English

Suppression of Voltage Decay through Ni³⁺ Barrier in Anionic-Redox Active Cathode for Na-Ion Batteries

• Zilin Hu ^{1, 2,} ,
• Yaoshen Niu ^1, ,
• Xiaohui Rong ^{1, 2, 3, ,} ,
• Yongsheng Hu ^{1, 2, 3, 4, ,}

• 1.

  Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

• 2.

  College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China

• 3.

  Yangtze River Delta Physics Research Center Co. Ltd., Liyang 213300, Jiangsu Province, China

• 4.

  Huairou Division, Institute of Physics, Chinese Academy of Sciences, Beijing 101400, China

Corresponding author: Email: rong@iphy.ac.cn (X.R.); Email: yshu@iphy.ac.cn (Y.H.)

• Received Date: 01 June 2023
  Accepted Date: 17 July 2023
  Revised Date: 29 June 2023
  Available Online: 15 June 2024
• Fund Project:

  the National Key R&D Program of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the Youth Innovation Promotion Association of the Chinese Academy of Sciences 

  the Beijing Municipal Natural Science Foundation 

  the Young Elite Scientists Sponsorship Program by CAST 

Abstract: The storage of intermittent wind and solar electricity requires grid-level energy storage devices, and due to the abundance and wide distribution of Na resources, Na-ion batteries (NIBs) are much more cost-effective and have shown greater potential for large-scale energy storage than Li-ion batteries (LIBs). However, the lack of suitable cathode hinders the practical use of NIBs, so exploring suitable cathode materials that can maintain a balance between high energy density and cost-effectiveness is essential for NIBs. Ni-Mn based layered oxides are important cathode materials for NIBs, offering relatively high potential through the multi-electron redox reaction of Ni⁴⁺/Ni³⁺/Ni²⁺ as well as the low-cost and non-toxic nature of Mn⁴⁺. P2-Na_0.67[Ni_0.33Mn_0.67]O₂ was the first reported Ni-Mn based Na-ion battery cathode with a high capacity of ~160 mAh∙g⁻¹ in the voltage range of 2.0–4.5 V, while irreversible P2-O2 phase transition above 4.1 V makes poor capacity retention and limits their applications. Moreover, a dilemma has emerged in that a costly element (Ni) is used for sodium-ion batteries, which is supposed to be low-cost. With the intensive research in recent years, introducing an appropriate amount of anionic redox can effectively improve energy density while simultaneously reducing the amount of high-cost transition metals, such as V, Co, and Ni. However, because of irreversible oxygen loss and Mn⁴⁺/Mn³⁺ redox activation, voltage decay is difficult to avoid for most of these anion-redox materials. In this research, we report a Li-substituted Na_x[Ni, Mn]O₂ cathode, the designed formula being Na_0.85[Li_0.2Ni_0.15Mn_0.65]O₂. This material shows a unique combination of both cationic redox (Ni⁴⁺/Ni³⁺/Ni²⁺) and anionic redox (O²⁻/O₂ⁿ⁻) during charge and discharge, showing a high capacity of ~150 mAh∙g⁻¹ (10 mA∙g⁻¹, 1.5–4.5 V) with only 0.15 Ni. With an optimized voltage range, the material shows a capacity of ~100 mAh∙g⁻¹ and stable cycling performance (80% of initial capacity after 100 cycles at 10 mA∙g⁻¹ within 2.5–4.25 V) and high-rate capability (the capacity of 500 mA∙g⁻¹ is 80% of 10 mA∙g⁻¹, 2.5–4.25 V). Moreover, we demonstrate an effective way to suppress the voltage decay and Mn reduction through Ni³⁺ as a redox barrier. Specifically, during the discharge process, the Mn⁴⁺/Mn³⁺ reduction process was replaced by the Ni³⁺/Ni²⁺ reduction process with higher redox potential in the layered oxides. In addition, the full Ni²⁺/Ni⁴⁺ redox can compensate for the partial oxygen redox loss in the subsequent cycles. We believe that introducing the anion redox through Li substitution and the use of Ni³⁺ as a redox barrier to suppress the voltage decay will provide a new way in the design of NIBs’ cathode materials, with potential benefits such as higher energy density, lower cost, and longer cycle life.

