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Corresponding Author

Zhi-Cong Shi(zhicong@gdut.edu.cn)

Abstract

Hard carbon is one of the most promising anode material for lithium ion batteries (LIBs) owing to its high stability, widespread availability, low-cost, and excellent performance. The electrochemical properties of hard carbon materials depend strongly on the type of precursors. It is, therefore, very important to choose an excellent hard carbon precursor. Polyacrylonitrile, petroleum pitch and peanut shells were used as raw materials to prepare different hard carbon anode materials for LIBs. These hard carbon anode materials were successfully synthesized in two steps. The selected precursor was firstly carbonized at 600℃ for 1 h in argon atmosphere using heating rate of 1℃·min-1, and then was further carbonized at 1200℃ for 1h in argon atmosphere using heating rate of 5℃·min-1. Under such a low heating rate, a relatively small specific surface area could be obtained as much as possible for the hard carbon anode material. The surface morphology and phase structure of as synthesized hard carbon materials were analyzed by scanning electron microscopy, X-ray diffractometer, nitrogen adsorption analyzer and Raman spectrometer. The ion carrier storage mechanism was further investigated using cyclic voltammetry by examining whether the ion insertion/extraction mechanism is surface-controlled pseudocapacitance or diffusion-limited intercalation. It was further verified that the lithium storage mechanism of hard carbon anode materials is in line with the “adsorption-intercalation” mechanism. The results indicated that polyacrylonitrile-derived hard carbon anode material had low impedance by EIS test. This may be the reason why the low voltage platform of polyacrylonitrile-derived hard carbon materials had a higher specific capacity. The electrochemical performance of different hard carbon materials were investigated through galvanostatic charge and discharge tests. The peanut shell-derived hard carbon material showed the highest initial specific capacity (579.1 mAh·g-1), but the lowest initial coulombic efficiency (49.35%). The petroleum pitch-derived one delivered the highest initial coulombic efficiency (85.97%), but the lowest initial specific capacity (301.7 mAh·g-1). Comparing the cycle performance of these three hard carbon materials, polyacrylonitrile-derived hard carbon materials exhibited the excellent cycling performance (87.17% of capacity over 500 cycles). This study would provide useful assistance to understand the precursor-derived electrochemical properties of hard carbon anode material in practical applications.

Graphical Abstract

Keywords

lithium ion battery, anode material, hard carbon, electrochemical performance

Publication Date

2021-04-28

Online Available Date

2021-02-18

Revised Date

2021-01-22

Received Date

2021-01-02

References

[1] Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batterie[J]. Nature, 2001,414(6861):359-367.
pmid: 11713543

[2] Li Q X(李巧霞), Mao H M(毛宏敏), Liu M S(刘明爽), Xu Q J(徐群杰). Status quo and prospect in hard carbon anode material for lithium ion battery[J]. J. Shanghai Univ. Electric. Power(上海电力学院学报) 2014,30(1):75-78.

[3] Guan Y B(官亦标), Shen J R(沈进冉), Li K L(李康乐), Xu B(徐斌). Research progress on capacitive liithium-ion battery[J]. Energy Storage Sci. & Technol.(储能科学与技术) 2019,8(5):799-806.

[4] Wu M H(武明昊), Chen J(陈剑), Wang C(王崇), Yi B L(衣宝廉). Research progress in anode materials for Li-ion battery[J]. Battery(电池) 2011,4(4):222-225.

[5] Yang G(杨果), Ma Z(马壮), Yang S B(杨绍斌), Shen D(沈丁). Synjournal of phenolic resin hard carbon with low specific surface area and its electrochemical properties[J]. Mater. Rev.(材料导报) 2019,33(22):3820-3824.

[6] Qian Y, Jiang S, Li Y, Yi Z, Zhou J, Li T Q, Han Y, Wang Y S, Tian J, Lin N, Qian Y T. In situ revealing the electroactivity of P-O and P-C bonds in hard carbon for high-capacity and long-life Li/K-ion batteries[J]. Adv. Energy Mater., 2019,9(34):1901676.
doi: 10.1002/aenm.v9.34 URL

[7] Gong J, Wu H, Yang Q. Structural and electrochemical properties of disordered carbon prepared by the pyrolysis of poly(p-phenylene) below 1000 ℃ for the anode of a lithium-ion battery[J]. Carbon, 1999,37(9):1409-1416.
doi: 10.1016/S0008-6223(99)00002-0 URL

[8] Han Y J, Hwang J U, Kim K S, Kim J H, Lee J D, Im J S. Optimization of the preparation conditions for pitch based anode to enhance the electrochemical properties of LIBs[J]. J. Ind. Eng. Chem., 2019,73(73):241-247.
doi: 10.1016/j.jiec.2019.01.031 URL

[9] Guo Z H, Wang C Y, Chen M M, Li M W. Hard carbon derived from coal tar pitch for use as the anode material in lithium ion batteries[J]. Int. J. Electrochem. Sci., 2013,8(8):2702-2709.

