Citric acid-modified silicon anode with dual carbon stress modulation for stable lithium storage

doi:10.1016/j.cjche.2025.06.012

Chinese Journal of Chemical Engineering ›› 2025, Vol. 87 ›› Issue (11): 229-238.DOI: 10.1016/j.cjche.2025.06.012

Citric acid-modified silicon anode with dual carbon stress modulation for stable lithium storage

Qianqian Fan¹, Jing Wang¹, Zhiyuan Gao¹, Zhenpeng Zhu¹, Xingmei Guo¹, Yuanjun Liu¹, Xiangjun Zheng¹, Zhongyao Duan¹, Qinghong Kong², Junhao Zhang¹

1. School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China;
2. School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, China

Received:2025-02-09 Revised:2025-05-13 Accepted:2025-06-09 Online:2025-07-22 Published:2025-11-28
Contact: Junhao Zhang,E-mail:jhzhang6@just.edu.cn
Supported by:
The work was financially supported by Industry foresight and common key technology research in Carbon Peak and Carbon Neutrality Special Project from Zhenjiang city (CG2023003), National Natural Science Foundation of China (22379056, 22409076).

Citric acid-modified silicon anode with dual carbon stress modulation for stable lithium storage

Qianqian Fan¹, Jing Wang¹, Zhiyuan Gao¹, Zhenpeng Zhu¹, Xingmei Guo¹, Yuanjun Liu¹, Xiangjun Zheng¹, Zhongyao Duan¹, Qinghong Kong², Junhao Zhang¹

1. School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China;
2. School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, China

通讯作者: Junhao Zhang,E-mail:jhzhang6@just.edu.cn
基金资助:
The work was financially supported by Industry foresight and common key technology research in Carbon Peak and Carbon Neutrality Special Project from Zhenjiang city (CG2023003), National Natural Science Foundation of China (22379056, 22409076).

Abstract

Abstract: To effectively enhanced structural stability and cycling performance, a dual carbon protection strategy is proposed to fabricate Si nanoparticles encapsulated in citric acid (CA)-derived inner carbon layer and zeolitic imidazolate framework-67 (ZIF-67) derived outer carbon layer (Si@C-CA@c-ZIF). The results reveal that citric acid-derived carbon facilitates a uniform ZIF-67 coating on the Si surface and serves as the inner carbon precursor to reduce volumetric expansion of Si particles, more importantly, it can enhance the transport of electrons and ions between Si particles and ZIF-67-derived carbon. The ZIF-67-derived outer carbon layer further restricts Si particle expansion and enhances conductivity. Evaluated as anode material for lithium ion batteries, the Si@C-CA@c-ZIF anode demonstrates outstanding lithium storage performance, the high specific capacity is high to 924 mA·h·g^-1 at 1.0 A·g^-1 after 10 cycles of activation, and it still maintains a reversible capacity of 703.3 mA·h·g^-1 after 1000 cycles, along with a capacity retention of 76.1%. This work highlights the effectiveness of the dual carbon framework in addressing the volume expansion and conductivity limitations of Si, with potential applications for other high-capacity anode materials.

Key words: Dual carbon stress modulation, Citric acid, Silicon anodes, Electrochemistry, Volume expansion, Kinetics

摘要： To effectively enhanced structural stability and cycling performance, a dual carbon protection strategy is proposed to fabricate Si nanoparticles encapsulated in citric acid (CA)-derived inner carbon layer and zeolitic imidazolate framework-67 (ZIF-67) derived outer carbon layer (Si@C-CA@c-ZIF). The results reveal that citric acid-derived carbon facilitates a uniform ZIF-67 coating on the Si surface and serves as the inner carbon precursor to reduce volumetric expansion of Si particles, more importantly, it can enhance the transport of electrons and ions between Si particles and ZIF-67-derived carbon. The ZIF-67-derived outer carbon layer further restricts Si particle expansion and enhances conductivity. Evaluated as anode material for lithium ion batteries, the Si@C-CA@c-ZIF anode demonstrates outstanding lithium storage performance, the high specific capacity is high to 924 mA·h·g^-1 at 1.0 A·g^-1 after 10 cycles of activation, and it still maintains a reversible capacity of 703.3 mA·h·g^-1 after 1000 cycles, along with a capacity retention of 76.1%. This work highlights the effectiveness of the dual carbon framework in addressing the volume expansion and conductivity limitations of Si, with potential applications for other high-capacity anode materials.

