Water solvated glass/amorphous solid ionic conductors

Patent metadata

Field	Value
Publication number	US-9890048-B2
Application number	US-201615178228-A
Country	US
Kind code	B2
Filing date	Jun 9, 2016
Priority date	Jun 18, 2015
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

The disclosure provides a water-solvated glass/amorphous solid that is an ionic conductor-an electronic insulator, and a dielectric as well as electrochemical devices and processes that use this material, such as batteries, including rechargeable batteries, fuel cells, capacitors, electrolysis cells, and electronic devices. The electrochemical devices and products use a combination of ionic and electronic conduction as well as internal electric dipoles.

First claim

The invention claimed is:

1. A method of forming a dried, water-solvated glass/amorphous solid, the method comprising:
transforming a crystalline sodium-ion (Na + ) or lithium-ion (Li + ) electronic insulator or its constituent precursors comprising at least one Na + or Li + bonded to oxygen (O), hydroxide (OH), and/or to at least one halide into a water-solvated glass/amorphous Na + or Li + ion-conducting solid having a water solvation limit by adding water in an amount less than or equal to the water solvation limit of the glass/amorphous solid;
heating the water-solvated glass/amorphous Na + or Li + ion-conducting solid in an alternating current (ac) or a direct current (dc) electric field to orient dipoles present in the water-solvated glass/amorphous Na + or Li + ion-conducting solid; and
cooling the water-solvated glass/amorphous Na + or Li + ion-conducting solid to room temperature such that dipoles present in the water-solvated glass/amorphous Na + or Li + ion-conducting solid remain oriented.

2. The method of claim 1 , further comprising adding a glass-forming oxide, sulfide, or hydroxide and heating to expel volatile constituents.

3. The method of claim 1 , wherein the crystalline, electronic insulator or its constituent precursors comprise a material with the general formula A 3-x H x OX, wherein 0≦x≦1, A is the at least one Na + or Li + , and X is the at least one halide.

4. The method of claim 1 , wherein the crystalline, electronic insulator or its constituent precursors comprises a glass-forming additive comprising at least one of an oxide, a hydroxide, and/or a sulfide.

5. The method of claim 4 , wherein the glass-forming additive comprises at least one of Ba(OH) 2 , Sr(OH) 2 , Ca(OH) 2 , Mg(OH) 2 , Al(OH) 3 , or BaO, SrO, CaO, MgO, AlO, B 2 O 3 , Al 2 O 3 , SiO 2 , S and/or Li 2 S.

6. The method of claim 5 , wherein the additive comprises at least two of Ba(OH) 2 , Sr(OH) 2 , Ca(OH) 2 , Mg(OH) 2 , Al(OH) 3 , or BaO, SrO, CaO, MgO, AlO, B 2 O 3 , Al 2 O 3 , SiO 2 , S and/or Li 2 S.

7. The method of claim 4 , wherein the additive comprises at least two of an oxide, a hydroxide, and/or a sulfide.

8. The method claim 4 , wherein the dried, water-solvated glass/amorphous solid comprises less than 2 mole percent of the glass-forming additive.

9. The method of claim 4 , wherein the additive adjusts the glass transition temperature T g of the water-solvated glass/amorphous solid.

10. The method of claim 1 , wherein the at least one halide comprises chlorine (Cl), bromine (Br) and/or iodine (I).

11. The method of claim 1 , wherein at least a portion of the at least one halide exits the water-solvated glass/amorphous solid as a hydrogen halide gas.

12. The method of claim 1 , wherein the hydroxide reacts to form H 2 O that exits the water-solvated glass/amorphous solid as gaseous H 2 O.

13. The method of claim 1 , further comprising heating the water-solvated glass/amorphous Na + or Li + ion-conducting solid to dry the water-solvated glass/amorphous Na + or Li + ion-conducting solid prior to heating the water-solvated glass/amorphous Na + or Li + ion-conducting solid in an alternating current (ac) or a direct current (dc) electric field.

14. The method of claim 13 , wherein heating the water-solvated glass/amorphous Na + or Li + ion-conducting solid to dry the water-solvated glass/amorphous Na + or Li + ion-conducting solid comprises heating to a temperature of at least 230° C.

15. The method of claim 1 , wherein heating the water-solvated glass/amorphous Na + or Li + ion-conducting solid comprises heating to a temperature between 50° C. and 110° C.

16. The method of claim 1 , wherein the water-solvated glass/amorphous Na + or Li + ion-conducting solid has a higher cation conductivity at room temperature than an otherwise identical material that is not heated in an alternating current (ac) or a direct current (dc) electric field.

Assignees

• Univ Texas
• Univ Do Porto
• Lneg Laboratorio Nac De Enegia E Geologia

Inventors

• Goodenough John B
• De Oliveira Braga Maria Helena Sousa Soares
• Do Amaral Ferreira Jose Jorge
• Singh Preetam

Classifications

• H01M8/124

  characterised by the process of manufacturing or by the material of the electrolyte · CPC title

• H01M8/1016 Primary

  characterised by the electrolyte material (H01M8/12 takes precedence) · CPC title

• C03C1/006 Primary

  to produce glass through wet route · CPC title

• C03C4/18

  for ion-sensitive glass · CPC title

• H01G11/56

  Solid electrolytes, e.g. gels; Additives therein · CPC title