Stabilized shear thickening electrolyte

Patent metadata

Field	Value
Publication number	US-10347945-B2
Application number	US-201715835696-A
Country	US
Kind code	B2
Filing date	Dec 8, 2017
Priority date	Dec 8, 2017
Publication date	Jul 9, 2019
Grant date	Jul 9, 2019

Abstract

A passively impact resistant composite electrolyte composition includes an aprotic electrolyte solvent, from 0.5 to 6M of an electrolyte salt, and shear thickening particles having a polydispersity index of no greater than 0.1, an average particle size in a range of 50 nm to 1 um, and an absolute zeta potential of greater than ±40 mV. The shear thickening particles have thereon an electrochemical double layer. The composition further includes a stabilizing surfactant. The stabilizing surfactant includes a first portion for adsorbing to the particles, and a second portion that is absorbed in the solvent. The length of the surfactant from the first portion to the second portion is greater than twice the thickness of the electrochemical double layer. Batteries and electrochemical devices incorporating the electrolyte composition are disclosed. Methods of making the electrolyte composition and of operating a battery are also disclosed.

First claim

We claim:

1. A passively impact resistant composite electrolyte composition comprising an aprotic electrolyte solvent, from 0.5 to 6M of an electrolyte salt, and shear thickening particles having a polydispersity index of no greater than 0.1, an average particle size in a range of 50 nm to 1 um, and an absolute zeta potential of greater than ±40 mV, the shear thickening particles having thereon an electrochemical double layer, the composition further comprising a stabilizing surfactant, the stabilizing surfactant comprising a first portion for adsorbing to the particles, and a second portion that is absorbed in the solvent, the length of the surfactant from the first portion to the second portion being greater than twice the thickness of the electrochemical double layer.

2. The passively impact resistant composite electrolyte composition of claim 1 , wherein the stabilizing surfactant is a polymer with a chain length of no more than 60 nm.

3. The passively impact resistant composite electrolyte composition of claim 1 , wherein the stabilizing surfactant is a polymer with a chain length of no more than 40 nm.

4. The passively impact resistant composite electrolyte composition of claim 1 , wherein the stabilizing surfactant is a polymer comprising from 1 to 1149 monomer units.

5. The passively impact resistant composite electrolyte composition of claim 1 , wherein the composition is stable to an operating voltage of 4.6 V in a cell.

6. The passively impact resistant composite electrolyte composition of claim 1 , wherein the stabilizing surfactant is electrochemically stable and electrically insulating.

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

8. The passively impact resistant composite electrolyte composition of claim 1 , wherein the stabilizing surfactant comprises poly(methyl methacrylate) (PMMA).

9. The passively impact resistant composite electrolyte composition of claim 1 , wherein the stabilizing surfactant is a polyelectrolyte.

10. The passively impact resistant composite electrolyte composition of claim 9 , 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(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).

11. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening particles are ceramic.

12. The passively impact resistant composite electrolyte composition of claim 11 , 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, B 2 O 3 , Li 3 N and Li 2 S.

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

14. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening 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 the shear thickening 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 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 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 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 shear thickening particles have an absolute zeta potential of greater than ±50 mV.

20. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening particles have an absolute zeta potential of greater than ±60 mV.

21. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening 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 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 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 particles are present in the electrolyte composition in an amount from 20 wt. % to 40 wt. % based on the total weight of the electrolyte composition.

25. The passively impact resistant composite electrolyte composition of claim 1 , wherein the shear thickening particles are present is the electrolyte composition in an amount from 10 wt. % to 50 wt. % based on the total weight of the electrolyte composition.

26. The passively impact resistant composite electrolyte composition of claim 1 , wherein the aprotic electrolyte solvent comprises at least one material selected from the group consisting of sulfones, dinitriles, ethylene carbonate, dimethyl carbonate, propylene carbonate, dimethoxyethane, dioxolane, ethyl methyl carbonate, N-alkyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide, N-alkyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide, and 1-ethyle-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide.

27. 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 tetrafluoro 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.

28. The passively impact resistant composite electrolyte composition of claim 1 , wherein steric stabilizing polymers are coupled to the shear thickening particles, the steric stabilizing polymers comprising at least one of monomer unit 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.

29. The passively

Assignees

• Ut Battelle Llc

Inventors

• Veith Gabriel M
• Armstrong Beth L
• Browning Katie L
• Wang Hsin
• Kalnaus Sergiy

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M4/48

  of inorganic oxides or hydroxides · CPC title

• H01M10/0567

  characterised by the additives · CPC title

• H01M10/0569 Primary

  characterised by the solvents · CPC title