关键词: Dual carbon stress modulation, Citric acid, Silicon anodes, Electrochemistry, Volume expansion, Kinetics

Qianqian Fan, Jing Wang, Zhiyuan Gao, Zhenpeng Zhu, Xingmei Guo, Yuanjun Liu, Xiangjun Zheng, Zhongyao Duan, Qinghong Kong, Junhao Zhang. Citric acid-modified silicon anode with dual carbon stress modulation for stable lithium storage[J]. Chinese Journal of Chemical Engineering, 2025, 87(11): 229-238.

References

[1] L.Q. Mai, M.Y. Yan, Y.L. Zhao, Track batteries degrading in real time, Nature 546 (7659) (2017) 469-470.
[2] H. Gu, M.Y. Gao, K. Shen, T.L. Zhang, J.H. Zhang, X.J. Zheng, X.M. Guo, Y.J. Liu, F. Cao, H.X. Gu, Q.H. Kong, S.L. Xiong, F127 assisted fabrication of Ge/rGO/CNTs nanocomposites with three-dimensional network structure for efficient lithium storage, Chin. Chem. Lett. 35 (9) (2024) 109273.
[3] Q.Q. Fan, J.H. Zhang, S.Y. Fan, B.J. Xi, Z.Y. Gao, X.M. Guo, Z.Y. Duan, X.J. Zheng, Y.J. Liu, S.L. Xiong, Advances in functional organosulfur-based mediators for regulating performance of lithium metal batteries, Adv. Mater. 36 (45) (2024) e2409521.
[4] L. Sun, Y. Liu, L.J. Wang, Z. Jin, Advances and future prospects of micro-silicon anodes for high-energy-density lithium-ion batteries: a comprehensive review, Adv. Funct. Mater. 34 (39) (2024) 2403032.
[5] J. Choi, H. Jeong, J. Jang, A.R. Jeon, I. Kang, M. Kwon, J. Hong, M. Lee, Weakly solvating solution enables chemical prelithiation of graphite-SiOx anodes for high-energy Li-ion batteries, J. Am. Chem. Soc. 143 (24) (2021) 9169-9176.
[6] H. Gu, Z.P. Zhu, Z.Y. Gao, J.H. Zhang, X.M. Guo, Y.J. Liu, X.J. Zheng, Q.Q. Fan, Z.Y. Duan, F. Cao, C.S. Li, Q.H. Kong, J. University, Ge-Si/C nanofiber composite with enhanced cyclic stability and rate capability for lithium-ion batteries, ACS Appl. Nano Mater. 8 (5) (2025) 2196-2204.
[7] J.L. Chen, X.M. Guo, M.Y. Gao, J. Wang, S.Q. Sun, K. Xue, S.Y. Zhang, Y.J. Liu, J.H. Zhang, Self-supporting dual-confined porous Si@c-ZIF@carbon nanofibers for high-performance lithium-ion batteries, Chem. Commun. 57 (81) (2021) 10580-10583.
[8] H.T. Xia, X.J. Mu, J.H. Zhou, W.P. Liu, G.J. Wu, F. Dang, D.M. Zhang, L. Miao, H.Q. Qin, Z.J. Zhang, X.X. Lei, A.J. Lu, Z.X. Mo, Realization of high-capacity coulombic efficiency in sodium alginate/carbon nanotube double network coated Si-anode for lithium-ion batteries, Sustain. Mater. Technol. 40 (2024) e00940.
