Pre-lithiated polyphenylene sulfide, polyphenylene sulfide-based solid electrolyte membrane, battery electrode sheet, quasi-solid-state lithium ion battery and method for manufacturing same

Patent metadata

Field	Value
Publication number	US-11289737-B2
Application number	US-202017413960-A
Country	US
Kind code	B2
Filing date	Nov 20, 2020
Priority date	Nov 21, 2019
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

Abstract

A method for manufacturing a pre-lithiated polyphenylene sulfide with a high solid solubility of lithium includes; placing NMP, Li2S, and LiOH into a high-pressure reactor to obtain a mixture, and heating the mixture to 150-250° C. for a high-temperature dehydration for 2-5 h, and then cooling the mixture to 100° C. and adding p-DCB to the mixture for a reaction at 150-250° C. for 80-200 min; dropwise adding hydrochloric acid in an identical amount as that of the LiOH neutralize LiOH, and removing NMP and H2O by evaporation or sublimation, to obtain a dry mixed powder; and to the dry mixed powder, adding a chloride ion complexing agent to obtain a mixture, stirring the mixture to homogeneity, and placing the mixture in a sealed reactor for a reaction at 150-250° C. for 80-200 min, followed by washing and drying, to obtain the pre-lithiated polyphenylene sulfide.

First claim

What is claimed is:

1. A method for manufacturing a pre-lithiated polyphenylene sulfide with a high solid solubility of lithium, comprising the following steps:
placing N-methylpyrrolidone (NMP), lithium sulfide (Li 2 S), and lithium hydroxide (LiOH) into a high-pressure reactor with a stirring function to obtain a first mixture, and heating the first mixture to 150-250° C. for a high-temperature dehydration for 2-5 h, and then cooling the first mixture to 100° C. and adding 1,4-dichlorobenzene (p-DCB) to the first mixture for a first reaction at 150-250° C. for 80-200 min;
dropwise adding hydrochloric acid in an identical amount as an amount of the LiOH on a molar basis to neutralize the LiOH, and removing the NMP and H 2 O by an evaporation or sublimation, to obtain a dry mixed powder; and
to the dry mixed powder, adding a chloride ion complexing agent to obtain a second mixture, stirring the second mixture to homogeneity, and placing the second mixture in a sealed reactor for a second reaction at 150-250° C. for 80-200 min, followed by washing and drying, to obtain the pre-lithiated polyphenylene sulfide with the high solid solubility of lithium.

2. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1 , wherein
the Li 2 S is formed by a high-temperature reaction of a lithium metal powder with a sulfur powder or the Li 2 S is formed by a carbothermal reduction reaction of lithium sulfate (Li 2 SO 4 ).

3. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1 , wherein
the NMP, the Li 2 S, and the LiOH are at a molar ratio of 1-5:1:0.05-0.2.

4. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1 , wherein
the Li 2 S and the p-DCB are at a molar ratio of 1.3-0.8:1.

5. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1 , wherein
the evaporation or sublimation comprises a hot-air drying method, a rotary evaporation method, and a freeze-drying method, to maximize a retention of solid-phase components and only remove the NMP and the H 2 O.

6. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1 , wherein
the chloride ion complexing agent is an organic metal-ion-free complexing agent, and
the chloride ion complexing agent is preferably calixcrown ether, caliximidazole, calixpyrrole, or calixarene.

7. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1 , wherein
the chloride ion complexing agent is added in an amount on the molar basis, wherein the amount of the chloride ion complexing agent is 0.01-0.2 times an amount of the p-DCB.

8. A pre-lithiated polyphenylene sulfide prepared by the method according to claim 1 .

9. A method for preparing an isotropic polyphenylene sulfide-based solid electrolyte membrane, comprising the following steps:
mixing a pre-lithiated polyphenylene sulfide powder and polytetrafluoroethylene (PTFE) uniformly in a mixer under a temperature condition where the PTFE is in a glassy state, to obtain a mixed powder, and air-grinding the mixed powder with a supersonic gas to allow a molecular chain of the PTFE to extend and open and form a physical adhesion with the pre-lithiated polyphenylene sulfide powder, without a chemical reaction;
then removing the supersonic gas in the mixed powder through an extruder to form a continuous cake-like wide strip, followed by hot pressing the continuous cake-like wide strip into a pre-lithiated polyphenylene sulfide membrane material with a hot roll at a temperature lower than 150° C., and winding the pre-lithiated polyphenylene sulfide membrane material up; and
preparing the isotropic polyphenylene sulfide-based solid electrolyte membrane.

10. The method for preparing the isotropic polyphenylene sulfide-based solid electrolyte membrane according to claim 9 , wherein
the pre-lithiated polyphenylene sulfide powder and the PTFE are mixed uniformly in the mixer at a temperature controlled below 10° C. for a mixing time of 0.5-4 h.

11. A polyphenylene sulfide-based solid electrolyte membrane prepared by the method according to claim 9 .

12. The polyphenylene sulfide-based solid electrolyte membrane according to claim 11 , wherein
the pre-lithiated polyphenylene sulfide powder and the PTFE are mixed uniformly in the mixer at a temperature controlled below 10° C. for a mixing time of 0.5-4 h.

Assignees

• Univ Jiangsu

Inventors

• Zhou Haitao
• Gao Hongquan
• Wu Jianchun
• Yu Chongchen
• Liu Menghao
• Hou Dong

Classifications

• C08G75/0254

  using metal sulfides · CPC title

• C08G75/02

  Polythioethers · CPC title

• C08G75/0204

  Polyarylenethioethers · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M2300/0082

  Organic polymers · CPC title