Citation: Lingbang Qiu, Jiangmin Jiang, Libo Wang, Lang Bai, Fei Zhou, Gaoyu Zhou, Quanchao Zhuang, Yanhua Cui. 原位电化学阻抗谱监测长寿命热电池Nb₁₂WO₃₃正极材料的高温双放电机制[J]. Acta Physico-Chimica Sinica, ;2025, 41(5): 100040. doi: 10.1016/j.actphy.2024.100040 shu

原位电化学阻抗谱监测长寿命热电池Nb₁₂WO₃₃正极材料的高温双放电机制

1.
Jiangsu Province Engineering Laboratory of High Efficient Energy Storage Technology and Equipments, School of Materials and Physics, China University of Mining and Technology, Xuzhou 221116, Jiangsu Province, China;
2.
Institute of Electronic Engineering, China Academy of Engineering Physics, Mianyang 621900, Sichuan Province, China

Received Date: 5 November 2024
Revised Date: 6 December 2024
Accepted Date: 6 December 2024

Fund Project: The project was supported by the National Natural Science Foundation of China (U2030206, 22209204), and the Natural Science Foundation of Jiangsu Province (BK20221140).

热电池作为一种一次贮备电池，具有高比能、高功率密度等优势，然而开发高比容量与高热稳定性的新型正极材料以适应新时期的热电池需求仍然存在巨大的挑战。Wadsley-Roth晶体剪切结构的铌钨氧化物作为锂离子电池负极材料表现出优异的倍率和循环循环性，其中Nb₁₂WO₃₃因内部具有独特的3D隧道，可以为Li⁺提供快速的脱嵌通道，因而具有优异的储锂性能。鉴于其具有较好的热稳定性及电化学稳定性，本文首次提出将Nb₁₂WO₃₃作为热电池正极材料，并在室温下使用电化学阻抗谱(EIS)来探究材料内部电子电导率阻抗变化规律。研究发现Nb₁₂WO₃₃电极电化学阻抗谱测试的Nyquist图显示在工作平台电位范围内，高、中频区出现了三个圆弧的独特现象，这主要归属于电子在Nb₁₂WO₃₃电极内部的传导，而与电子电导相关的电阻呈现先增大后降低的规律。采用该材料构筑的热电池单体电池在500 °C、500 mA∙g^-1的电流密度(截止电压1.5 V)下放电，其具有436.8 mAh∙g^-1的高比容量，脉冲放电的平均极化内阻为0.52 Ω。因此，Nb₁₂WO₃₃作为高比容量、高热稳定性热电池的正极材料非常具有潜力，本研究为其他铌钨氧化物作为热电池正极材料的研究开辟了新道路。
- Thermal battery,
- Niobium tungsten oxide,
- Cathode material,
- Electrochemical impedance spectroscopy,
- Distribution of relaxation time
1. [1]
  Li, R.; Guo, W.; Qian, Y. J. Front. Chem. 2022, 10, 832972. doi: 10.3389/fchem.2022.832972
2. [2]
  Masset, P.; Guidotti, R. A. J. Power Sources 2007, 164 (1), 397. doi: 10.1016/j.jpowsour.2006.10.080
3. [3]
  Choi, Y.; Cho, S.; Lee, Y.-S. J. Ind. Eng. Chem. 2014, 20 (5), 3584. doi: 10.1016/j.jiec.2013.12.052
4. [4]
  Meng, X.; Liu, H.; Bi, S.; Fan, S.; Cao, L.; Yi, T.; Li, X. J. Energy Storage 2024, 78, 109905. doi: 10.1016/j.est.2023.109905
5. [5]
  Masset, P. J.; Guidotti, R. A. J. Power Sources 2008, 177 (2), 595. doi: 10.1016/j.jpowsour.2007.11.017
6. [6]
  Jin, C.; Fu, L.; Zhu, J.; Yang, W.; Li, D.; Zhou, L. J. Mater. Chem. A 2018, 6 (16), 7123. doi: 10.1039/c8ta00346g
7. [7]
  Ko, J.; Kang, S.; Cheong, H.-W.; Yoon, Y.-S. J. Korean Ceram. Soc. 2019, 56 (3), 233. doi: 10.4191/kcers.2019.56.3.05