[9] P.L. Yu, Z.W. Li, D.C. Zhang, Q. Xiong, J. Yu, C.Y. Zhi, Hierarchical yolk-shell silicon/carbon anode materials enhanced by vertical graphene sheets for commercial lithium-ion battery applications, Adv. Funct. Mater. 35 (2) (2025) 2413081.
[10] Z.Y. He, C.X. Zhang, Z.X. Zhu, Y.X. Yu, C. Zheng, F. Wei, Advances in carbon nanotubes and carbon coatings as conductive networks in silicon-based anodes, Adv. Funct. Mater. 34 (48) (2024) 2408285.
[11] S.Y. Zhang, Y.C. Xue, Y.T. Zhang, C.X. Zhu, X.M. Guo, F. Cao, X.J. Zheng, Q.H. Kong, J.H. Zhang, T.X. Fan, KOH-assisted aqueous synthesis of bimetallic metal-organic frameworks and their derived selenide composites for efficient lithium storage, Int. J. Miner. Metall. Mater. 30 (4) (2023) 601-610.
[12] K.M. Chen, Z.W. Li, J.H. Zhou, J. Gao, H.Q. Qin, W.P. Liu, X.X. Lei, X.Y. Wang, L. Miao, Hollow nitrogen-doped carbon layer-coated nano-silicon as anode material for high-performance lithium-ion batteries, Appl. Mater. Today 42 (2025) 102561.
[13] R.S. Gao, J. Tang, X.L. Yu, S. Tang, K. Ozawa, T. Sasaki, L.C. Qin, In situ synthesis of MOF-derived carbon shells for silicon anode with improved lithium-ion storage, Nano Energy 70 (2020) 104444.
[14] B.Q. Chen, D.M. Xu, S.M. Chai, Z. Chang, A.Q. Pan, Enhanced silicon anodes with robust SEI formation enabled by functional conductive binder, Adv. Funct. Mater. 34 (34) (2024) 2401794.
[15] Q.Q. Wu, Y.T. Zhong, R.M. Chen, G.Y. Ling, X.H. Wang, Y.R. Shen, C. Hao, Cu-Ag-C@Ni3S4 with core shell structure and rose derived carbon electrode materials: an environmentally friendly supercapacitor with high energy and power density, Ind. Crops Prod. 222 (2024) 119676.
[16] B.J. Chen, L.H. Zu, Y. Liu, R.J. Meng, Y.T. Feng, C.X. Peng, F. Zhu, T.Z. Hao, J.J. Ru, Y.G. Wang, J.H. Yang, Space-confined atomic clusters catalyze superassembly of silicon nanodots within carbon frameworks for use in lithium-ion batteries, Angew. Chem. Int. Ed 59 (8) (2020) 3137-3142.
[17] Y.Z. Zhou, Y.J. Yang, G.L. Hou, D. Yi, B. Zhou, S.M. Chen, T.D. Lam, F.L. Yuan, D. Golberg, X. Wang, Stress-relieving defects enable ultra-stable silicon anode for Li-ion storage, Nano Energy 70 (2020) 104568.
[18] D. Jin, X.F. Yang, Y.Q. Ou, M.M. Rao, Y.T. Zhong, G.M. Zhou, D.Q. Ye, Y.C. Qiu, Y.P. Wu, W.S. Li, Thermal pyrolysis of Si@ZIF-67 into Si@N-doped CNTs towards highly stable lithium storage, Sci. Bull. 65 (6) (2020) 452-459.
