Lithium-site substituted argyrodite-type Li6PS5I solid electrolytes with enhanced ionic conduction for all-solid-state batteries

被引：4

作者：

Gao, Ling ^{[1
]}

Xie, YuLin ^{[1
]}

Tong, Yan ^{[1
]}

Xu, Miao ^{[2
]}

You, JiaLe ^{[1
]}

Wei, HuiPing ^{[1
]}

Yu, XiangXiang ^{[1
]}

Xu, SiQi ^{[1
]}

Zhang, Yi ^{[1
]}

Che, Yong ^{[3
,4
]}

Tang, Ya ^{[5
]}

Suzuki, Kota ^{[6
]}

Kanno, Ryoji ^{[6
]}

Zhao, GuoWei ^{[1
]}

机构：

[1] Huanggang Normal Univ, Coll Chem & Chem Engn, Huanggang 438000, Peoples R China

[2] Shanghai Inst Space Power Sources, State Key Lab Space Power Sources Technol, Shanghai 200245, Peoples R China

[3] Shanghai Enpower Technol Co Ltd, Shanghai 201802, Peoples R China

[4] Beijing Enpower Technol Co Ltd, Beijing 102628, Peoples R China

[5] Shanghai Univ, Sch Sci, Dept Chem, Shanghai 200444, Peoples R China

[6] Tokyo Inst Technol, Inst Innovat Res, Res Ctr All Solid State Battery, Yokohama 2268502, Japan

来源：

SCIENCE CHINA-TECHNOLOGICAL SCIENCES | 2023年 / 66卷 / 07期

关键词：

argyrodite; Li6PS5I; solid electrolytes; ionic conductor; ionic conductivity; ENCODING CRYSTAL-STRUCTURE; CUBIC LI-ARGYRODITES; SUPERIONIC ARGYRODITES; ELECTROCHEMICAL PROPERTIES; STRUCTURAL DISORDER; ENERGY; PREDICTION; STABILITY; HALIDES; BR;

D O I：

10.1007/s11431-022-2365-8

中图分类号：

T [工业技术];

学科分类号：

08 ;

摘要：

Argyrodites, Li6PS5X (X=Cl, Br, I), have piqued the interest of researchers by offering promising lithium ionic conductivity for their application in all-solid-state batteries (ASSBs). However, other than Li6PS5Cl (651Cl) and Li6PS5Br (651Br), Li6PS5I (651I) shows poor ionic conductivity (10(-7) S cm(-1) at 298 K). Herein, we present Al-doped 651I with I-/S2- site disordering to lower activation energy (E-a) and improve ionic conductivity. They formed argyrodite-type solid solutions with a composition of (Li6-3xAlx)PS5I in 0 <= x <= 0.10, and structural analysis revealed that Al3+ is located at Li sites. Also, the Al-doped samples contained anion I-/S2- site disorders in the crystal structures and smaller lattice parameters than the non-doped samples. Impedance spectroscopy measurements indicated that Al-doping reduced the ionic diffusion barrier, E-a, and increased the ionic conductivity to 10(-5) S cm(-1); the (Li5.7Al0.1)PS5I had the highest ionic conductivity in the studied system, at 2.6x10(-5) S cm(-1). In a lab-scale ASSB, with (Li5.7Al0.1)PS5I functioned as a solid electrolyte, demonstrating the characteristics of a pure ionic conductor with negligible electronic conductivity. The evaluated ionic conduction is due to decreased Li+ content and I-/S2- disorder formation. Li-site cation doping enables an in-depth understanding of the structure and provides an additional approach to designing better-performing SEs in the argyrodite system.

引用

页码：2059 / 2068

页数：10

共 76 条

[1] Influence of Aliovalent Cation Substitution and Mechanical Compression on Li-Ion Conductivity and Diffusivity in Argyrodite Solid Electrolytes [J].

Adeli, Parvin ;

Bazak, J. David ;

Huq, Ashfia ;

Goward, Gillian R. ;

Nazar, Linda F. .

CHEMISTRY OF MATERIALS, 2021, 33 (01) :146-157

[2] Boosting Solid-State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide Substitution [J].

Adeli, Parvin ;

Bazak, J. David ;

Park, Kern Ho ;

Kochetkov, Ivan ;

Huq, Ashfia ;

Goward, Gillian R. ;

Nazar, Linda F. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (26) :8681-8686

[3] Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries [J].

Arnold, William ;

Shreyas, Varun ;

Li, Yang ;

Koralalage, Milinda Kalutara ;

Jasinski, Jacek B. ;

Thapa, Arjun ;

Sumanasekera, Gamini ;

Ngo, Anh T. ;

Narayanan, Badri ;

Wang, Hui .

ACS APPLIED MATERIALS & INTERFACES, 2022, 14 (09) :11483-11492

[4] Halide doping effect on solvent-synthesized lithium argyrodites Li6PS5X (X = Cl, Br, I) superionic conductors [J].

Arnold, William ;

Buchberger, Dominika A. ;

Li, Yang ;

Sunkara, Mahendra ;

Druffel, Thad ;

Wang, Hui .

JOURNAL OF POWER SOURCES, 2020, 464

[5] Competing Structural Influences in the Li Superionic Conducting Argyrodites Li6PS5-xSexBr (0 ≤ x ≤ 1) upon Se Substitution [J].

Bernges, Tim ;

Culver, Sean P. ;

Minafra, Nicolo ;

Koerver, Raimund ;

Zeier, Wolfgang G. .

INORGANIC CHEMISTRY, 2018, 57 (21) :13920-13928

[6] Mechanochemical synthesis of Li-argyrodite Li6PS5X (X = Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application [J].

Boulineau, Sylvain ;

Courty, Matthieu ;

Tarascon, Jean-Marie ;

Viallet, Virginie .

SOLID STATE IONICS, 2012, 221 :1-5

[7] Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges [J].

Canepa, Pieremanuele ;

Gautam, Gopalakrishnan Sai ;

Hannah, Daniel C. ;

Malik, Rahul ;

Liu, Miao ;

Gallagher, Kevin G. ;

Persson, Kristin A. ;

Ceder, Gerbrand .

CHEMICAL REVIEWS, 2017, 117 (05) :4287-4341

[8] High capacity all-solid-state Cu-Li2S/Li6PS5Br/In batteries [J].

Chen, Maohua ;

Rao, Rayavarapu Prasada ;

Adams, Stefan .

SOLID STATE IONICS, 2014, 262 :183-187

[9] Sn-O dual-doped Li-argyrodite electrolytes with enhanced electrochemical performance [J].

Chen, Ting ;

Zeng, Dewu ;

Zhang, Long ;

Yang, Meng ;

Song, Dawei ;

Yan, Xinlin ;

Yu, Chuang .

JOURNAL OF ENERGY CHEMISTRY, 2021, 59 :530-537

[10] Diffusion Mechanism of Li Argyrodite Solid Electrolytes for Li-Ion Batteries and Prediction of Optimized Halogen Doping: The Effect of Li Vacancies, Halogens, and Halogen Disorder [J].

de Klerk, Niek J. J. ;

Roslon, Trek ;

Wagemaker, Marnix .

CHEMISTRY OF MATERIALS, 2016, 28 (21) :7955-7963

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