8. [8]
  Giagloglou, K.; Payne, J. L.; Crouch, C.; Gover, R. K.; Connor, P. A.; Irvine, J. T. J. Electrochem. Soc. 2018, 165 (14), A3510. doi: 10.1149/2.1231814jes
9. [9]
  Jin, C.; Fu, L.; Ge, B.; Pu, X.; Li, W.; Zhou, L. J. Alloy. Compd. 2019, 800, 518. doi: 10.1016/j.jallcom.2019.06.128
10. [10]
  Liao, Z.; Fu, L.; Zhu, J.; Yang, W.; Li, D.; Zhou, L. J. Power Sources 2020, 463, 228237. doi: 10.1016/j.jpowsour.2020.228237
11. [11]
  Luo, Z.; Fu, L.; Zhu, J.; Yang, W.; Li, D.; Zhou, L. J. Power Sources 2020, 448, 227569. doi: 10.1016/j.jpowsour.2019.227569
12. [12]
  Guo, S. N.; Guo, H.; Wang, X.; Zhu, Y.; Hu, J.; Yang, M.; Zhao, L.; Wang, J. J. Electrochem. Soc. 2019, 166 (15), A3599. doi: 10.1149/2.0371915jes
13. [13]
  Xu, C.; Jin, C.; Wang, X.; Gong, X.; Yin, J.; Zhao, L.; Pu, X.; Li, W. Electrochim. Acta 2022, 401, 139496. doi: 10.1016/j.electacta.2021.139496
14. [14]
  Hillel, T.; Ein-Eli, Y. J. Power Sources 2013, 229, 112. doi: 10.1016/j.jpowsour.2012.11.128
15. [15]
  Yang, Y.; Zhao, J. Adv. Sci. 2021, 8, 2004855. doi: 10.1002/advs.202004855
16. [16]
  Roth, R. S.; Waring, J. L. J. Res. Natl. Bur. Stand. A Phys. Chem. 1966, 70A (4), 281. doi: 10.6028/jres.070A.025
17. [17]
  Cava, R. J.; Murphy, D. W.; Zahurak, S. M. J. Electrochem. Soc. 1983, 130 (12), 2345. doi: 10.1149/1.2119583
18. [18]
  Roth, R. S.; Wadsley, A. D. Acta Crystallogr. A 1965, 19 (1), 32. doi: 10.1107/S0365110X65002724
19. [19]
  Roth, R. S.; Wadsley, A. D. Acta Crystallogr. A 1965, 19 (1), 38. doi: 10.1107/S0365110X65002736
20. [20]
  Shen, C.; Jiang, S. N.; Ding, C. M.; Xue, W. S.; Xie, K. Y. T. Nonferr. Metal. Soc. 2022, 32 (11), 3679. doi: 10.1016/S1003-6326(22)66048-5
21. [21]
  Stephenson, N. C. Acta Crystallogr. B 1968, 24 (5), 637. doi: 10.1107/S0567740868002979
22. [22]
  Griffith, K. J.; Wiaderek, K. M.; Cibin, G.; Marbella, L. E.; Grey, C. P. Nature 2018, 559 (7715), 556. doi: 10.1038/s41586-018-0347-0
23. [23]
  Yan, L.; Lan, H.; Yu, H.; Qian, S.; Cheng, X.; Long, N.; Zhang, R.; Shui, M.; Shu, J. J. Mater. Chem. A 2017, 5 (19), 8972. doi: 10.1039/C7TA01784G
24. [24]
  Cheng, Q. L.; Zhang, W. H.; Tao, B. Acta Phys. -Chim. Sin. 2015, 31 (7), 1345.
25. [25]
  Wei, R. F.; Li, D. F; Yin, H.; Wang, X. L.; Li, C. Acta Phys. -Chim. Sin. 2023, 39 (2), 2207035.
26. [26]
  Aurbach, D.; Levi, M. D.; Gamulski, K.; Markovsky, B.; Salitra, G.; Levi, E.; Heider, U.; Heider, L.; Oesten, R. J. Power Sources 1999, 81, 472. doi: 10.1016/S0378-7753(99)00204-9