[19] C.L. Jiang, L. Xiang, S.J. Miao, L. Shi, D.H. Xie, J.X. Yan, Z.J. Zheng, X.M. Zhang, Y.B. Tang, Flexible interface design for stress regulation of a silicon anode toward highly stable dual-ion batteries, Adv. Mater. 32 (17) (2020) e1908470.
[20] J.J. Zhao, J. Chen, M.M. Zhou, Q. Zhang, X.C. Li, J.Q. Pan, Ultra-firm phthalocyanine-based tetragonal covalent organic framework layer @ nano silicon anode for high durability Li-ion battery, Chem. Eng. J. 488 (2024) 151110.
[21] Y.H. Song, L. Zuo, S.H. Chen, J.F. Wu, H.Q. Hou, L. Wang, Porous nano-Si/carbon derived from zeolitic imidazolate Frameworks@Nano-Si as anode materials for lithium-ion batteries, Electrochim. Acta 173 (2015) 588-594.
[22] Z.Y. Wang, H.H. Zhang, X.Y. Zhang, X.M. Wang, X. Zhang, Solvent-free and large-scale synthesis of SiO x/C nanocomposite with carbon encapsulation for high-performance lithium-ion battery anodes, Compos. Part B Eng. 247 (2022) 110308.
[23] T.L. Zhang, M.R. Wu, H. Gu, H.W. Yu, M. Zhou, X.M. Guo, Y.J. Liu, X.J. Zheng, Q.H. Kong, J.H. Zhang, Double carbon modified CoS2/NiS2 as anode material for efficient lithium storage performance, J. Energy Storage 73 (2023) 108981.
[24] Y.Y. Yu, C. Yang, Y. Jiang, J.D. Zhu, J.H. Zhang, M.J. Jiang, Consecutive covalent bonds reconstruct robust dual-interfaces by carbonized binder to enable conductive-additive-free durable silicon anode, Nano Energy 130 (2024) 110108.
[25] X.K. Wang, Y. Pan, X.H. Wang, Y.N. Guo, C.H. Ni, J.B. Wu, C. Hao, High performance hybrid supercapacitors assembled with multi-cavity nickel cobalt sulfide hollow microspheres as cathode and porous typha-derived carbon as anode, Ind. Crops Prod. 189 (2022) 115863.
[26] H. Chen, Y.Y. Xiong, J. Li, J. Abed, D. Wang, A. Pedrazo-Tardajos, Y.P. Cao, Y.T. Zhang, Y. Wang, M. Shakouri, Q.F. Xiao, Y.F. Hu, S. Bals, E.H. Sargent, C.Y. Su, Z.Y. Yang, Epitaxially grown silicon-based single-atom catalyst for visible-light-driven syngas production, Nat. Commun. 14 (1) (2023) 1719.
[27] J. Ma, J. Yu, G.Y. Chen, Y. Bai, S.K. Liu, Y.G. Hu, M. Al-Mamun, Y. Wang, W.B. Gong, D. Liu, Y.F. Li, R. Long, H.J. Zhao, Y.J. Xiong, Rational design of N-doped carbon-coated cobalt nanoparticles for highly efficient and durable photothermal CO₂ conversion, Adv. Mater. 35 (42) (2023) e2302537.
[28] K. Xiao, J. Wang, Z. Chen, Y. Qian, Z. Liu, L. Zhang, X. Chen, J. Liu, X. Fan, Z.X. Shen, Improving polysulfides adsorption and redox kinetics by the Co4 N nanoparticle/N-doped carbon composites for lithium-sulfur batteries, Small 15 (25) (2019) e1901454.
