Study and Improvement on Expansion Property of Silicon Oxide

Authors

Wei-Chuan Qiao, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;
Fang-Ru Li, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;
Jin-Lin Xiao, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;
Li-Juan Qu, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;
Xiao Zhao, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;
Meng Zhang, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;Follow
Chun-Lei Pang, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;
Zi-Kun Li, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;
Jian-Guo Ren, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;Follow
Xue-Qin He, BTR New Material Group Co., Ltd., Shenzhen 518106, Guangdong, China;

Corresponding Author

Meng Zhang(zhangmeng@btrchina.com);
Jian-Guo Ren(renjianguo@btrchina.com）

Abstract

The silicon-based anode materials have the potential to meet the ever-increasing demand for energy density in lithium-ion batteries market owing to their high theoretical specific capacity. Unfortunately, their commercialization was hindered by the continuous volume expansion. Herein, the expansion characteristics and corresponding mechanism of the silicon oxide and graphite-silicon oxide composites were investigated by in-situ displacement detection systematically. The results showed that the expansion property was improved by material process modifications. During the de/lithiation processes of graphite, the expansion ratio in 30% ~ 50% SOC changed little because of the small interlayer spacing variation of the intercalated graphite. Unlike the graphite anode, there was no obvious platform in the expansion ratio curve of silicon oxide except for the first lithiation process. As for the graphite-silicon oxide composite, the expansion ratio was influenced by two-component materials. In order to figure out how the expansion ratio of the composite changed, the capacity contributions of graphite and silicon oxide at various states of charge were calculated. It was found that the graphite dominated the initial stage of the first and second delithiation processes, while delithiation of silicon oxide started from 36% SOC, leading to the steep decline of the expansion ratio curves. During the second lithiation process, the capacity of the first 20% SOC mainly came from silicon oxide, after which the capacity proportion of graphite increased gradually. In 40% ~ 50% SOC region, the capacity contribution of silicon oxide was negligible, resulting in the reduction of expansion increase rate. The calculated capacity contribution of the component materials corresponded to the evaluation of expansion ratio, indicating the reliability of the calculation method, which could be applied in other graphite-silicon oxide composites with different proportions. The irreversible expansion of graphite mainly occurred at the first three charges processes, while the irreversible expansion of silicon oxide increased significantly over all cycling processes. The reversible expansion of silicon oxide decreased gradually as the capacity fading. And the total expansion of silicon oxide tended to be decreased from the third cycle because the decrement of reversible expansion surpassed the increment of irreversible expansion. Finally, the expansion ratio especially the irreversible expansion of silicon oxide was effectively reduced by optimizing the surface coating, prelithiation and particle size. These results could provide favorable guidance for developing high-performance silicon-based anode materials with stable structure and low expansion ratio.

Graphical Abstract

Keywords

Li-ion battery, silicon oxide material, graphite-silicon oxide composite, expansion property, expansion improvement

DOI Link

https://doi.org/10.13208/j.electrochem.210812

Publication Date

2022-05-28

Online Available Date

2021-09-17

Revised Date

2021-08-27

Received Date

2021-08-12

Recommended Citation

Wei-Chuan Qiao, Fang-Ru Li, Jin-Lin Xiao, Li-Juan Qu, Xiao Zhao, Meng Zhang, Chun-Lei Pang, Zi-Kun Li, Jian-Guo Ren, Xue-Qin He. Study and Improvement on Expansion Property of Silicon Oxide[J]. Journal of Electrochemistry, 2022 , 28(5): 210812.
DOI: 10.13208/j.electrochem.210812
Available at: https://jelectrochem.xmu.edu.cn/journal/vol28/iss5/5

References

[1] Choi J W, Aurbach D. Promise and reality of post-lithium-ion batteries with high energy densities[J]. Nat. Rev. Mater., 2016, 1(4): 16013.
doi: 10.1038/natrevmats.2016.13 URL

[2] Li M, Lu J, Chen Z, Chen Z W, Amine K. 30 years of lithium-ion batteries[J]. Adv. Mater., 2018, 30(33): 1800561.
doi: 10.1002/adma.201800561 URL

[3] Zhang W J. A review of the electrochemical performance of alloy anodes for lithium-ion batteries[J]. J. Power Sour-ces, 2011, 196(1): 13-24.

[4] Zhang W J. Lithium insertion/extraction mechanism in alloy anodes for lithium-ion batteries[J]. J. Power Sources, 2011, 196(3): 877-885.
doi: 10.1016/j.jpowsour.2010.08.114 URL

[5] Obrovac M N, Chevrier V L. Alloy negative electrodes for Li-ion batteries[J]. Chem. Rev., 2014, 114(23): 11444-11502.
doi: 10.1021/cr500207g pmid: 25399614

[6] Kasavajjula U, Wang C S, Appleby A J. Nano-and bulk-silicon-based insertion anodes for lithium-ion secondary cells[J]. J. Power Sources, 2007, 163(2): 1003-1039.
doi: 10.1016/j.jpowsour.2006.09.084 URL

[7] McDowell M T, Lee S W, Nix W D, Cui Y. 25th anniversary article: understanding the lithiation of silicon and other alloying anodes for lithium-ion batteries[J]. Adv. Mater., 2013, 25(36): 4966-4984.
doi: 10.1002/adma.201301795 URL

[8] Liang B, Liu Y P, Xu Y H. Silicon-based materials as high capacity anodes for next generation lithium ion batteries[J]. J. Power Sources, 2014, 267: 469-490.
doi: 10.1016/j.jpowsour.2014.05.096 URL

[9] Obrovac M N. Si-alloy negative electrodes for Li-ion batteries[J]. Curr. Opin. Electrochem., 2018, 9: 8-17.

