Theoretical Design of Defects as a Driving Force for Ion Transport in Li₃OBr Solid Electrolyte

Abstract

Due to ever-increasing concerns about safety issues in using Li ionic batteries, solid electrolytes have extensively explored. The Li-rich anti-perovskite Li₃OBr has been considered as a promising solid electrolyte candidate, but it still suffers challenges to achieve a high ionic conductivity owing to the high intrinsic symmetry of the crystal lattice. Herein, we presented a design strategy that introduces various point defects and grain boundaries to break the high lattice symmetry of Li₃OBr crystal, and their effect and microscopic mechanism of promoting the migration of Li-ion were explored theoretically. It has been found that Li_i^· are the dominant defects responsible for the fast Li-ion diffusion in bulk Li₃OBr and its surface, but they are easily trapped by the grain boundaries, leading to the annihilating of the Frenkel defect pair V'_Li + Li_i^· and thus limits the V'_Li diffusion at the grain boundaries. The V_Br^· defect near the grain boundaries can effectively drive V'_Li across the grain boundary, thereby converting the carrier of Li⁺ migration from Li_i^· in the bulk and surface to V'_Li at the grain boundary, and thus improving the ionic conductivity in the whole Li₃OBr crystal. This work provides a comprehensive insight into the Li⁺ transport and conduction mechanism in the Li₃OBr electrolyte. It opens a new way of improving the conductivity for all-solid-state Li electrolyte material through the defect design.

Keywords

defects / density functional theory / ionic migration / solid electrolyte

References

[1] D. Campanella , D. Belanger , A. Paolella , J. Power Sources 2021, 482, 228949.

[2] F. Zhu , M. S. Islam , L. Zhou , Z. Gu , T. Liu , X. Wang , J. Luo , C. W. Nan , Y. Mo , C. Ma , Nat. Commun. 2020, 11, 1828.

[3] T. Famprikis , P. Canepa , J. A. Dawson , M. S. Islam , C. Masquelier , Nat. Mater. 2019, 18, 1278.

[4] Y. Guo , H. Li , T. Zhai , Adv. Mater. 2017, 29, 1700007.

[5] T. Krauskopf , F. H. Richter , W. G. Zeier , J. Janek , Chem. Rev. 2020, 120, 7745.

[6] Y. Inaguma , L. Q. Chen , I. Mitsuru , Solid State Commun. 1993, 86, 689.

[7] S. Stramare , V. Thangadurai , W. Weppner , Chem. Mater. 2003, 15, 3974.

[8] R. Kanno , M. Murayama , J. Electrochem. Soc. 2001, 148, A742.

[9] Y. Kato , S. Hori , T. Saito , K. Suzuki , M. Hirayama , A. Mitsui , M. Yonemura , H. Iba , R. Kanno , Nat. Energy 2016, 1, 16030.

[10] X. Yu , J. Bates , G. Jellison , F. Hart , J. Electrochem. Soc. 1997, 144, 524.

[11] R. Murugan , V. Thangadurai , W. Weppner , Angew. Chem. Int. Ed. 2007, 46, 7778.

[12] M. O’Keeffe , J. O. Bovin , Science 1979, 206, 599.

[13] Y. Zhao , L. L. Daemen , J. Am. Chem. Soc. 2012, 134, 15042.

[14] M. Dondelinger , J. Swanson , G. Nasymov , C. Jahnke , Q. Qiao , J. Wu , C. Widener , A. M. Numan-Al-Mobin , A. Smirnova , Electrochim. Acta 2019, 306, 498.

[15] M. H. Chen , A. Emly , A. Van der Ven , Phys. Rev. B 2015, 91, 214306.

[16] X. Lü , J. W. Howard , A. Chen , J. Zhu , S. Li , G. Wu , P. Dowden , H. Xu , Y. Zhao , Q. Jia , Adv. Sci. 2016, 3, 1500359.

[17] R. Mouta , E. M. Diniz , C. W. A. Paschoal , J. Mater. Chem. A 2016, 4, 1586.

[18] Y. Li , W. Zhou , S. Xin , S. Li , X. Zhu , X. Lü , Z. Cui , Q. Jia , J. Zhou , Y. Zhao , J. B. Goodenough , Angew. Chem. Int. Ed. 2016, 55, 9965.

[19] J. Zhu , S. Li , Y. Zhang , J. Howard , X. Lü , Y. Li , Y. Wang , R. Kumar , Y. Zhao , Appl. Phys. Lett. 2016, 109, 101904.

