GAI G S, et al. Preparing spherical graphite[J]. The Chinese Journal of Process Engineering, 2004, 4(S1): 309-313.

Sample name	TAP/(g/cm³)	SSA/(m²/g)	D50/μm
raw material	0.435	11.47	5.019
Purified material	0.452	11.87	5.143
H-SG/C-2	0.647	8.62	6.941
H-SG/C-5	0.716	6.66	10.491
H-SG/C-10	0.764	5.02	11.967
H-SG/C-15	0.832	4.51	12.892

Sample name	Discharge capacity/(mAh/g)	Charge capacity/(mAh/g)	Efficiency/%
Before purification	367.0	306.8	83.59
After purification	395.2	340.3	86.10
H-SG/C-2	395.8	347.4	87.77
H-SG/C-5	389.5	349.7	89.79
H-SG/C-10	384.1	350.9	91.36
H-SG/C-15	387.7	355.3	91.64

Sample name	Heating rate/(℃/min)	Soaking temperature/℃	Soaking time/h	High temperature soaking/℃	Soaking time/h
SG/C-V2	2	250	1	600	2
				800
				1000
SG/C-V5	5	250	1	600	2
				800
				1000
SG/C-V10	10	250	1	600	2
				800
				1000

Sample name	TAP/(g/cm³)	SSA/(m²/g)	D50/μm
SG/C-V10-600	0.680	7.77	15.259
SG/C-V10-1000	0.708	7.52	15.452
SG/C-V2-600	0.927	3.06	11.243
SG/C-V2-1000	0.922	3.15	11.674

[1]	李悦, 王博, 吴楠. 石墨烯/Si/SiO _x 纳米复合材料的制备及储锂性能研究[J]. 储能科学与技术, 2023, 12(9): 2752-2759.
[2]	曾少鸿, 吴伟雄, 刘吉臻, 汪双凤, 叶石丰, 冯振宇. 锂离子电池浸没式冷却技术研究综述[J]. 储能科学与技术, 2023, 12(9): 2888-2903.
[3]	李纪伟, 刘睿涵, 吕桃林, 潘隆, 马常军, 李清波, 赵芝芸, 杨文, 解晶莹. 基于局部离群点检测和标准差方法的锂离子电池组早期故障诊断[J]. 储能科学与技术, 2023, 12(9): 2917-2926.
[4]	黄晓伟, 李少鹏, 张校刚. 负极补锂锂化裕度对电芯性能的影响及机理研究[J]. 储能科学与技术, 2023, 12(9): 2727-2734.
[5]	江婉薇, 梁呈景, 钱历, 刘梅城, 朱孟想, 马骏. 锡基三维石墨烯泡沫调控及其锂电池负极性能[J]. 储能科学与技术, 2023, 12(9): 2746-2751.
[6]	高欣, 王若谷, 高文菁, 邓泽军, 梁睿祺, 杨騉. 基于运行数据的储能电站电池组一致性评估方法[J]. 储能科学与技术, 2023, 12(9): 2937-2945.
[7]	官亦标, 沈进冉, 刘家亮, 渠展展, 高飞, 刘施阳, 郭翠静, 周淑琴, 付珊珊. 以安全高质量应用为导向的储能锂离子电池综合性能评价标准[J]. 储能科学与技术, 2023, 12(9): 2946-2953.
[8]	陈欣, 李云伍, 梁新成, 李法霖, 张志冬. 基于模态分解的Transformer-GRU联合电池健康状态估计[J]. 储能科学与技术, 2023, 12(9): 2927-2936.
[9]	唐程波, 锁要红, 何昭坤. 基于正弦函数的液冷板上流体流向对锂离子电池散热性能的影响[J]. 储能科学与技术, 2023, 12(8): 2547-2555.
[10]	左安昊, 方儒卿, 李哲. 锂离子电池单颗粒动力学表征方法综述[J]. 储能科学与技术, 2023, 12(8): 2457-2481.
[11]	陈满, 程志翔, 赵春朋, 彭鹏, 雷旗开, 金凯强, 王青松. 锂离子电池储能集装箱爆炸危害数值模拟[J]. 储能科学与技术, 2023, 12(8): 2594-2605.
[12]	黄永浩, 臧国景, 朱霨亚, 廖友好, 李伟善. LiF添加剂改善含锂陶瓷隔膜与4.35 V LiNi_0.8Co_0.1Mn_0.1O₂ 正极的界面稳定性[J]. 储能科学与技术, 2023, 12(8): 2361-2369.
[13]	杨佳兴, 张恒运, 徐屹东. 基于电化学-热耦合模型的锂离子电池组件产热分析[J]. 储能科学与技术, 2023, 12(8): 2615-2625.
[14]	张吉禄, 董育辰, 宋强, 袁思鸣, 郭孝东. 多晶及单晶高镍三元材料LiNi_0.9Co_0.05Mn_0.05O₂ 的可控制备及其电化学储锂特性[J]. 储能科学与技术, 2023, 12(8): 2382-2389.
[15]	郭煜, 王亦伟, 钟隽, 杜进桥, 田杰, 李艳, 蒋方明. 基于增量容量曲线的锂离子电池微内短路故障诊断方法[J]. 储能科学与技术, 2023, 12(8): 2536-2546.