[29] F. Yuan, Y.N. Li, Y.Q. Wang, Z.J. Li, Q.J. Wang, H.L. Sun, D. Zhang, W. Wang, B. Wang, Cobalt nanoparticles synergize with oxygen-containing functional groups to realize fast and stable potassium storage for carbon anode, Adv. Funct. Mater. 33 (46) (2023) 2304753.
[30] H. Wu, G.H. Yu, L.J. Pan, N. Liu, M.T. McDowell, Z.N. Bao, Y. Cui, Stable Li-ion battery anodes by in situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles, Nat. Commun. 4 (2013) 1943.
[31] M.Y. Gao, Z.H. Tang, M.R. Wu, J.L. Chen, Y.C. Xue, X.M. Guo, Y.J. Liu, Q.H. Kong, J.H. Zhang, Self-supporting N, P doped Si/CNTs/CNFs composites with fiber network for high-performance lithium-ion batteries, J. Alloys Compd. 857 (2021) 157554.
[32] W.W. Zeng, L. Wang, X. Peng, T.F. Liu, Y.Y. Jiang, F. Qin, L. Hu, P.K. Chu, K.F. Huo, Y.H. Zhou, Enhanced ion conductivity in conducting polymer binder for high-performance silicon anodes in advanced lithium-ion batteries, Adv. Energy Mater. 8 (11) (2018) 1702314.
[33] L. Wang, Z.H. Wang, L.L. Xie, L.M. Zhu, X.Y. Cao, ZIF-67-derived N-doped Co/C nanocubes as high-performance anode materials for lithium-ion batteries, ACS Appl. Mater. Interfaces 11 (18) (2019) 16619-16628.
[34] X.M. Fan, T. Cai, S.Y. Wang, Z.H. Yang, W.X. Zhang, Carbon nanotube-reinforced dual carbon stress-buffering for highly stable silicon anode material in lithium-ion battery, Small 19 (30) (2023) e2300431.
[35] Q. Wang, J.C. Su, H.L. Chen, D.Q. Wang, X.Y. Tian, Y.J. Zhang, X. Feng, S. Wang, J. Li, H.L. Jin, Highly conductive nitrogen-doped sp2/sp3 hybrid carbon as a conductor-free charge storage host, Adv. Funct. Mater. 32 (51) (2022) 2209201.
[36] M.Y. Gao, Y.C. Xue, Y.T. Zhang, C.X. Zhu, H.W. Yu, X.M. Guo, S.S. Sun, S.L. Xiong, Q.H. Kong, J.H. Zhang, Growing Co-Ni-Se nanosheets on 3D carbon frameworks as advanced dual functional electrodes for supercapacitors and sodium ion batteries, Inorg. Chem. Front. 9 (15) (2022) 3933-3942.
[37] J.L. Chen, J. Wang, S.Y. Zhang, K. Xue, J.H. Zhang, F. Cao, Q.H. Kong, X.M. Guo, Si nanoparticles confined in N, P- doped double carbon as efficient anode materials for lithium ion batteries, J. Alloys Compd. 935 (2023) 167850.
[38] H.W. Yu, M.Y. Gao, M. Zhou, H. Gu, X.J. Zheng, X.M. Guo, Y.J. Liu, F. Cao, Q.H. Kong, J.H. Zhang, F127/PDA dual-assisted fabricating high dispersed Ge nanoparticles/N-doped porous carbon composites with efficient lithium storage, J. Mater. Res. Technol. 26 (2023) 5055-5064.

