English

Tailoring Electrode-Electrolyte Interfaces via a Simple Slurry Additive for Stable High-Voltage Lithium-Ion Batteries

• Aoyu Huang ^1, ,
• Jun Xu ^1, ,
• Yu Huang ^1, ,
• Gui Chu ^1, ,
• Mao Wang ^1, ,
• Lili Wang ^{2, ,} ,
• Yongqi Sun ^3, ,
• Zhen Jiang ^4, ,
• Xiaobo Zhu ^{1, ,}

• 1.

  College of Materials Science and Engineering, Changsha University of Science and Technology, Changsha 410114, China

• 2.

  Key Laboratory of Materials and Technologies for Advanced Batteries, LIB Technology Center of Anhui Province, Hefei University, Hefei 230601, China

• 3.

  School of Metallurgy and Environment and National Center for International Cooperation of Clean Metallurgy, Central South University, Changsha 410083, China

• 4.

  School of Mechanical, Materials, Mechatronic and Biomedical Engineering, University of Wollongong, Wollongong, NSW, 2522 Australia

Corresponding author: Email: wangll@hfuu.edu.cn (L.W.); Email: xbzhu@csust.edu.cn (X.Z.)

• Received Date: 07 August 2024
  Accepted Date: 30 August 2024
  Revised Date: 30 August 2024
  Available Online: 15 April 2025
• Fund Project:

  the National Natural Science Foundation of China 

  Natural Science Foundation of Hunan Province 

  the Key Projects for the Excellent Talent Foundation of Education Department of Anhui Province 

Abstract: 5 Ⅴ-class LiNi_0.5Mn_1.5O₄ (LNMO) cathode material is emerging as a promising cobalt-free alternative to meet the growing demand for affordable, high-performance lithium-ion batteries (LIBs). However, LNMO faces significant electrochemical challenges, particularly interfacial instability with commercial electrolytes due to its high operating potentials. This instability leads to the dissolution of transition metals and consequently electrode crosstalk, which severely deteriorates electrochemical performance. Surface coating is extensively investigated to reduce interfacial side reactions for enhanced cycling stability. Traditional methods typically require multiple steps, including dispersion, mixing, drying, and calcination, which can be time-consuming and complex. Additionally, the resulting ceramic coatings are often rigid and unevenly distributed due to lattice mismatches, potentially leading to poor interfacial contact and increased resistance. In this study, tetraethyl orthosilicate (TEOS) is proposed as a streamlined slurry additive to in situ form an ethoxy-functional polysiloxane (EPS) film on the surface of LNMO particles during electrode preparation. Post-mortem X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) analyses reveal the crucial role of the EPS film in addressing interfacial instability issues. First, the EPS film serves as an artificial cathode-electrolyte interface (CEI) with a robust Si―O―Si bonding network, which is less vulnerable under high potentials. Second, the remaining ethoxy-functional groups in EPS scavenge HF by forming stable Si―F bonds, thereby suppressing the detrimental transition metal dissolution and crosstalk. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) further confirm the stability of the EPS film and the enhanced structural stability of the modified LNMO. Galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) results demonstrate that EPS reduces the overall impedance and improves ion diffusion kinetics by forming stable electrode-electrolyte interfaces. As a result, compared to the baseline, the optimized LNMO cathode exhibits significantly improved cycling stability in both half cells (84.6% vs. 51.4% capacity retention after 1000 cycles) and full cells when paired with commercial graphite anodes (83.3% vs. 53.4% retention after 500 cycles). This strategy, further validated under elevated temperatures of 50 ℃ and in pouch-type cells, is expected to pave the way for the development of next-generation high-performance LIBs.

