Shear activated impact resistant electrolyte

Patent metadata

Field	Value
Publication number	US-10347934-B2
Application number	US-201615382082-A
Country	US
Kind code	B2
Filing date	Dec 16, 2016
Priority date	Sep 26, 2014
Publication date	Jul 9, 2019
Grant date	Jul 9, 2019

Abstract

A passively impact resistant composite electrolyte composition includes an electrolyte solvent, up to 6M of an electrolyte salt, and shear thickening ceramic particles having an outer surface. The shear thickening ceramic particles have an absolute zeta potential of greater than ±40 mV. The shear thickening ceramic particles have a polydispersity index of no greater than 0.1, and an average particle size of in a range of 50 nm to 1 um. The ceramic particles have bonded to the outer surface steric stabilizing polymers. The steric stabilizing polymers have a chain length of from 0.5 nm to 100 nm. A passively impact resistant laminated battery and a method of making the electrolyte composition are also disclosed.

First claim

We claim:

1. A passively impact resistant composite electrolyte composition comprising an electrolyte solvent, up to 6M of an electrolyte salt, and shear thickening ceramic particles having an outer surface, the shear thickening ceramic particles having an absolute zeta potential of greater than ±40 mV, a polydispersity index of no greater than 0.1, and an average particle size in a range of 50 nm to 1 um, the ceramic particles having bonded to the outer surface steric stabilizing polymers, the steric stabilizing polymers having a chain length of from 0.5 nm to 100 nm.

2. The passively impact resistant composite electrolyte composition of claim 1 , wherein the steric stabilizing polymers having a chain length of greater than double the thickness of an electrochemical double layer surrounding the particles.

3. The passively impact resistant composite electrolyte composition of claim 1 , wherein the steric stabilizing polymers have a chain length of no more than 60 nm.

4. The passively impact resistant composite electrolyte composition of claim 1 , wherein the steric stabilizing polymers have a chain length of no more than 40 nm.

5. The passively impact resistant composite electrolyte composition of claim 1 , wherein the steric stabilizing polymers comprise from 1 to 145 monomer units.

6. The passively impact resistant composite electrolyte composition of claim 1 , wherein the composition is stable to an operating voltage of 4.6V (versus Li/Li + ) in a cell.

7. The passively impact resistant composite electrolyte composition of claim 1 , wherein the steric stabilizing polymers are at least one selected from the group containing of hydrolytically stable, electrically insulating and ionically conducting.

8. The passively impact resistant composite electrolyte composition of claim 1 , wherein the steric stabilizing polymers comprise monomer units selected from the group consisting of styrenes, acrylates, methacrylates, acrylonitrile, acrylamides, and methacrylamides, 4-vinylpyridine, 2,2′-dichloroethene, 2-methyl-1,3-butadiene acrylic acids and methacrylic acids, vinyl ester, N-vinyl carbazole, N-vinyl pyrrolidone and mixtures thereof.

9. The passively impact resistant composite electrolyte composition of claim 1 , wherein the steric stabilizing polymers comprise poly(methyl methacrylate) (PMMA).

10. The passively impact resistant composite electrolyte composition of claim 1 , wherein the steric stabilizing polymers are bonded to at least one selected from the group consisting of Si polymer, oxygen groups, surface hydroxyls, an Si—Ox groups of the ceramic particles.

11. The passively impact resistant composite electrolyte composition of claim 1 , comprising at least one steric stabilizing polymer per square nanometer of the outer surface of the ceramic particles.

12. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic particles comprise at least one material selected from the group consisting of TiO 2 , Al 2 O 3 , ZrO 2 , Y 2 O 3 , HfO 2 , GeO 2 , Sc 2 O 3 , CeO 2 , MgO, SiO 2 , BN, and B 2 O 3 .

13. The passively impact resistant composite electrolyte composition of claim 1 , wherein said shear thickening ceramic particles comprise silica.

14. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic particles have a polydispersity index of no greater than 0.09.

15. The passively impact resistant composite electrolyte composition in accordance with claim 1 , wherein said shear thickening ceramic particles have a polydispersity index of no greater than 0.07.

16. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic particles have a polydispersity index of no greater than 0.05.

17. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic particles have an average particle size of in a range of 100 nm to 500 nm.

18. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic particles have an average particle size of in a range of 150 nm to 300 nm.

19. The passively impact resistant composite electrolyte composition of claim 1 , wherein the polymer is a polyelectrolyte.

20. The passively impact resistant composite electrolyte composition of claim 19 , wherein the polyelectrolyte is at least one selected from the group consisting of pectin, carrageenan, alginates, polyacrylic acid, poly(sodium styrene sulfonate) (PSS), polymethacrylic acid, poly vinyl amine, poly 2-vinylpyridine, carboxymethyl cellulose, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile), poly(styrene sulfonic acid), poly(4-styrenesulfonic acid-co-maleic acid), and poly(vinylsulfonic acid).

21. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic particles are essentially free of materials that volatilize at 80° C.

22. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic particles are essentially free of materials that volatilize at 110° C.

23. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic particles are essentially free of materials that volatilize at 120° C.

24. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic particles are present in the composition in an amount in the range of 10 to 50 weight percent.

25. The passively impact resistant composite electrolyte composition of claim 1 , wherein the electrolyte solvent comprises at least one material selected from the group consisting of ethylene carbonate, dimethyl carbonate, propylene carbonate, dimethoxyethane, dioxolane, sulfone, dinitriles, ethyl methyl carbonate, and an ionic liquid.

26. The passively impact resistant composite electrolyte composition of claim 1 , wherein the electrolyte salt comprises at least one material selected from the group consisting of lithium hexafluorophosphate, lithium triflate, lithium perchlorate, lithium tetrafluoride borate, lithium hexafluoro lithium arsenate, lithium bis(trifluoromethane sulphone)imide, lithium bis(oxalate) borate, sodium perchlorate, sodium tetrafluoro borate, sodium hexafluoro arsenate, sodium bis(trifluoromethane sulphone)imide, sodium bis(oxalate) borate.

27. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening ceramic is functionalized with at least one material selected from the group consisting of a styrene, an acrylate, a methacrylate, a vinyl ester, an acrylamide, a methacrylamide, an acrylonitrile, N-vinyl carbazole, and N-vinyl pyrrolidone.

28. A passively impact resistant battery comprising: an anode; a cathode; and a passively impact resistant composite electrolyte disposed between said anode and said cathode, the electrolyte comprising a passively impact resistant composite electrolyte composition comprising an electrolyte solvent, up to 6M of an electrolyte salt, and shear thickening ceramic particles having an outer surface, the shear thickening ceramic particles having an absolute zeta potential of greater than ±40 mV, a polydispersity i

Assignees

• Ut Battelle Llc
• Shen Brian H

Inventors

• Veith Gabriel M
• Armstrong Beth L
• Shen Brian H
• Tenhaeff Wyatt E
• Kalnaus Sergiy
• Wang Hsin

Classifications

• H01M10/0567

  characterised by the additives · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M12/08

  composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type · CPC title

• H01M2300/0037

  Mixture of solvents · CPC title