Key words:
• Na-ion battery
•  /  Anion-redox
•  /  Voltage decay
•  /  Single-phase solid solution reaction

• 1. [1]

     Li, Y.; Lu, Y.; Zhao, C.; Hu, Y.-S.; Titirici, M.-M.; Li, H.; Huang, X.; Chen, L. Energy Stor. Mater. 2017, 7, 130. doi: 10.1016/j.ensm.2017.01.002

  2. [2]

     Zhao, E.; Nie, K.; Yu, X.; Hu, Y. S.; Wang, F.; Xiao, J.; Li, H.; Huang, X. Adv. Funct. Mater. 2018, 28, 1707543. doi: 10.1002/adfm.201707543

  3. [3]

     Zhao, C.; Liu, L.; Qi, X.; Lu, Y.; Wu, F.; Zhao, J.; Yu, Y.; Hu, Y.-S.; Chen, L. Adv. Energy Mater. 2018, 8, 1703012. doi: 10.1002/aenm.201703012

  4. [4]

     Zhao, C.; Lu, Y.; Yue, J.; Pan, D.; Qi, Y.; Hu, Y.-S.; Chen, L. J. Energy Chem. 2018, 27, 1584. doi: 10.1016/j.jechem.2018.03.004

  5. [5]

     Lu, Z.; Dahn, J. R. J. Electrochem. Soc. 2001, 148, 1225. doi: 10.1149/1.1407247

  6. [6]

     Lee, D. H.; Xu, J.; Meng, Y. S. Phys. Chem. Chem. Phys. 2013, 15, 3304. doi: 10.1039/c2cp44467d

  7. [7]

     Kim, D.; Kang, S.-H.; Slater, M.; Rood, S.; Vaughey, J. T.; Karan, N.; Balasubramanian, M.; Johnson, C. S. Adv. Energy Mater. 2011, 1, 333. doi: 10.1002/aenm.201000061

  8. [8]

     Clément, R. J.; Xu, J.; Middlemiss, D. S.; Alvarado, J.; Ma, C.; Meng, Y. S.; Grey, C. P. J. Mater. Chem. A 2017, 5, 4129. doi: 10.1039/c6ta09601h

  9. [9]

     Wang, P. F.; You, Y.; Yin, Y. X.; Wang, Y. S.; Wan, L. J.; Gu, L.; Guo, Y. G. Angew. Chem. Int. Ed. 2016, 55, 7445. doi: 10.1002/anie.201602202

  10. [10]

      Xu, J.; Lee, D. H.; Clément, R. J.; Yu, X.; Leskes, M.; Pell, A. J.; Pintacuda, G.; Yang, X.-Q.; Grey, C. P.; Meng, Y. S. Chem. Mater. 2014, 26, 1260. doi: 10.1021/cm403855t

  11. [11]

      Yoshida, H.; Yabuuchi, N.; Kubota, K.; Ikeuchi, I.; Garsuch, A.; Schulz-Dobrick, M.; Komaba, S. Chem. Commun. 2014, 50, 3677. doi: 10.1039/c3cc49856e

  12. [12]

      Wu, X.; Guo, J.; Wang, D.; Zhong, G.; McDonald, M. J.; Yang, Y. J. Power Sources 2015, 281, 18. doi: 10.1016/j.jpowsour.2014.12.083

  13. [13]

      Kubota, K.; Yoda, Y.; Komaba, S. J. Electrochem. Soc. 2017, 164, A2368. doi: 10.1149/2.0311712jes

  14. [14]

      Kubota, K.; Kumakura, S.; Yoda, Y.; Kuroki, K.; Komaba, S. Adv. Energy Mater. 2018, 8, 1703415. doi: 10.1002/aenm.201703415

  15. [15]

      Komaba, S.; Yabuuchi, N.; Nakayama, T.; Ogata, A.; Ishikawa, T.; Nakai, I. Inorg. Chem. 2012, 51, 6211. doi: 10.1021/ic300357d

  16. [16]

      Qi, X.; Wang, Y.; Jiang, L.; Mu, L.; Zhao, C.; Liu, L.; Hu, Y.-S.; Chen, L.; Huang, X. Part. Part. Syst. Charact. 2016, 33, 538. doi: 10.1002/ppsc.201500129

  17. [17]

      Wang, P. F.; Yao, H. R.; Liu, X. Y.; Zhang, J. N.; Gu, L.; Yu, X. Q.; Yin, Y. X.; Guo, Y. G. Adv. Mater. 2017, 29, 1700210. doi: 10.1002/adma.201700210

  18. [18]

      Zheng, L.; Obrovac, M. N. Electrochim. Acta 2017, 233, 284. doi: 10.1016/j.electacta.2017.03.033

  19. [19]

      Zheng, S.; Zhong, G.; McDonald, M. J.; Gong, Z.; Liu, R.; Wen, W.; Yang, C.; Yang, Y. J. Mater. Chem. A 2016, 4, 9054. doi: 10.1039/c6ta02230h

  20. [20]

      Yabuuchi, N.; Hara, R.; Kajiyama, M.; Kubota, K.; Ishigaki, T.; Hoshikawa, A.; Komaba, S. Adv. Energy Mater. 2014, 4, 1301453. doi: 10.1002/aenm.201301453

  21. [21]

      Du, K.; Zhu, J.; Hu, G.; Gao, H.; Li, Y.; Goodenough, J. B. Energy Environ. Sci. 2016, 9, 2575. doi: 10.1039/c6ee01367h

