Citation: Chong Tang, Zhong Qiu, Chen Li, Tengfei Zhang, Renhong Chen, Yifa Sheng, Xinhui Xia, Yongqi Zhang, Jun Liu. Rational synthesis of vertical graphene supported TiN@N-Li₄Ti₅O₁₂ as advanced high-rate electrodes for lithium-ion batteries[J]. Chinese Chemical Letters, ;2025, 36(11): 110589. doi: 10.1016/j.cclet.2024.110589 shu

Rational synthesis of vertical graphene supported TiN@N-Li₄Ti₅O₁₂ as advanced high-rate electrodes for lithium-ion batteries

Chong Tang ^a ,
Zhong Qiu ^b ,
Chen Li ^b ,
Tengfei Zhang ^b ,
Renhong Chen ^a ,
Yifa Sheng ^a ,
Xinhui Xia ^{c, *,} ,
Yongqi Zhang ^{b, *,} ,
Jun Liu ^{a, *,}

a.
Engineering and Research Center for Integrated New Energy Photovoltaics and Energy Storage Systems of Hunan Province, School of Electrical Engineering, University of South China, Hengyang 421001, China
b.
Institute of Fundamental and Frontier Science, University of Electronic Science and Technology of China, Chengdu 611371, China
c.
College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, China

helloxxh@zju.edu.cn

yqzhang@uestc.edu.cn

2021000103@usc.edu.cn

Received Date: 26 September 2024
Revised Date: 15 October 2024
Accepted Date: 29 October 2024
Available Online: 30 October 2024

Figures(5)

