High-air-stability inorganic sulfide solid electrolyte and preparation method and application thereof

A sulfide electrolyte, inorganic sulfide technology, applied in solid electrolyte, electrolyte battery manufacturing, inorganic chemistry and other directions, can solve the problems of restricting the application of all-solid-state lithium batteries, unstable inorganic sulfide electrolyte, and reduced structural ionic conductivity, etc. Achieve the effects of excellent ionic conductivity, good air stability and low production cost

Active Publication Date: 2019-08-02
CHINA AUTOMOTIVE BATTERY RES INST CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] However, the reported inorganic sulfide electrolytes containing P element are all unstable under air conditions.
This type of sulfide electrolyte has an irreversible chemical reaction with oxygen, water vapor, carbon dioxide, etc. in the air atmosphere, resulting in structural changes and a decrease in ion conductivity, which seriously restricts its application in all-solid-state lithium batteries.

Method used

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  • High-air-stability inorganic sulfide solid electrolyte and preparation method and application thereof
  • High-air-stability inorganic sulfide solid electrolyte and preparation method and application thereof
  • High-air-stability inorganic sulfide solid electrolyte and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Embodiment 1 prepares Li 10 Ge(P 1-a Sb a ) 2 S 12 Solid electrolyte material (0.01≤a≤1)

[0054] 15 mmol Li 2 S (0.69 g), 3 mmol of GeS 2 (0.411 g), (3-3a) mmol of P 2 S 5 , 3a mmoles of Sb 2 S 5 The powder is ground and mixed in a mortar, where 0.01≤a≤1. When a=0.01, the batching of each raw material is as follows: Li 2 S is 0.69 g, GeS 2 is 0.411 g, P 2 S 5 0.66 g, Sb 2 S 5 is 0.012 grams; as a=0.1, the batching of each raw material is as follows: Li 2 S is 0.69 g, GeS 2 is 0.411 g, P 2 S 5 0.599 g, Sb 2 S 5is 0.121 grams. And so on. After grinding and mixing, put it into a 50 milliliter zirconia ball mill jar for ball milling, the ball milling speed is 400 rpm, and the ball milling time is 12 hours. The ball-milled samples were pressed into discs using a powder tablet press at a pressure of 100 MPa, and then sealed in a vacuum quartz tube for calcination. The calcination temperature is controlled by a temperature program, from room temperatu...

Embodiment 2

[0056] Embodiment 2 prepares Li 6 (P 1-a Sb a )S 5 Cl solid electrolyte material (0.01≤a≤1)

[0057] 20 mmol Li 2 S (0.92 g), 8 mmol of LiCl (0.336 g), (4-4a) mmol of P 2 S 5 and 4a mmol of Sb 2 S 5 The powder is ground and mixed in a mortar, where 0.01≤a≤1. When a=0.025, the batching of each raw material is as follows: Li 2 S is 0.92g, LiCl is 0.336g, P 2 S 5 0.866 g, Sb 2 S 5 is 0.03 grams; as a=0.1, the batching of each raw material is as follows: Li 2 S is 0.92g, LiCl is 0.336g, P 2 S 5 0.799 g, Sb 2 S 5 is 0.121 grams. And so on. After grinding and mixing, put it into a 50 milliliter zirconia ball mill jar for ball milling, the ball milling speed is 400 rpm, and the ball milling time is 12 hours. The ball-milled samples were pressed into discs using a powder tablet press at a pressure of 100 MPa, and then sealed in a vacuum quartz tube for calcination. The calcination temperature is controlled by a temperature program, from room temperature to 550 deg...

Embodiment 3

[0059] Embodiment 3 prepares Li 10 Sn(P 0.95 Sb 0.05 ) 2 S 12 solid electrolyte material

[0060] 15 mmol Li 2 S (0.69 g), 3 mmol of SnS 2 (0.549 g), 2.85 mmol of P 2 S 5 (0.633 g), 0.15 mmol of Sb 2 S 5 (0.061 g) powder was ground and mixed in a mortar and pestle. After grinding and mixing, put it into a 50 milliliter zirconia ball mill jar for ball milling, the ball milling speed is 400 rpm, and the ball milling time is 12 hours. The ball-milled samples were pressed into discs using a powder tablet press at a pressure of 100 MPa, and then sealed in a vacuum quartz tube for calcination. The calcination temperature is controlled by a temperature program, from room temperature to 550 degrees Celsius over 4 hours, and kept at this temperature for 4 hours, and then controlled to cool down to 50 degrees Celsius for 4 hours to obtain Li 10 Sn(P 0.95 Sb 0.05 ) 2 S 12 solid electrolyte material.

[0061] Figure 9 for Li 10 Sn(P 0.95 Sb 0.05 ) 2 S 12 X-ray diff...

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PUM

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Abstract

The invention relates to a high-air-stability inorganic sulfide solid electrolyte and a preparation method and application thereof. The Sb element is applied to replace part or all of P element in thesulfide electrolyte so as to obtain the electrolyte with higher air stability and higher ion mobility and the electrolyte can be applied to the all-solid-state lithium secondary battery. The obtainedinorganic sulfide electrolyte materials are Li10M(P1-aSba)2S12, Li6 (P1-aSba)S5X, and Li3(P1-aSba)S4, wherein M is one or more of Ge, Si, and Sn, X is one or more of F, Cl, Br and I and 0.01<=a<=1.

Description

technical field [0001] The invention belongs to the technical field of lithium ion batteries, and in particular relates to a method for improving the air stability of an inorganic sulfide solid electrolyte, the obtained material and its application field in all-solid lithium secondary batteries. Background technique [0002] Since the commercialization of lithium-ion secondary batteries in the early 1990s, they have developed rapidly due to their advantages such as high energy density and long service life. However, the currently widely used lithium-ion batteries are liquid-phase batteries, which contain flammable organic electrolytes, so there are serious safety hazards. In recent years, the occurrence of frequent safety accidents on liquid-phase lithium-ion power batteries has greatly restricted the further use of this system. The use of non-flammable inorganic solid materials as the electrolyte of lithium-ion batteries can not only eliminate the leakage of the organic el...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0562H01M10/058H01M10/0525C01G30/00
CPCH01M10/0562H01M10/058H01M10/0525C01G30/002C01G30/003C01P2002/72C01P2006/40Y02E60/10Y02P70/50C01G17/006C01G19/006C01D15/00H01M10/052H01M2300/0068H01M4/131H01M4/62
Inventor 孙学良梁剑文李晓娜黄欢卢世刚张立赵尚骞
Owner CHINA AUTOMOTIVE BATTERY RES INST CO LTD
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