English

Research Progress of Theoretical Studies on Polarons in Cathode Materials of Lithium-Ion Batteries

• Ye Yaokun ^†, ,
• Hu Zongxiang ^†, ,
• Liu Jiahua ,
• Lin Weicheng ,
• Chen Taowen ,
• Zheng Jiaxin ^, ,
• Pan Feng ^,

• School of Advanced Materials, Peking University, Shenzhen Graduate School, Shenzhen 518055, Guangdong Province, China

Corresponding author: Email: zhengjx@pkusz.edu.cn (J.Z.); Email: panfeng@pkusz.edu.cn (F.P.)

• Received Date: 02 November 2020
  Accepted Date: 10 December 2020
  Revised Date: 10 December 2020
  Available Online: 15 November 2021
• Fund Project:

  The project was supported by the National Key R&D Program of China (2016YFB0700600), the National Natural Science Foundation of China (21603007, 51672012), the Guangdong Key-lab Project (2017B0303010130), and the Shenzhen Science and Technology Innovation Committee (ZDSYS20170728102618)

• ^†These authors contributed equally to this work.

Abstract: In addition to their extensive commercial application in electronic devices such as cell phones and laptops, lithium-ion batteries (LIBs) are most suitable to fulfill the energy storage requirements of electric vehicles because of their recognized safety, portability, and high energy density. Cathodes are the most important part of LIBs, and various cathode materials have been widely investigated over the past decades. Polaron formation has been attracting increasing attention in the research of cathode materials, as it limits electron conduction. In particular, polarons are responsible for low electronic conductivity in cathode materials like olivine phosphate. Polaron is a typical crystal defect caused by the integrated motion of lattice distortion and its trapping electrons. Research on the mechanism of polaron formation will provide theoretical guidance for the design of high-electronic-conductivity cathode materials and improvement of the electrochemical performance of LIBs. Theoretical calculation is a direct and important method to study polaron formation in a specific crystal material, because the presence of polarons and their formation mechanisms can be effectively verified through this method. In this article, we first introduce the basic physical concept of polarons and their dynamical model according to the Marcus and Emin-Holstein-Austin-Mott theories. A comparison of the general properties of large and small polarons, summarized in this chapter, reveals that small polaron formation more likely occurs in cathode materials. Moreover, the theoretical characterization, electrical impact, control and challenges of polarons are reviewed. Although a universal necessary and suitable condition for the theoretical characterization of polarons has not yet been found, we still propose three criteria that are proven to be feasible and practical for the theoretical identification of polarons when applied in combination. Experimental characterizations are also introduced briefly for reference, because the comparison with the experiment is suggested to be necessary and mandatory. The electrical impact caused by polarons results in low electronic conductivity, which has been broadly reported in layered, olivine, and spinel cathode materials. Doping can weaken the influence of polarons and, thus, significantly enhance the electronic conductivity, thereby becoming the most prevalent strategy for tuning polarons. Although theoretical calculations have been widely and effectively conducted in the study of polarons, some challenges may still be faced because of the intrinsic shortcomings of the traditional density functional theory, which need to be addressed. Finally, further research on polarons from the perspective of basic theory and practical applications is prospected.

Key words:
• Polaron
•  /  Lithium-ion battery
•  /  Cathode materials
•  /  Electronic conductivity
•  /  First-principle calculations

• 1. [1]

     Goodenough, J. B.; Kim, Y. Chem. Mater. 2010, 22, 587. doi: 10.1021/cm901452z

  2. [2]

     Whittingham, M. S. Chem. Rev. 2014, 114, 11414. doi: 10.1021/cr5003003

  3. [3]

     黄可龙, 王兆翔, 刘素琴.锂离子电池原理与关键技术.北京:化学工业出版社, 2007: 60–288.Huang, K. L.; Wang, Z. X.; Liu, S. Q. Principle and Key Technology of Lithium Ion Battery; Chemical Industry Press: Beijing, 2007; pp. 60–288.