[20] S. Li , J. Zhu , Y. Wang , J. Howard , X. Lü , Y. Li , R. Kumar , L. Wang , L. L. Daemen , Y. Zhao , Solid State Ionics 2016, 284, 14.

[21] X. Lü , G. Wu , J. W. Howard , A. Chen , Y. Zhao , L. L. Daemen , Q. Jia , Chem. Commun. 2014, 50, 11520.

[22] Y. Zhang , Y. Zhao , C. Chen , Phys. Rev. B 2013, 87, 134303.

[23] F. Hussain , P. Li , Z. Li , J. Yang , Adv. Theory Simul. 2019, 2, 1800138.

[24] Z. H. Lu , C. Chen , Z. M. Baiyee , X. Chen , C. M. Niu , F. Ciucci , Phys. Chem. Chem. Phys. 2015, 17, 32547.

[25] M. Wu , B. Xu , X. Lei , K. Huang , C. Ouyang , J. Mater. Chem. A 2018, 6, 1150.

[26] M. Wu , B. Xu , W. Luo , B. Sun , J. Shi , C. Ouyang , Appl. Sur. Sci. 2020, 510, 145394.

[27] A. Emly , E. Kioupakis , A. Van der Ven , Chem. Mater. 2013, 25, 4663.

[28] N. Kamaya , K. Homma , Y. Yamakawa , M. Hirayama , R. Kanno , M. Yonemura , T. Kamiyama , Y. Kato , S. Hama , K. Kawamoto , A. Mitsui , Nat. Mater. 2011, 10, 682.

[29] D. Qian , B. Xu , H. M. Cho , T. Hatsukade , K. J. Carroll , Y. S. Meng , Chem. Mater. 2012, 24, 2744.

[30] M. Imaeda , T. Mizoguchi , Y. Sato , H. S. Lee , S. D. Findlay , N. Shibata , T. Yamamoto , Y. Ikuhara , Phys. Rev. B 2008, 78, 245320.

[31] J. Xu , J. B. Liu , B. X. Liu , J. F. Wang , B. Huang , Adv. Funct. Mater. 2019, 29, 1805870.

[32] J. A. Dawson , P. Canepa , T. Famprikis , C. Masquelier , M. Islam , J. Am. Chem. Soc. 2018, 140, 362.

[33] T. Oyama , N. Wada , H. Takagi , M. Yoshiya , Phys. Rev. B 2010, 82, 134107.

[34] M. Herbig , D. Raabe , Phys. Rev. Lett. 2014, 112, 126103.

[35] H. C. Rogers , Science 1968, 159, 1057.

[36] D. Zhao , Y. Li , Acta Mater. 2019, 168, 52.

[37] Z. Deng , B. Radhakrishnan , S. Ping Ong , Chem. Mater. 2015, 27, 3749.

[38] G. Kresse , J. Furthmüller , Phys. Rev. B 1996, 54, 11169.

[39] P. E. Blöchl , Phys. Rev. B 1994, 50, 17953.

[40] G. Kress , D. Joubert , Phys. Rev. B 1999, 59, 1758.

[41] J. P. Perdew , M. Ernzerhof , K. Burke , J. Chem. Phys. 1996, 105, 9982.

[42] J. P. Perdew , K. Burke , M. Ernzerhof , Phys. Rev. Lett. 1996, 77, 3865.

[43] H. J. Monkhorst , J. D. Pack , Phys. Rev. B 1976, 13, 5188.

[44] J. Heyd , G. E. Scuseria , M. Ernzerhof , J. Chem. Phys. 2003, 118, 8207.

[45] A. V. Krukau , O. A. Vydrov , A. F. Izmaylov , G. E. Scuseria , J. Chem. Phys. 2006, 125, 224106.

[46] G. Henkelman , B. P. Uberuaga , H. Jónsson , J. Chem. Phys. 2000, 113, 9901.

[47] G. Shen , D. Ikuta , S. Sinogeikin , Q. Li , Y. Zhang , C. F. Chen , Phys. Rev. Lett. 2012, 109, 205503.

[48] G. G. Xu , K. H. Zhong , J. M. Zhang , Z. G. Huang , J. Appl. Phys. 2014, 116, 063703.

[49] Z. Deng , Z. Zhu , I. Chu , S. Ping Ong , Chem. Mater. 2017, 29, 281.

RIGHTS & PERMISSIONS

2023 The Authors. Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.