27. [27]
  Aurbach, D.; Levi, M. D.; Levi, E.; Teller, H.; Markovsky, B.; Salitra, G.; Heider, U.; Heider, L. J. Electrochem. Soc. 1998, 145 (9), 3024. doi: 10.1149/1.1838758
28. [28]
  Bao, W.; Zhuang, Q.; Xu, S.; Cui, Y.; Shi, Y.; Qiang, Y. Ionics 2013, 19 1005. doi: 10.1007/s11581-012-0823-8
29. [29]
  Zhuang, Q.-C.; Wei, T.; Du, L.-L.; Cui, Y.-L.; Fang, L.; Sun, S.-G. J. Phys. Chem. C 2010, 114 (18), 8614. doi: 10.1021/jp9109157
30. [30]
  Zhuang, Q.; Xu, J.; Fan, X.; Dong, Q.; Jiang, Y.; Huang, L.; Sun, S. Chinese Sci. Bull. 2007, 52 (9), 1187. doi: 10.1007/s11434-007-0169-1
31. [31]
  Holzapfel, M.; Martinent, A.; Alloin, F.; Le Gorrec, B.; Yazami, R.; Montella, C. J. Electroanal. Chem. 2003, 546, 41. doi: 10.1016/S0022-0728(03)00144-X
32. [32]
  Shi, W. Y.; Jia, C.; Zhang, Y. L.; Lü, Z. W.; Han, M. F. Acta Phys. -Chim. Sin. 2019, 35 (5), 509.
33. [33]
  Cui, T. H.; Li, H. Y.; Lü, Z. W.; Wang, Y. G.; Han, M. F.; Sun, Z. H.; Sun, K. H. Acta Phys. -Chim. Sin. 2022, 38 (8), 2011009.
34. [34]
  Yang, Y.; Zhu, H.; Xiao, J.; Geng, H.; Zhang, Y.; Zhao, J.; Li, G.; Wang, X.-L.; Li, C. C.; Liu, Q. Adv. Mater. 2020, 32 (12), 1905295. doi: 10.1002/adma.201905295
35. [35]
  Koçer, C. P.; Griffith, K. J.; Grey, C. P.; Morris, A. J. J. Am. Chem. Soc. 2019, 141 (38), 15121. doi: 10.1021/jacs.9b06316
36. [36]
  Han, J.-T.; Goodenough, J. B. Chem. Mater. 2011, 23 (15), 3404. doi: 10.1021/cm201515g
37. [37]
  Lu, X. X.; Dong, S. Y.; Chen, Z. J.; Wu, L. Y.; Zhang, X. G. Acta Phys. -Chim. Sin. 2020, 36 (5), 1906024.
38. [38]
  Takashima, T.; Tojo, T.; Inada, R.; Sakurai, Y. J. Power Sources 2015, 276, 113. doi: 10.1016/j.jpowsour.2014.11.109
39. [39]
  Lin, C.; Wang, G.; Lin, S.; Li, J.; Lu, L. Chem. Commun. 2015, 51 (43), 8970. doi: 10.1039/C5CC01494H
40. [40]
  Yu, H.; Cheng, X.; Zhu, H.; Zheng, R.; Liu, T.; Zhang, J.; Shui, M.; Xie, Y.; Shu, J. Nano Energy 2018, 54, 227. doi: 10.1016/j.nanoen.2018.10.025
41. [41]
  Yu, H.; Zhang, J.; Zheng, R.; Liu, T.; Peng, N.; Yuan, Y.; Liu, Y.; Shu, J.; Wang, Z.-B. Mater. Chem. Front. 2020, 4 (2), 631. doi: 10.1039/C9QM00694J
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

原位电化学阻抗谱监测长寿命热电池Nb12WO33正极材料的高温双放电机制

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通讯作者: 陈斌, bchen63@163.com

原位电化学阻抗谱监测长寿命热电池Nb₁₂WO₃₃正极材料的高温双放电机制