  4. [4]

     Goodenough, J. B. Acc. Chem. Res. 2011, 46, 1053. doi: 10.1021/ar2002705

  5. [5]

     Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Chem. Rev. 2017, 117, 10403. doi: 10.1021/acs.chemrev.7b00115

  6. [6]

     Reimers, J. N.; Dahn, J. R. J. Electrochem. Soc. 2019, 139, 2091. doi: 10.1149/1.2221184

  7. [7]

     Saravanan, K.; Reddy, M. V.; Balaya, P.; Gong, H.; Chowdari, B. V. R.; Vittal, J. J. J. Mater. Chem. 2009, 19, 605. doi: 10.1039/b817242k

  8. [8]

     Doherty, C. M.; Caruso, R. A.; Smarsly, B. M.; Adelhelm, P.; Drummond, C. J. Chem. Mater. 2009, 21, 5300. doi: 10.1021/cm9024167

  9. [9]

     胡江涛, 郑家新, 潘锋.物理化学学报, 2019, 35, 361. doi: 10.3866/PKU.WHXB201805102Hu, J. T.; Zheng, J. X.; Pan, F. Acta Phys. -Chim. Sin. 2019, 35, 361. doi: 10.3866/PKU.WHXB201805102

  10. [10]

      Xiao, W.; Xin, C.; Li, S.; Jie, J.; Gu, Y.; Zheng, J.; Pan, F. J. Mater. Chem. A 2018, 6, 9893. doi: 10.1039/c8ta01428k

  11. [11]

      David, W. I. F.; Thackeray, M. M.; Picciotto, L. A.; Goodenough, J. B. J. Solid State Chem. 1986, 67, 316. doi: 10.1016/0022-4596(87)90369-0

  12. [12]

      Mishra, S. K.; Ceder, G. Phys. Rev. B 1999, 59, 6120. doi: 10.1103/PhysRevB.59.6120

  13. [13]

      Maxisch, T.; Zhou, F.; Ceder, G. Phys. Rev. B 2006, 73, 104301. doi: 10.1103/PhysRevB.73.104301

  14. [14]

      Kong, F.; Longo, R. C.; Park, M.-S.; Yoon, J.; Yeon, D.-H.; Park, J.-H.; Wang, W.-H.; Kc, S.; Doo, S.-G.; Cho, K. J. Mater. Chem. A 2015, 3, 8489. doi: 10.1039/c5ta01445j

  15. [15]

      Zheng, J.; Teng, G.; Yang, J.; Xu, M.; Yao, Q.; Zhuo, Z.; Yang, W.; Liu, Q.; Pan, F. J. Phys. Chem. Lett. 2018, 9, 6262. doi: 10.1021/acs.jpclett.8b02725

  16. [16]

      Gu, Y.; Weng, M.; Teng, G.; Zeng, H.; Jie, J.; Xiao, W.; Zheng, J.; Pan, F. Phys. Chem. Chem. Phys. 2019, 21, 4578. doi: 10.1039/c8cp06083e

  17. [17]

      Hoang, K. J. Mater. Chem. 2014, 2, 18271. doi: 10.1039/c4ta04116j

  18. [18]

      Wang, Z.; Brock, C.; Matt, A.; Bevan, K. H. Phys. Rev. B 2017, 96, 125150. doi: 10.1103/PhysRevB.96.125150

  19. [19]

      Feng, T.; Li, L.; Shi, Q.; Dong, S.; Li, B.; Li, K.; Li, G. Phys. Chem. Chem. Phys. 2020, 22, 2054. doi: 10.1039/c9cp05768d

  20. [20]

      Meng, Y. S.; Arroyo-de Dompablo, M. E. Energy Environ. Sci. 2009, 2, 589. doi: 10.1039/b901825e

  21. [21]

      Meng, Y. S.; Elena Arroyo-de Dompablo, M. Acc. Chem. Res. 2013, 46, 1171. doi: 10.1021/ar2002396

  22. [22]

      Stoneham, A. M.; Gavartin, J.; Shluger, A. L.; Kimmel, A. V.; Ramo, D. M.; Rønnow, H. M.; Aeppli, G.; Renner, C. J. Phys. Condens. Matter 2007, 19, 255208. doi: 10.1088/0953-8984/19/25/255208

  23. [23]

      李正中.固体理论.第2版.北京:高等教育出版社, 2017: 343–367.Li, Z. Z. Solid Theory, 2nd ed.; Higher Education Press: Beijing, 2017; pp. 343–367.