Key words:
• LiNi_0.5Mn_1.5O₄
•  /  High voltage
•  /  Cathode-electrolyte interface
•  /  Slurry additive
•  /  Transition metal dissolution
•  /  Lithium-ion battery

• 1. [1]

     Yoshino, A. Angew. Chem. -Int. Edit. 2012, 51, 5798. doi: 10.1002/anie.201105006

  2. [2]

     Grey, C. P.; Hall, D. S. Nat. Commun. 2020, 11, 6279. doi: 10.1038/s41467-020-19991-4

  3. [3]

     Zhu, X. B.; Lin, T. G.; Manning, E.; Zhang, Y. C.; Yu, M. M.; Zuo, B.; Wang, L. Z. J. Nanopart. Res. 2018, 20, 160. doi: 10.1007/s11051-018-4235-1

  4. [4]

     Ryu, H. -H.; Sun, H. H.; Myung, S. -T.; Yoon, C. S.; Sun, Y. -K. Energy Environ. Sci. 2021, 14, 844. doi: 10.1039/d0ee03581e

  5. [5]

     She, Q.; Xu, J.; Huang, A. Y.; Zhou, R.; Shao, Q.; Wang, J. Q.; Wang, Y.; Sun, Y. Q.; Zhu, X. B. Chem. Eng. Sci. 2024, 284, 119526. doi: 10.1016/j.ces.2023.119526

  6. [6]

     Liang, G. M.; Peterson, V. K.; See, K. W.; Guo, Z. P.; Pang, W. K. J. Mater. Chem. A. 2020, 8, 15373. doi: 10.1039/d0ta02812f

  7. [7]

     Yu, X. W.; Yu, W. A.; Manthiram, A. Small Methods 2021, 5, 2001196. doi: 10.1002/smtd.202001196

  8. [8]

     Yao, W. L.; Chouchane, M.; Li, W. K.; Bai, S.; Liu, Z.; Li, L. T.; Chen, A. X.; Sayahpour, B.; Shimizu, R.; Raghavendran, G.; et al. Energy Environ. Sci. 2023, 16, 1620. doi: 10.1039/d2ee03840d

  9. [9]

     Tong, Z. Y.; Zhu, X. B. Next Energy 2024, 5, 100158. doi: 10.1016/j.nxener.2024.100158

  10. [10]

      Amin, R.; Muralidharan, N.; Petla, R. K.; Ben Yahia, H.; Al-Hail, S. A. J.; Essehli, R.; Daniel, C.; Khaleel, M. A.; Belharouak, I. J. Power Sources 2020, 467, 228318. doi: 10.1016/j.jpowsour.2020.228318

  11. [11]

      Zhong, Q. M.; Bonakdarpour, A.; Zhang, M. J.; Gao, Y.; Dahn, J. J. Electrochem. Soc. 1997, 144, 205. doi: 10.1149/1.1837386

  12. [12]

      Zhu, X. B.; Huang, A. Y.; Martens, I.; Vostrov, N.; Sun, Y. Q.; Richard, M. I.; Schülli, T. U.; Wang, L. Z. Adv. Mater. 2024, 36, 2403482. doi: 10.1002/adma.202403482

  13. [13]

      Li, J. C.; Ma, C.; Chi, M.; Liang, C. D.; Dudney, N. J. Adv. Energy Mater. 2015, 5, 1401408. doi: 10.1002/aenm.201401408

  14. [14]

      Ma, J.; Hu, P.; Cui, G. L.; Chen, L. Q. Chem. Mat. 2016, 28, 3578. doi: 10.1021/acs.chemmater.6b00948

  15. [15]

      Jia, H.; Xu, W. Trends Chem. 2022, 4, 627. doi: 10.1016/j.trechm.2022.04.010

  16. [16]

      韩卓, 张丹丰, 王海先, 郑国瑞, 柳明, 贺艳兵. 物理化学学报, 2024, 40, 2307034. doi: 10.3866/PKU.WHXB202307034Han, Z.; Zhang, D. F.; Wang, H. X.; Zheng, G. R.; Liu, M.; He, Y. B. Acta Phys. -Chim. Sin. 2024, 40, 2307034. doi: 10.3866/PKU.WHXB202307034

  17. [17]