The Li₄Ti₅O₁₂ (LTO) is demonstrated to be one of the most promising anode materials for lithium-ion batteries (LIBs) to provide safe and high-power density cells but suffer from poor electrical conductivity. In this study, we present a TiN-decorated N-LTO on a vertical graphene (VG) array (TiN@N-LTO) as a potential anode material for lithium-ion batteries (LIBs). The use of atomic layer deposition (ALD) enables the formation of a thin layer of LTO on VG, with precise control over the thickness. The VG serves as highly conductive channels, facilitating the transfer of electrons. Moreover, the introduction of nitrogen heteroatoms into the LTO under an active N₂ plasma atmosphere has been shown to enhance its intrinsic conductivity, which is achieved by reducing the bandgap and expanding the diffusion pathways of ions. Concurrently, a small number of metallic TiN are formed and deposited on the surface of N-LTO, thereby further improving its conductivity. COMSOL simulations and DFT calculations demonstrate that the introduced TiN acts as a "conductive bridge", improving the charge distribution of LTO electrodes and enhancing the Li⁺ transport rate. The TiN@N-LTO exhibits a high rate performance (169.51, 131.61 and 101.08 mAh/g at 0.2, 2 and 20 C, respectively) and remarkable cycling stability (a capacity retention of 99.6% after 5000 cycles at 10 C).
- Lithium-ion batteries,
- Li₄Ti₅O₁₂,
- Nitrogen doping,
- TiN,
- Plasma
1. [1]
  S. Shen, Y. Chen, J. Zhou, et al., Adv. Ener. Mater. 13 (2023) 2204259. doi: 10.1002/aenm.202204259
2. [2]
  S. Shen, Y. Chen, X. Gu, et al., Adv. Mater. 36 (2024) 2400245. doi: 10.1002/adma.202400245
3. [3]
  Q. Zhao, X. Chen, W. Hou, et al., SusMat 2 (2022) 104–112. doi: 10.1002/sus2.43
4. [4]
  L. Huang, S. Shen, Y. Zhong, et al., Adv. Mater. 34 (2021) 2107415.
5. [5]
  M. Liu, J. Xu, L. Shao, et al., Chem. Commun. 60 (2024) 6860–6872. doi: 10.1039/d4cc01974a
6. [6]
  T. Tang, C. Li, S. Li, et al., Chin. Chem. Lett. 35 (2024) 109887. doi: 10.1016/j.cclet.2024.109887
7. [7]
  C. Zeng, R. Zheng, F. Fan, et al., Energy Stor. Mater. 72 (2024) 103788.
8. [8]
  F. Fan, R. Zheng, T. Zeng, et al., Chem. Eng. J. 477 (2023) 147181. doi: 10.1016/j.cej.2023.147181
9. [9]
  C. Wang, T. Ouyang, X. Wang, et al., J. Ener. Chem. 99 (2024) 384–392. doi: 10.1016/j.jechem.2024.07.066
10. [10]
  C. Zeng, F. Fan, R. Zheng, et al., ACS Appl. Mater. Interfaces 16 (2024) 11377–11388. doi: 10.1021/acsami.3c15370
11. [11]
  P. Liu, Z. Qiu, F. Cao, et al., J. Mater. Sci. Technol. 177 (2024) 68–78. doi: 10.1016/j.jmst.2023.09.001
12. [12]
  N. Piao, P.F. Wang, L. Chen, et al., Nano Ener. 105 (2023) 108040. doi: 10.1016/j.nanoen.2022.108040
13. [13]
  Z. Qiu, S. Shen, P. Liu, et al., Adv. Funct. Mater. 33 (2023) 2214987. doi: 10.1002/adfm.202214987
14. [14]
  P. Liu, S. Shen, Z. Qiu, et al., Adv. Mater. 36 (2024) 2312812. doi: 10.1002/adma.202312812
15. [15]
  S. Wang, Y. Yang, W. Quan, et al., Nano Ener. 32 (2017) 294–301. doi: 10.1016/j.nanoen.2016.12.052
16. [16]
  R. Li, Z. Bai, W. Hou, et al., Chin. Chem. Lett. 34 (2023) 108263. doi: 10.1016/j.cclet.2023.108263
17. [17]
  Y. Zhao, Z. Gu, W. Weng, et al., Chin. Chem. Lett. 34 (2023) 107232. doi: 10.1016/j.cclet.2022.02.037
18. [18]
  C. Li, C. Zheng, F. Cao, Y. Zhang, X. Xia, J. Electron. Mater. 51 (2022) 4107–4114. doi: 10.1007/s11664-022-09687-4
19. [19]
  B. Cao, M. Du, Z. Guo, et al., Carbon Fut. 1 (2024) 9200017. doi: 10.26599/cf.2024.9200017
20. [20]
  Y. Cheng, B. Liu, X. Li, et al., Carbon Ener. 6 (2024) e599. doi: 10.1002/cey2.599
21. [21]
  P. Zhang, B. Cao, R.A. Soomro, N. Sun, B. Xu, Chin. Chem. Lett. 32 (2021) 282–285. doi: 10.1016/j.cclet.2020.10.006
22. [22]
  Y. Ren, F. Meng, S. Zhang, et al., Carbon Ener. 4 (2022) 446–457. doi: 10.1002/cey2.177
23. [23]
  J. Wang, Q. Kang, J. Yuan, et al., Carbon Ener. 3 (2021) 153–166. doi: 10.1002/cey2.94
24. [24]
  Z. Yao, X. Xia, D. Xie, et al., Adv. Funct. Mater. 28 (2018) 1802756. doi: 10.1002/adfm.201802756
25. [25]
  E.F. Rodriguez, F. Xia, D. Chen, A.F. Hollenkamp, R.A. Caruso, J. Mater. Chem. A 4 (2016) 7772–7780. doi: 10.1039/C6TA01954D
