Preparation and lithium storage characteristics of high-performance anode materials based on spheroidized tailings of natural flake graphite

doi:10.19799/j.cnki.2095-4239.2023.0274

Abstract

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

CLC Number:

TM 242

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.

Figures/Tables 19

Table 1

Table 2

Fig. 1

Table 3

Fig. 2

Table 4

Table 5

Fig. 3

Fig. 4

Fig. 5

Table 6

Fig. 6

Table 7

Fig. 7

Table 8

Fig. 8

Table 9

Fig. 9

Fig. 10

References 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]	Shaohong ZENG, Weixiong WU, Jizhen LIU, Shuangfeng WANG, Shifeng YE, Zhenyu FENG. A review of research on immersion cooling technology for lithium-ion batteries [J]. Energy Storage Science and Technology, 2023, 12(9): 2888-2903.
[2]	Jiwei LI, Ruihan LIU, Taolin LU, Long PAN, Changjun MA, Qingbo LI, Zhiyun ZHAO, Wen YANG, Jingying XIE. Early fault diagnosis of lithium-ion battery packs based on improved local outlier detection and standard deviation method [J]. Energy Storage Science and Technology, 2023, 12(9): 2917-2926.
[3]	Xin CHEN, Yunwu LI, Xincheng LIANG, Falin LI, Zhidong ZHANG. Battery health state estimation of combined Transformer-GRU based on modal decomposition [J]. Energy Storage Science and Technology, 2023, 12(9): 2927-2936.
[4]	Wanwei JIANG, Chengjing LIANG, Li QIAN, Meicheng LIU, Mengxiang ZHU, Jun MA. Regulating tin-based three-dimensional graphene foam and its performance as a lithium-ion battery anode [J]. Energy Storage Science and Technology, 2023, 12(9): 2746-2751.
[5]	Anhao ZUO, Ruqing FANG, Zhe LI. Kinetic characterization of electrode materials for lithium-ion batteries via single-particle microelectrodes [J]. Energy Storage Science and Technology, 2023, 12(8): 2457-2481.
[6]	Jiaxing YANG, Hengyun ZHANG, Yidong XU. Heat generation analysis for lithium-ion battery components using electrochemical and thermal coupled model [J]. Energy Storage Science and Technology, 2023, 12(8): 2615-2625.
[7]	Jilu ZHANG, Yuchen DONG, Qiang SONG, Siming YUAN, Xiaodong GUO. Controllable synthesis and electrochemical mechanism related to polycrystalline and single-crystalline Ni-rich layered LiNi_0.9Co_0.05Mn_0.05O₂ cathode materials [J]. Energy Storage Science and Technology, 2023, 12(8): 2382-2389.
[8]	Yu GUO, Yiwei WANG, Juan ZHONG, Jinqiao DU, Jie TIAN, Yan LI, Fangming JIANG. Fault diagnosis method for microinternal short circuits in lithium-ion batteries based on incremental capacity curve [J]. Energy Storage Science and Technology, 2023, 12(8): 2536-2546.
[9]	Qingsong ZHANG, Fangwei BAO, Jiangjao NIU. Risk analysis method of thermal runaway gas explosion in lithium-ion batteries [J]. Energy Storage Science and Technology, 2023, 12(7): 2263-2270.
[10]	Yubo ZHANG, Youyuan WANG, Dongning HUANG, Ziyi WANG, Weigen CHEN. Prognostic method of lithium-ion battery lifetime degradation under various working conditions [J]. Energy Storage Science and Technology, 2023, 12(7): 2238-2245.
[11]	Qinpei CHEN, Xuehui WANG, Wenzhong MI. Experiential study on the toxic and explosive characteristics of thermal runaway gas generated in electric-vehicle lithium-ion battery systems [J]. Energy Storage Science and Technology, 2023, 12(7): 2256-2262.
[12]	Wenda ZAN, Rui ZHANG, Fei DING. Development and application of electrochemical models for lithium-ion batteries [J]. Energy Storage Science and Technology, 2023, 12(7): 2302-2318.
[13]	Shuqin LIU, Xiaoyan WANG, Zhendong ZHANG, Zhenxia DUAN. Experimental and simulation research on liquid-cooling system of lithium-ion battery packs [J]. Energy Storage Science and Technology, 2023, 12(7): 2155-2165.
[14]	Maosong FAN, Mengmeng GENG, Guangjin ZHAO, Kai YANG, Fangfang WANG, Hao LIU. Research on battery sorting technology for echelon utilization based on multifrequency impedance [J]. Energy Storage Science and Technology, 2023, 12(7): 2202-2210.
[15]	Yi WANG, Xuebing CHEN, Yuanxi WANG, Jieyun ZHENG, Xiaosong LIU, Hong LI. Overview of multilevel failure mechanism and analysis technology of energy storage lithium-ion batteries [J]. Energy Storage Science and Technology, 2023, 12(7): 2079-2094.