      Rinkel, B. L. D.; Hall, D. S.; Temprano, I.; Grey, C. P. J. Am. Chem. Soc. 2020, 142, 15058. doi: 10.1021/jacs.0c06363

  18. [18]

      Zhu, X. B.; Schulli, T.; Wang, L. Z. Chem. Res. Chin. Univ. 2020, 36, 24. doi: 10.1007/s40242-020-9103-8

  19. [19]

      Jayawardana, C.; Rodrigo, N.; Parimalam, B.; Lucht, B. L. ACS Energy Lett. 2021, 6, 3788. doi: 10.1021/acsenergylett.1c01657

  20. [20]

      Zhan, C.; Wu, T. P.; Lu, J.; Amine, K. Energy Environ. Sci. 2018, 11, 243. doi: 10.1039/c7ee03122j

  21. [21]

      Pieczonka, N. P. W.; Liu, Z. Y.; Lu, P.; Olson, K. L.; Moote, J.; Powell, B. R.; Kim, J. -H. J. Phys. Chem. C 2013, 117, 15947. doi: 10.1021/jp405158m

  22. [22]

      Zhu, X. B.; She, Q.; Wang, M.; Wang, Z. L.; Hu, Y. X.; Yuan, D.; Sun, Y. Q.; Schülli, T. U.; Wang, L. Z. Adv. Funct. Mater. 2024, 34, 2311025. doi: 10.1002/adfm.202311025

  23. [23]

      Zhu, X. B.; Sun, D.; Luo, B.; Hu, Y. X.; Wang, L. Z. Electrochim. Acta 2018, 284, 30. doi: 10.1016/j.electacta.2018.07.153

  24. [24]

      Xu, M.; Yang, M.; Chen, M. F.; Gu, L. H.; Luo, L. S.; Chen, S. Y.; Chen, J. Z.; Liu, B.; Han, X. J. Energy Chem. 2023, 76, 266. doi: 10.1016/j.jechem.2022.09.021

  25. [25]

      Maiti, S.; Sclar, H.; Grinblat, J.; Talianker, M.; Elias, Y.; Wu, X. H.; Kondrakov, A.; Aurbach, D. Small Methods 2022, 6, 2200674. doi: 10.1002/smtd.202200674

  26. [26]

      Kuenzel, M.; Kim, G. -T.; Zarrabeitia, M.; Lin, S. D.; Schuer, A. R.; Geiger, D.; Kaiser, U.; Bresser, D.; Passerini, S. Mater. Today 2020, 39, 127. doi: 10.1016/j.mattod.2020.04.003

  27. [27]

      Zhu, X. B.; Schülli, T. U.; Yang, X. W.; Lin, T. G.; Hu, Y. X.; Cheng, N. Y.; Fujii, H.; Ozawa, K.; Cowie, B.; Gu, Q. F. Nat. Commun. 2022, 13, 1565. doi: 10.1038/s41467-022-28963-9

  28. [28]

      Maiti, S.; Sclar, H.; Wu, X. H.; Grinblat, J.; Talianker, M.; Kondrakov, A.; Markovsky, B.; Aurbach, D. Energy Storage Mater. 2023, 56, 25. doi: 10.1016/j.ensm.2023.01.004

  29. [29]

      张思东, 刘园, 祁慕尧, 曹安民. 物理化学学报, 2021, 37, 2011007. doi: 10.3866/PKU.WHXB202011007Zhang, S. D.; Liu, Y.; Qi, M. Y.; Cao, A. M. Acta Phys. -Chim. Sin. 2021, 37, 2011007. doi: 10.3866/PKU.WHXB202011007

  30. [30]

      Pieczonka, N. P. W.; Borgel, V.; Ziv, B.; Leifer, N.; Dargel, V.; Aurbach, D.; Kim, J. H.; Liu, Z. Y.; Huang, X. S.; Krachkovskiy, S. A. Adv. Energy Mater. 2015, 5, 1501008. doi: 10.1002/aenm.201501008