[10] Chen T, Wu J, Zhang Q L, Su X. Recent advancement of SiO_x based anodes for lithium-ion batteries[J]. J. Power Sources, 2017, 363: 126-144.
doi: 10.1016/j.jpowsour.2017.07.073 URL

[11] Wu Y K(吴永康), Fu R S(傅儒生), Liu Z P(刘兆平), Xia Y G(夏永高), Shao G J(邵光杰). Development of silicon suboxide anodes for lithium-ion batteries[J]. J. Chin. Ceram. SOC.(硅酸盐学报), 2018, 46(11):1645-1652.

[12] Liu Z H, Yu Q, Zhao Y L, He R H, Xu M, Feng S H, Li S D, Zhou L, Mai L Q. Silicon oxides: A promising family of anode materials for lithium-ion batteries[J]. Chem. Soc. Rev., 2019, 48(1): 285-309.
doi: 10.1039/C8CS00441B URL

[13] Jiao M L, Wang Y F, Ye C L, Wang C Y, Zhang W K, Liang C. High-capacity SiO_x (0 ≤ x ≤2) as promising anode materials for next-generation lithium-ion batteries[J]. J. Alloys Compd., 2020, 842: 155774.
doi: 10.1016/j.jallcom.2020.155774 URL

[14] Ohzuku T, Matoba N, Sawai K. Direct evidence on anomalous expansion of graphite-negative electrodes on first charge by dilatometry[J]. J. Power Sources, 2001, 97-98: 73-77.
doi: 10.1016/S0378-7753(01)00590-0 URL

[15] Hahn M, Buqa H, Ruch P W, Goers D, Spahr M E, Ufheil J, Novák P, Kötz R. A dilatometric study of lithium intercalation into powder-type graphite electrodes[J]. Electro-chem. Solid-State Lett., 2008, 11(9): A151-A154.

[16] Rieger B, Schlueter S, Erhard S V, Schmalz J, Reinhart G, Jossen A. Multi-scale investigation of thickness changes in a commercial pouch type lithium-ion battery[J]. J. Energy Storage, 2016, 6: 213-221.
doi: 10.1016/j.est.2016.01.006 URL

[17] Rieger B, Erhard S V, Rumpf K, Jossen A. A new method to model the thickness change of a commercial pouch cell during discharge[J]. J. Electrochem. Soc., 2016, 163(8): A1566-A1575.
doi: 10.1149/2.0441608jes URL

[18] Jones E M C, Çapraz ÖÖ, White S R, Sottos N R. Reversible and irreversible deformation mechanisms of composite graphite electrodes in lithium-ion batteries[J]. J. Electrochem. Soc., 2016, 163(9): A1965-A1974.
doi: 10.1149/2.0751609jes URL

[19] Bauer M, Wachtler M, Stöwe H, Persson J V, Danzer M A. Understanding the dilation and dilation relaxation behavior of graphite-based lithium-ion cells[J]. J. Power So-urces, 2016, 317: 93-102.

[20] Sauerteig D, Ivanov S, Reinshagen H, Bund A. Reversible and irreversible dilation of lithium-ion battery electrodes investigated by in-situ dilatometry[J]. J. Power Sources, 2017, 342: 939-946.
doi: 10.1016/j.jpowsour.2016.12.121 URL

[21] Kim T, Park S, Oh S M. Solid-state NMR and electrochemical dilatometry study on Li⁺ uptake/extraction me-chanism in SiO electrode[J]. J. Electrochem. Soc., 2007, 154(12): A1112-A1117.
doi: 10.1149/1.2790282 URL

[22] Louli A J, Li J, Trussler S, Fell C R, Dahn J R. Volume, pressure and thickness evolution of Li-ion pouch cells with silicon-composite negative electrodes[J]. J. Electro-chem. Soc., 2017, 164(12): A2689-A2696.
doi: 10.1149/2.1691712jes URL

[23] Louli A J, Ellis L D, Dahn J R. Operando pressure measurements reveal solid electrolyte interphase growth to rank Li-ion cell performance[J]. Joule, 2019, 3(3): 745-761.
doi: 10.1016/j.joule.2018.12.009

[24] Zhang X Y, He J, Zhou J, Chen H S, Song W L, Fang D N. Thickness evolution of commercial Li-ion pouch cells with silicon-based composite anodes and NCA cathodes[J]. Sci. China Techonl. Sci., 2021, 64(1): 83-90.

[25] Reimers J N, Dahn J R. Electrochemical and in situ X-ray diffraction studies of lithium intercalation in Li_xCoO₂[J]. J. Electrochem. Soc., 1992, 139(8): 2091-2097.
doi: 10.1149/1.2221184 URL