  22. [22]

      Rong, X.; Liu, J.; Hu, E.; Liu, Y.; Wang, Y.; Wu, J.; Yu, X.; Page, K.; Hu, Y.-S.; Yang, W.; et al. Joule 2018, 2, 125. doi: 10.1016/j.joule.2017.10.008

  23. [23]

      de la Llave, E.; Talaie, E.; Levi, E.; Nayak, P. K.; Dixit, M.; Rao, P. T.; Hartmann, P.; Chesneau, F.; Major, D. T.; Greenstein, M.; et al. Chem. Mater. 2016, 28, 9064. doi: 10.1021/acs.chemmater.6b04078

  24. [24]

      Rong, X.; Hu, E.; Lu, Y.; Meng, F.; Zhao, C.; Wang, X.; Zhang, Q.; Yu, X.; Gu, L.; Hu, Y.-S.; et al. Joule 2019, 3, 503. doi: 10.1016/j.joule.2018.10.022

  25. [25]

      Yabuuchi, N.; Hara, R.; Kubota, K.; Paulsen, J.; Kumakura, S.; Komaba, S. J. Mater. Chem. A 2014, 2, 16851. doi: 10.1039/c4ta04351k

  26. [26]

      Dai, K.; Wu, J.; Zhuo, Z.; Li, Q.; Sallis, S.; Mao, J.; Ai, G.; Sun, C.; Li, Z.; Gent, W. E.; et al. Joule 2019, 3, 518. doi: 10.1016/j.joule.2018.11.014

  27. [27]

      Mortemard de Boisse, B.; Nishimura, S.-i.; Watanabe, E.; Lander, L.; Tsuchimoto, A.; Kikkawa, J.; Kobayashi, E.; Asakura, D.; Okubo, M.; Yamada, A. Adv. Energy Mater. 2018, 8, 1800409. doi: 10.1002/aenm.201800409

  28. [28]

      Li, Y.; Wang, X.; Gao, Y.; Zhang, Q.; Tan, G.; Kong, Q.; Bak, S.; Lu, G.; Yang, X. Q.; Gu, L.; et al. Adv. Energy Mater. 2018, 9, 1803087. doi: 10.1002/aenm.201803087

  29. [29]

      Song, B.; Tang, M.; Hu, E.; Borkiewicz, O. J.; Wiaderek, K. M.; Zhang, Y.; Phillip, N. D.; Liu, X.; Shadike, Z.; Li, C.; et al. Chem. Mater. 2019, 31, 3756. doi: 10.1021/acs.chemmater.9b00772

  30. [30]

      Seo, D. H.; Lee, J.; Urban, A.; Malik, R.; Kang, S.; Ceder, G. Nat. Chem. 2016, 8, 692. doi: 10.1038/nchem.2524

  31. [31]

      Zhao, C.; Wang, Q.; Lu, Y.; Hu, Y.-S.; Li, B.; Chen, L. J. Phys. D 2017, 50, 183001. doi: 10.1088/1361-6463/aa646d

  32. [32]

      Rong, X.; Gao, F.; Lu, Y.; Yang, K.; Hu, Y. Chin. Chem. Lett. 2018, 29, 1791. doi: 10.1016/j.cclet.2018.11.023

  33. [33]

      Ku, K.; Hong, J.; Kim, H.; Park, H.; Seong, W. M.; Jung, S.-K.; Yoon, G.; Park, K.-Y.; Kim, H.; Kang, K. Adv. Energy Mater. 2018, 8, 1800606. doi: 10.1002/aenm.201800606

  34. [34]

      Hong, J.; Seo, D.-H.; Kim, S.-W.; Gwon, H.; Oh, S.-T.; Kang, K. J. Mater. Chem. 2010, 20, 10179. doi: 10.1039/c0jm01971b

  35. [35]

      Evstigneeva, M. A.; Nalbandyan, V. B.; Petrenko, A. A.; Medvedev, B. S.; Kataev, A. A. Chem. Mater. 2011, 23, 1174. doi: 10.1021/cm102629g

  36. [36]

      Li, Y.; Deng, Z.; Peng, J.; Chen, E.; Yu, Y.; Li, X.; Luo, J.; Huang, Y.; Zhu, J.; Fang, C.; et al. Chem. Eur. J. 2018, 24, 1057. doi: 10.1002/chem.201705466

  37. [37]

      Wang, Y.; Yu, X.; Xu, S.; Bai, J.; Xiao, R.; Hu, Y. S.; Li, H.; Yang, X. Q.; Chen, L.; Huang, X. Nat. Commun. 2013, 4, 2365. doi: 10.1038/ncomms3365

  38. [38]

      Xia, H.; Lu, L.; Ceder, G. J. Power Sources 2006, 159, 1422. doi: 10.1016/j.jpowsour.2005.12.01

•