  31. [31]

      Ma, Y.; Wang, C. D.; Ma, J.; Xu, G. J.; Chen, Z.; Du, X. F.; Zhang, S.; Zhou, X. H.; Cui, G. L.; Chen, L. Q. Sci. China-Chem. 2021, 64, 92. doi: 10.1007/s11426-020-9879-8

  32. [32]

      Xu, G. J.; Pang, C. G.; Chen, B. B.; Ma, J.; Wang, X.; Chai, J. C.; Wang, Q. F.; An, W. Z.; Zhou, X. H.; Cui, G. L.; et al. Adv. Energy Mater. 2018, 8, 1701398. doi: 10.1002/aenm.201701398

  33. [33]

      Tan, C. L.; Yang, J.; Pan, Q. C.; Li, Y.; Li, Y.; Cui, L. S.; Fan, X. P.; Zheng, F. H.; Wang, H. Q.; Li, Q. Y. Chem. Eng. J. 2021, 410, 128422. doi: 10.1016/j.cej.2021.128422

  34. [34]

      Zhang, J.; Li, J. P.; Cao, L. H.; Cheng, W. H.; Guo, Z. Y.; Zuo, X. X.; Wang, C.; Cheng, Y. -J.; Xia, Y. G.; Huang, Y. D. Nano Res. 2024, 17, 333. doi: 10.1007/s12274-023-5960-z

  35. [35]

      Colombo, F.; Müller, M.; Weber, A.; Keim, N.; Jeschull, F.; Bauer, W.; Ehrenberg, H. Energy Adv. 2023, 2, 2093. doi: 10.1039/D3YA00246B

  36. [36]

      Zhang, J.; Cao, L. H.; Li, J. P.; Yang, M.; Yu, J. X.; Cheng, Y. -J.; Huang, Y. D.; Xia, Y. G. Energy Storage Mater. 2024, 64, 103060. doi: 10.1016/j.ensm.2023.103060

  37. [37]

      Yang, Z.; Li, Z. M.; Huang, Y. X.; Zhang, M. L.; Liu, C. F.; Zhang, D. Y.; Cao, G. Z. J. Power Sources 2020, 471, 228480. doi: 10.1016/j.jpowsour.2020.228480

  38. [38]

      Wang, H.; Ge, W. J.; Li, W.; Wang, F.; Liu, W. J.; Qu, M. -Z.; Peng, G. C. ACS Appl. Mater. Interfaces 2016, 8, 18439. doi: 10.1021/acsami.6b04644

  39. [39]

      Takeshita, S.; Ono, T. Angew. Chem. -Int. Edit. 2023, 62, e202306518. doi: 10.1002/anie.202306518

  40. [40]

      Liu, R.; Yan, H. X.; Zhang, Y. B.; Yang, K. M.; Du, S. Chem. Eng. J. 2022, 433, 133827. doi: 10.1016/j.cej.2021.133827

  41. [41]

      Zhu, X. B.; Li, X. N.; Zhu, Y. C.; Jin, S. S.; Wang, Y.; Qian, Y. T. Electrochim. Acta 2014, 121, 253. doi: 10.1016/j.electacta.2013.12.176

  42. [42]

      Martens, I.; Vostrov, N.; Mirolo, M.; Colalongo, M.; Kus, P.; Richard, M. -I.; Wang, L. Z.; Zhu, X. B.; Schulli, T. U.; Drnec, J. ACS Mater. Lett. 2022, 4, 2528. doi: 10.1021/acsmaterialslett.2c00787

  43. [43]

      Piao, N.; Wang, P. -F.; Chen, L.; Deng, T.; Fan, X. L.; Wang, L.; He, X. M. Nano Energy 2023, 105, 108040. doi: 10.1016/j.nanoen.2022.108040

  44. [44]

      Moorhead-Rosenberg, Z.; Huq, A.; Goodenough, J. B.; Manthiram, A. Chem. Mater. 2015, 27, 6934. doi: 10.1021/acs.chemmater.5b01356