[10] Concheso A, Santamaría R, Granda M, Menendez R, Jimenez-Mateos J M, Alcantara R, Lavela P, Tirado J L. Influence of oxidative stabilization on the electrochemical behaviour of coal tar pitch derived carbons in lithium batteries[J]. Electrochim. Acta, 2005,50(5):1225-1232.
doi: 10.1016/j.electacta.2004.07.054 URL

[11] Fromm O, Heckmann A, Rodehorst U C, Frerichs J, Becker D, Winter M, Placke T. Carbons from biomass precursors as anode materials for lithium ion batteries: new insights into carbonization and graphitization behavior and into their correlation to electrochemical performance[J]. Carbon, 2018,128(128):147-163.
doi: 10.1016/j.carbon.2017.11.065 URL

[12] Nishi Y. Carbonaceous materials for lithium ion secondary battery anodes[J]. Mol. Cryst. Liq. Cryst., 2000,340(1):419-424.
doi: 10.1080/10587250008025503 URL

[13] Yan J(颜剑), Su Y S(苏玉长), Su J T(苏继桃), Lu P T(卢普涛). Research progress on anode materials for lithium-ion batteries[J]. Chinese Battery Ind.(电池工业) 2006,11(4):277-281.

[14] Chen K H, Vishwas G, Min J N, Wied M, Muller S, Wood V, Sakamoto J, Thornton K, Dasgupta N P. Enabling 6C fast charging of Li-ion batteries with graphite/hard carbon hybrid anodes[J]. Adv. Energy Mater., 2020,9(13):2003336.

[15] Yu H Y, Liang H J, Gu Z Y, Meng Y F, Yang M, Yu M X, Zhao C D, Wu X L. Waste-to-wealth: low-cost hard carbon anode derived from unburned charcoal with high capacity and long cycle life for sodium-ion/lithium-ion batteries[J]. Electrochim. Acta, 2020,361(361):137041.
doi: 10.1016/j.electacta.2020.137041 URL

[16] Lin X Y, Liu Y Z, Tan H, Zhang B. Advanced lignin-derived hard carbon for Na-ion batteries and a comparison with Li and K ion storage[J]. Carbon, 2020,157(157):316-323.
doi: 10.1016/j.carbon.2019.10.045 URL

[17] Cao Y L, Xiao L F, Sushko M L, Wang W, Schwenzer B, Xiao J, Nie Z M, Saraf L V, Yang Z G, Liu J. Sodium ion insertion in hollow carbon nanowires for battery[J]. Nano Lett., 2012,12(7):3783-3787.
doi: 10.1021/nl3016957 URL

[18] Saurel D, Orayech B, Xiao B W, Carriazo D, Li X L, Rojo T. From charge storage mechanism to performance: a roadmap toward high specific energy sodium-ion batteries through carbon anode optimization[J]. Adv. Energy Mater., 2018,8(17):1703268.
doi: 10.1002/aenm.v8.17 URL

[19] Xiao L F, Lu H Y, Fang Y J, Sushko M L, Cao Y L, Ai X P, Yang H X, Liu J. Low-defect and low-porosity hard carbon with high coulombic efficiency and high capacity for practical sodium ion battery anode[J]. Adv. Energy Mater., 2018,8(20):1703238.
doi: 10.1002/aenm.201703238 URL

[20] Qiu S, Xiao L F, Sushko M L, Han K S, Shao Y Y, Yan M Y, Liang X M, Mai L Q, Feng J W, Cao Y L, Ai X P, Yang H X, Liu J. Manipulating adsorption-insertion mechanisms in nanostructured carbon materials for high-efficiency sodium ion storage[J]. Adv. Energy Mater., 2017,7(17):1700403.
doi: 10.1002/aenm.201700403 URL

[21] Alvin S, Setiadi H S, Hwang J, Chang W, Kwak S K, Kim J. Revealing the intercalation mechanisms of lithium, sodium, and potassium in hard carbon[J]. Adv. Energy Mater., 2020,10(20):2000283.
doi: 10.1002/aenm.v10.20 URL

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