Citric acid-modified silicon anode with dual carbon stress modulation for stable lithium storage

Citric acid-modified silicon anode with dual carbon stress modulation for stable lithium storage

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Huagui Jin, Xuebin An, Shizhao Wang, Yunshan Wang, Gang Yang, Yong Sun. Study of defluorination by thermal treatment of phosphogypsum under steam atmosphere [J]. Chinese Journal of Chemical Engineering, 2025, 85(9): 206-216.
[2]	Yang Lv, Gaoyang Li, Jianpeng Sun, Honghui Ou, Yang Li, Guidong Yang. Stability investigation and techno-economic assessment of gliding arc plasma coupled electrocatalytic ammonia synthesis system [J]. Chinese Journal of Chemical Engineering, 2025, 85(9): 251-259.
[3]	Yongbin Shen, Qihe Ma, Hua Yuan, Chuang Liu, Likun Yang, Hao Huang, Bowen Shi, Zhenhua Li, Shunyu Liang, Hu Li, Zhengping Dong. Selective catalytic deoxygenation of 1-octanol from Fischer-Tropsch C10 mixed oil [J]. Chinese Journal of Chemical Engineering, 2025, 85(9): 270-279.
[4]	Zhe Wang, Zhengpeng Zhu, Kai Xue, Xingmei Guo, Yuanjun Liu, Xiangjun Zheng, Qianqian Fan, Zhongyao Duan, Qinghong Kong, Junhao Zhang. Fabrication of Sb-based alloys/carbon nanofibers with uniform dispersion as anode material for high efficiency sodium storage [J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 208-216.
[5]	Yilun Dong, Kang Xue, Zexing He, Chongjun Li, Ruijie Gao, Zhenfeng Huang, Chengxiang Shi, Xiangwen Zhang, Lun Pan, Jijun Zou. Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions [J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 217-228.
[6]	Xintuo Chen, Wencong Chen, Yu Zhou, Liangliang Zhang, Jianfeng Chen. Investigation of reaction pathways and kinetics in the gas-phase noncatalytic oxidation of hexafluoropropylene [J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 286-297.
[7]	Siwen Huang, Kui Wang, Haibo Wang, Li Lv, Tao Zhang, Wenxiang Tang, Zongpeng Zou, Shengwei Tang. Comprehensive utilization of titanium-bearing blast furnace slag by H₂SO₄ roasting and stepwise precipitation [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 24-37.
[8]	Zhengyang Liu, Xianlong Liu, Shuang Ma, Xiaolei Guo, Minhua Ai, Chengxiang Shi, Zhenfeng Huang, Xiangwen Zhang, Jijun Zou, Lun Pan. One-step synthesis of caged hydrocarbon fuel via photoinduced intramolecular cycloaddition of 5-vinyl-2-norbornene [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 61-69.
[9]	Yaqi Qu, Hualiang An, Xinqiang Zhao, Yanji Wang. Heterogeneously catalyzed self-condensation of n-butanal [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 89-99.
[10]	Wei Zhang, Yuming Zhang, Haixin Wu, Xinyu Yang, Pei Qiao, Jiazhou Li, Zhewen Chen, Yan Wang. Investigation on the pyrolysis behaviors and kinetics of walnut shell lignocellulosic biomass with additives [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 303-314.
[11]	Yahui Gao, Gendi Song, Yanjie Xu, Yuyu Sun, Yong Feng, Huijun Tan, Wenjie Tian. In-situ synthesis of mixed-valence manganese oxide@S, P self-codoped carbon@reduced graphene oxide composites by enhanced surface interaction for high-performance all-solid-state supercapacitors [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 315-327.
[12]	Aleksey K. Sagidullin, Sergey S. Skiba, Tatyana P. Adamova, Andrey Y. Manakov. Investigation of the formation processes of CO₂ hydrate films on the interface of liquid carbon dioxide with humic acids solutions [J]. Chinese Journal of Chemical Engineering, 2025, 79(3): 53-61.
[13]	Yiyang Qiu, Chong Liu, Xueting Meng, Yuesen Liu, Jiangtao Fan, Guojun Lan, Ying Li. Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination [J]. Chinese Journal of Chemical Engineering, 2025, 79(3): 145-154.
[14]	Qin Cheng, Pengfei Ma, Ruize Yin, Chaodi Wang, Weiwei Xiong, Zhongyao Duan, Fu Yang, Junhao Zhang. Zn²⁺ significantly enhances the performance of petal-like Co-naphthalenetetracarboxylic acid MOF as an anode material for lithium-ion batteries [J]. Chinese Journal of Chemical Engineering, 2025, 79(3): 164-171.
[15]	Feng Gao, Sixiao Zhu, Liping Chang, Weiren Bao, Jinghong Ma, Junjie Liao. Kinetics of hydrogen sulfide removal from coke oven gas over faujasite zeolite: Experimental and modeling studies [J]. Chinese Journal of Chemical Engineering, 2025, 78(2): 232-244.