  45. [45]

      Gaberšček, M. Curr. Opin. Electrochem. 2022, 32, 100917. doi: 10.1016/j.coelec.2021.100917

  46. [46]

      Yu, F. -D.; Que, L. -F.; Xu, C. -Y.; Wang, M. -J.; Sun, G.; Duh, J. -G.; Wang, Z. -B. Nano Energy 2019, 59, 527. doi: 10.1016/j.nanoen.2019.03.012

  47. [47]

      Zhu, X. B.; Wang, L. Z. EcoMat 2020, 2, e12043. doi: 10.1002/eom2.12043

  48. [48]

      Lu, D. S.; Xu, M. Q.; Zhou, L.; Garsuch, A.; Lucht, B. L. J. Electrochem. Soc. 2013, 160, A3138. doi: 10.1149/2.022305jes

  49. [49]

      Jiang, H. R.; Zeng, C. H.; Zhu, W.; Luo, J. W.; Liu, Z. D.; Zhang, J. C.; Liu, R.; Xu, Y. H.; Chen, Y. A.; Hu, W. B. Nano Res. 2024, 17, 2671. doi: 10.1007/s12274-023-6076-1

  50. [50]

      Cui, Z. H.; Zou, F.; Celio, H.; Manthiram, A. Adv. Funct. Mater. 2022, 32, 2203779. doi: 10.1002/adfm.202203779

  51. [51]

      Jiao, X. W.; Rao, L. L.; Yap, J. W.; Yu, C. -Y.; Kim, J. -H. J. Power Sources 2023, 561, 232748. doi: 10.1016/j.jpowsour.2023.232748

  52. [52]

      Tian, T.; Lu, L. L.; Yin, Y. C.; Tan, Y. H.; Zhang, T. W.; Li, F.; Yao, H. B. Small 2022, 18, 2106898. doi: 10.1002/smll.202106898

  53. [53]

      Rath, P. C.; Wang, Y. -W.; Patra, J.; Umesh, B.; Yeh, T. -J.; Okada, S.; Li, J.; Chang, J. -K. Chem. Eng. J. 2021, 415, 128904. doi: 10.1016/j.cej.2021.128904

  54. [54]

      Li, J. C.; Zhang, Q. L.; Xiao, X. C.; Cheng, Y. -T.; Liang, C. D.; Dudney, N. J. J. Am. Chem. Soc. 2015, 137, 13732. doi: 10.1021/jacs.5b06178

  55. [55]

      Yoon, T.; Park, S.; Mun, J.; Ryu, J. H.; Choi, W.; Kang, Y. -S.; Park, J. -H.; Oh, S. M. J. Power Sources 2012, 215, 312. doi: 10.1016/j.jpowsour.2012.04.103

  56. [56]

      Michalak, B.; Berkes, B. z. B.; Sommer, H.; Bergfeldt, T.; Brezesinski, T.; Janek, J. Anal. Chem. 2016, 88, 2877. doi: 10.1021/acs.analchem.5b04696

  57. [57]

      Yoon, T.; Soon, J.; Lee, T. J.; Ryu, J. H.; Oh, S. M. J. Power Sources 2021, 503, 230051. doi: 10.1016/j.jpowsour.2021.230051

  58. [58]

      Tatara, R.; Karayaylali, P.; Yu, Y.; Zhang, Y.; Giordano, L.; Maglia, F.; Jung, R.; Schmidt, J. P.; Lund, I.; Shao-Horn, Y. J. Electrochem. Soc. 2019, 166, A5090. doi: 10.1149/2.0121903jes

  59. [59]

      Dos Santos, F. C.; Harb, S. V.; Menu, M. -J.; Turq, V.; Pulcinelli, S. H.; Santilli, C. V.; Hammer, P. RSC Adv. 2015, 5, 106754. doi: 10.1039/C5RA20885H

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