  24. [24]

      Geneste, G.; Amadon, B.; Torrent, M.; Dezanneau, G. Phys. Rev. B 2017, 96, 134123. doi: 10.1103/PhysRevB.96.134123

  25. [25]

      Deskins, N. A.; Dupuis, M. Phys. Rev. B. 2007, 75, 195212. doi: 10.1103/PhysRevB.75.195212

  26. [26]

      Reticcioli, M.; Diebold, U.; Kresse, G.; Franchini, C. Small Polarons in Transition Metal Oxides. Springer: Cham, 2020; pp. 1035–1073.

  27. [27]

      Lany, S.; Zunger, A. Phys. Rev. B 2009, 80, 085202. doi: 10.1103/PhysRevB.80.085202

  28. [28]

      Zheng, J.; Ye, Y.; Pan, F. Natl. Sci. Rev. 2020, 7, 242. doi: 10.1093/nsr/nwz178

  29. [29]

      Li, S.; Liu, J.; Liu, B. Chem. Mater. 2017, 29, 2202. doi: 10.1021/acs.chemmater.6b05022

  30. [30]

      Wang, X.; Xiao, R.; Li, H.; Chen, L. J. Materiomics 2017, 3, 178. doi: 10.1016/j.jmat.2017.02.002

  31. [31]

      Zuo, C.; Hu, Z.; Qi, R.; Liu, J.; Li, Z.; Lu, J.; Dong, C.; Yang, K.; Huang, W.; Chen, C.; et al. Adv. Energy Mater. 2020, 10, 2000363. doi: 10.1002/aenm.202000363

  32. [32]

      Setvin, M.; Franchini, C.; Hao, X.; Schmid, M.; Janotti, A.; Kaltak, M.; Van de Walle, C. G.; Kresse, G.; Diebold, U. Phys. Rev. Lett. 2014, 113, 086402. doi: 10.1103/PhysRevLett.113.086402

  33. [33]

      Sezen, H.; Buchholz, M.; Nefedov, A.; Natzeck, C.; Heissler, S.; Di Valentin, C.; Woll, C. Sci. Rep. 2014, 4, 3808. doi: 10.1038/srep03808

  34. [34]

      Yang, S.; Brant, A. T.; Giles, N. C.; Halliburton, L. E. Phys. Rev. B 2013, 87, 125201. doi: 10.1103/PhysRevB.87.125201

  35. [35]

      Guo, C.; Meng, X.; Fu, H.; Wang, Q.; Wang, H.; Tian, Y.; Peng, J.; Ma, R.; Weng, Y.; Meng, S.; et al. Phys. Rev. Lett. 2020, 124, 206801. doi: 10.1103/PhysRevLett.124.206801

  36. [36]

      Marianetti, C. A.; Kotliar, G.; Ceder, G. Nat. Mater. 2004, 3, 627. doi: 10.1038/nmat1178

  37. [37]

      Daheron, L.; Dedryvere, R.; Martinez, H.; Menetrier, M.; Denage, C.; Delmas, C.; Gonbeau, D. Chem. Mater. 2008, 20, 583. doi: 10.1021/cm702546s

  38. [38]

      Park, M.; Zhang, X.; Chung, M.; Less, G. B.; Sastry, A. M. J. Power Sources 2010, 195, 7904. doi: 10.1016/j.jpowsour.2010.06.060

  39. [39]

      Padhi, A. K.; Nanjundaswamy, K. S.; Goodenough, J. B. J. Electrochem. Soc. 1997, 144, 1188. doi: 10.1149/1.1837571

  40. [40]

      Li, H.; Wang, Z.; Chen, L.; Huang, X. Adv. Mater. 2009, 21, 4593. doi: 10.1002/adma.200901710

  41. [41]

      Ouyang, C.; Shi, S.; Wang, Z.; Huang, X.; Chen, L. Phys. Rev. B 2004, 69, 104303. doi: 10.1103/PhysRevB.69.104303

  42. [42]