26. [26]
  K.S. Park, A. Benayad, D.J. Kang, J. Am. Chem. Soc. 130 (2008) 14930–14931. doi: 10.1021/ja806104n
27. [27]
  Y. Zhang, B. Ouyang, J. Xu, et al., Angew. Chem. Int. Ed. 55 (2016) 8670–8674. doi: 10.1002/anie.201604372
28. [28]
  X. Chang, N. Sun, H. Zhou, R.A. Soomro, B. Xu, Chin. Chem. Lett. 34 (2023) 107312. doi: 10.1016/j.cclet.2022.03.035
29. [29]
  Y. Liu, X. Yan, B. Xu, et al., Chem. Eng. J. 361 (2019) 1371–1380. doi: 10.1016/j.cej.2018.10.185
30. [30]
  Y.T.M. Tamaki, N. Yamamoto, et al., Plasmas Ions 3 (2000) 33–39. doi: 10.1016/S1288-3255(00)00108-8
31. [31]
  J. Wang, L. Yan, B. Liu, et al., Chin. Chem. Lett. 34 (2023) 107526. doi: 10.1016/j.cclet.2022.05.040
32. [32]
  Z. Su, S. Li, L. Ma, et al., Adv. Mater. 35 (2022) 2208573.
33. [33]
  M. Shahien, M. Yamada, T. Yasui, M. Fukumoto, Surf. Coat. Technol. 216 (2013) 308–317. doi: 10.1016/j.surfcoat.2012.11.062
34. [34]
  M.G. Verde, L. Baggetto, N. Balke, et al., ACS Nano 10 (2016) 4312–4321. doi: 10.1021/acsnano.5b07875
35. [35]
  Y. Lin, J. Wu, X. Huang, G. Pan, X. Xia, J. Energy Chem. 51 (2020) 372–377. doi: 10.1016/j.jechem.2020.04.037
36. [36]
  H. Liu, H. Du, W. Zhao, et al., Energy Stor. Mater. 40 (2021) 490–498.
37. [37]
  Y. Zhang, F. Du, X. Yan, et al., ACS Appl. Mater Interfaces 6 (2014) 4458–4465. doi: 10.1021/am5002053
1. [1]
  Xueqi Du , Ge Gao , Guoxiang Pan , Zhong Qiu , Yongqi Zhang , Shenghui Shen , Tianqi Yang , Xinqi Liang , Ping Liu , Xinhui Xia . Utilizing BBr₃ plasma to create high-quality solid electrolyte interphases for enhanced lithium metal anodes. Chinese Chemical Letters, 2025, 36(11): 110753-. doi: 10.1016/j.cclet.2024.110753
2. [2]
  Gang Hu , Chun Wang , Qinqin Wang , Mingyuan Zhu , Lihua Kang . The controlled oxidation states of the H₄PMo₁₁VO₄₀ catalyst induced by plasma for the selective oxidation of methacrolein. Chinese Chemical Letters, 2025, 36(2): 110298-. doi: 10.1016/j.cclet.2024.110298
3. [3]
  Zhong-Hui Sun , Yu-Qi Zhang , Zhen-Yi Gu , Dong-Yang Qu , Hong-Yu Guan , Xing-Long Wu . CoPSe nanoparticles confined in nitrogen-doped dual carbon network towards high-performance lithium/potassium ion batteries. Chinese Chemical Letters, 2025, 36(1): 109590-. doi: 10.1016/j.cclet.2024.109590
4. [4]
  Xinlin Zhang , Cheng Tang , Haitao Li , Jie Sun , Aijun Du , Minghong Wu , Haijiao Zhang . Robust assembly of TiO₂ quantum dots onto Ti₃C₂T_x for excellent lithium storage capability. Chinese Chemical Letters, 2025, 36(6): 110088-. doi: 10.1016/j.cclet.2024.110088
5. [5]
  Wenbi Wu , Yinchu Dong , Haofan Liu , Xuebing Jiang , Li Li , Yi Zhang , Maling Gou . Modification of plasma protein for bioprinting via photopolymerization. Chinese Chemical Letters, 2024, 35(8): 109260-. doi: 10.1016/j.cclet.2023.109260
6. [6]
  Wenrui Jia , Chenghuan Qiao , Dongfang Zhao , Juanshan Du , Yaohua Wu , Yongqi Liang , Qinglian Wu , Xiaochi Feng , Huazhe Wang , Wanqian Guo . Insight into nitrogen-doped biochar prepared from Chinese medicine compound residue for peracetic acid activation in sulfamethoxazole degradation: Electron transfer mechanism. Chinese Chemical Letters, 2025, 36(11): 110886-. doi: 10.1016/j.cclet.2025.110886
7. [7]
  Yihong Li , Zhong Qiu , Lei Huang , Shenghui Shen , Ping Liu , Haomiao Zhang , Feng Cao , Xinping He , Jun Zhang , Yang Xia , Xinqi Liang , Chen Wang , Wangjun Wan , Yongqi Zhang , Minghua Chen , Wenkui Zhang , Hui Huang , Yongping Gan , Xinhui Xia . Plasma enhanced reduction method for synthesis of reduced graphene oxide fiber/Si anode with improved performance. Chinese Chemical Letters, 2024, 35(11): 109510-. doi: 10.1016/j.cclet.2024.109510
8. [8]
  Mei-Chen Liu , Qing-Song Liu , Yi-Zhou Quan , Jia-Ling Yu , Gang Wu , Xiu-Li Wang , Yu-Zhong Wang . Phosphorus-silicon-integrated electrolyte additive boosts cycling performance and safety of high-voltage lithium-ion batteries. Chinese Chemical Letters, 2024, 35(8): 109123-. doi: 10.1016/j.cclet.2023.109123
9. [9]