      Hoang, K.; Johannes, M. Chem. Mater. 2011, 23, 3003. doi: 10.1021/cm200725j

  43. [43]

      Chung, S. Y.; Bloking, J. T.; Chiang, Y. M. Nat. Mater. 2002, 1, 123. doi: 10.1038/nmat732

  44. [44]

      Thackeray, M. M.; David, W. I. F.; Bruce, P. G.; Goodenough, J. B. Mater. Res. Bull. 1983, 18, 461. doi: 10.1016/0025-5408(83)90138-1

  45. [45]

      Iguchi, E.; Nakamura, N.; Aoki, A. Philos. Mag. B 2009, 78, 65. doi: 10.1080/13642819808206727

  46. [46]

      Marzec, J.; Swierczek, K.; Przewoznik, J.; Molenda, J.; Simon, D. R.; Kelder, E. M.; Schoonman, J. Solid State Ion. 2002, 146, 225. doi: 10.1016/s0167-2738(01)01022-0

  47. [47]

      Massarotti, V.; Capsoni, D.; Bini, M.; Chiodelli, G.; Azzoni, C. B.; Mozzati, M. C.; Paleari, A. J. Solid State Chem. 1999, 147, 509. doi: 10.1006/jssc.1999.8406

  48. [48]

      Ouyang, C.; Du, Y.; Shi, S.; Lei, M. Phys. Lett. A 2009, 373, 2796. doi: 10.1016/j.physleta.2009.05.071

  49. [49]

      Mandal, S.; Rojas, R. M.; Amarilla, J. M.; Calle, P.; Kosova, N. V.; Anufrienko, V. F.; Rojo, J. M. Chem. Mater. 2002, 14, 1598. doi: 10.1021/cm011219v

  50. [50]

      Lazarraga, M. G.; Pascual, L.; Gadjov, H.; Kovacheva, D.; Petrov, K.; Amarilla, J. M.; Rojas, R. M.; Martin-Luengo, M. A.; Rojo, J. M. J. Mater. Chem. 2004, 14, 1640. doi: 10.1039/b314157h

  51. [51]

      Pham, H.; Wang, L. Phys. Chem. Chem. Phys. 2015, 17, 541. doi: 10.1039/C4CP04209C

  52. [52]

      Ong, S. P.; Mo, Y.; Ceder, G. Phys. Rev. B 2012, 85, 081105. doi: 10.1103/PhysRevB.85.081105

  53. [53]

      Liu, Z.; Balbuena, P. B.; Mukherjee, P. P. J. Phys. Chem. C 2017, 121, 17169. doi: 10.1021/acs.jpcc.7b06869

  54. [54]

      Liu, T.; Cui, M.; Dupuis M. J. Phys. Chem. C 2020, 124, 23038. doi: 10.1021/acs.jpcc.0c07408

  55. [55]

      Johannes, M. D.; Hoang K.; Allen, J. L.; Gaskell, K. Phys. Rev. B 2012, 85, 115106. doi: 10.1103/PhysRevB.85.115106

  56. [56]

      Zhou, F.; Marianetti, C. A.; Cococcioni, M.; Morgan, D.; Ceder, G. Phys. Rev. B 2004, 69, 201101. doi: 10.1103/PhysRevB.69.201101

  57. [57]

      Jain, A.; Hautier, G.; Ong, S. P.; Moore, C. J.; Fischer, C. C.; Persson, K. A.; Ceder, G. Phys. Rev. B 2011, 84, 045115. doi: 10.1103/PhysRevB.84.045115

  58. [58]

      Heyd, J.; Scuseria, G. E.; Ernzerhof, M. J. Chem. Phys. 2003, 118, 8207. doi: 10.1063/1.1564060

  59. [59]

      Weng, M.; Li, S.; Zheng, J.; Pan, F.; Wang, L. W. J. Phys. Chem. Lett. 2018, 9, 281. doi: 10.1021/acs.jpclett.7b03041

  60. [60]

      Sun, J.; Ruzsinszky, A.; Perdew, J. P. Phys. Rev. Lett. 2015, 115, 036402. doi: 10.1103/PhysRevLett.115.036402

•