  Peng Wang , Guanyu Zhao , Yicai Pan , Yujing Li , Chenxi Fu , Shipeng Sun , Junqi Gai , Jinping Mu , Xue Bai , Xiaohui Li , Jinfeng Sun , Xiaodong Shi , Rui He . Dual-salt electrolyte strategy enables stable interface reaction and high-performance lithium-ion batteries at low temperature. Chinese Chemical Letters, 2025, 36(11): 111190-. doi: 10.1016/j.cclet.2025.111190
10. [10]
  Wendi Dou , Guangying Wan , Tiefeng Liu , Lin Han , Wu Zhang , Chuang Sun , Rensheng Song , Jianhui Zheng , Yujing Liu , Xinyong Tao . Conductive composite binder for recyclable LiFePO₄ cathode. Chinese Chemical Letters, 2024, 35(11): 109389-. doi: 10.1016/j.cclet.2023.109389
11. [11]
  Guihuang Fang , Wei Chen , Hongwei Yang , Haisheng Fang , Chuang Yu , Maoxiang Wu . Improved performance of LiMn_0.8Fe_0.2PO₄ by addition of fluoroethylene carbonate electrolyte additive. Chinese Chemical Letters, 2024, 35(6): 108799-. doi: 10.1016/j.cclet.2023.108799
12. [12]
  Guihuang Fang , Ying Liu , Yangyang Feng , Ying Pan , Hongwei Yang , Yongchuan Liu , Maoxiang Wu . Tuning the ion-dipole interactions between fluoro and carbonyl (EC) by electrolyte design for stable lithium metal batteries. Chinese Chemical Letters, 2025, 36(1): 110385-. doi: 10.1016/j.cclet.2024.110385
13. [13]
  Xingang Kong , Yabei Su , Cuijuan Xing , Weijie Cheng , Jianfeng Huang , Lifeng Zhang , Haibo Ouyang , Qi Feng . Facile synthesis of porous TiO₂/SnO₂ nanocomposite as lithium ion battery anode with enhanced cycling stability via nanoconfinement effect. Chinese Chemical Letters, 2024, 35(11): 109428-. doi: 10.1016/j.cclet.2023.109428
14. [14]
  Hui Gu , Mingyue Gao , Kuan Shen , Tianli Zhang , Junhao Zhang , Xiangjun Zheng , Xingmei Guo , Yuanjun Liu , Fu Cao , Hongxing Gu , Qinghong Kong , Shenglin Xiong . F127 assisted fabrication of Ge/rGO/CNTs nanocomposites with three-dimensional network structure for efficient lithium storage. Chinese Chemical Letters, 2024, 35(9): 109273-. doi: 10.1016/j.cclet.2023.109273
15. [15]
  Sheng Zhao , Junjie Lu , Bifu Sheng , Siying Zhang , Hao Li , Jizhang Chen , Xiang Han . High-performance room temperature solid-state lithium battery enabled by PP-PVDF multilayer composite electrolyte. Chinese Chemical Letters, 2025, 36(6): 110008-. doi: 10.1016/j.cclet.2024.110008
16. [16]
  Peng Zhou , Ziang Jiang , Yang Li , Peng Xiao , Feixiang Wu . Sulphur-template method for facile manufacturing porous silicon electrodes with enhanced electrochemical performance. Chinese Chemical Letters, 2024, 35(8): 109467-. doi: 10.1016/j.cclet.2023.109467
17. [17]
  Jianjun Fang , Kunchen Xie , Yongli Song , Kangyi Zhang , Fei Xu , Xiaoze Shi , Ming Ren , Minzhi Zhan , Hai Lin , Luyi Yang , Shunning Li , Feng Pan . Break the capacity limit of Li4Ti5O12 anodes through oxygen vacancy engineering. Chinese Journal of Structural Chemistry, 2025, 44(2): 100504-100504. doi: 10.1016/j.cjsc.2024.100504
18. [18]
  Wenjie Ma , Yakun Tang , Yue Zhang , Lang Liu , Bin Tang , Dianzeng Jia , Yuliang Cao . Cation-disordered Li₂FeTiO₄ nanoparticles with multiple cation and anion redox for symmetric lithium-ion batteries. Chinese Chemical Letters, 2025, 36(9): 110346-. doi: 10.1016/j.cclet.2024.110346
19. [19]
  Mianying Huang , Zhiguang Xu , Xiaoming Lin . Mechanistic analysis of Co2VO4/X (X = Ni, C) heterostructures as anode materials of lithium-ion batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100309-100309. doi: 10.1016/j.cjsc.2024.100309
20. [20]
  Ming Zhong , Xue Guo , Yang Liu , Kun Zhao , Hui Peng , Suijun Liu , Xiaobo Zhang . Molybdenum-glycerate@zeolitic imidazolate framework spheres derived hierarchical nitrogen-doped carbon-encapsulated bimetallic selenides heterostructures for improved lithium-ion storage. Chinese Chemical Letters, 2025, 36(5): 109873-. doi: 10.1016/j.cclet.2024.109873

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(20)
HTML views(1)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Rational synthesis of vertical graphene supported TiN@N-Li4Ti5O12 as advanced high-rate electrodes for lithium-ion batteries

Metrics

通讯作者: 陈斌, bchen63@163.com

Rational synthesis of vertical graphene supported TiN@N-Li₄Ti₅O₁₂ as advanced high-rate electrodes for lithium-ion batteries