Water solvated glass/amorphous solid ionic conductors

Patent metadata

Field	Value
Publication number	US-2016368777-A1
Application number	US-201615178228-A
Country	US
Kind code	A1
Filing date	Jun 9, 2016
Priority date	Jun 18, 2015
Publication date	Dec 22, 2016
Grant date	—

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

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 by adding water in an amount less than or equal to the water solvation limit of the glass/amorphous solid.

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 alkali metal, 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, Al , B 2 O 3 , Al 2 O 3 , SiO 2 , S and/or Li 2 S.

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

7 . 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, Al, B 2 O 3 , Al 2 O 3 , SiO 2 , S and/or Li 2 S.

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 . A method of forming an H + -conductive water-solvated electrolyte the method comprising transforming a crystalline material comprising at least one alkali and/or alkaline-earth cation bonded to at least one acidic polyanion into a glass/amorphous solid by adding water in an amount less than or equal to its solvation limit in the crystalline material such that water dissociates into hydroixide (OH − ) anions that coordinate to the cations to form polyanions and the water also dissociates into protons (H + ) that are mobile in a framework of an acidic oxide and the polyanions.

14 . The method of claim 13 , wherein the acidic polyanion comprises (SO 4 ) 2− and/or (PO 4 ) 3− .

15 . The method of claim 13 , wherein the alkaline-earth cation comprises lithium oin (Li + ) and/or sodium ion (Na + ).

16 . A method of forming a water-solvated glass/amorphous solid, the method comprising transforming a crystalline electronic insulator comprising at least one acidic polyanion and at least one cation into a water-solvated glass/amorphous proton (H + )-conducting solid by adding water in an amount less than or equal to the water solvation limit of the crystalline electronic insulator.

17 . The method of claim 15 , wherein the at least one cation is stabilized in the form of at least one stable hydroxide polyanion.

18 . The method of claim 15 , wherein the at least one acidic polyanion comprises a phosphate (PO 4 ) 3− polyanion and/or a sulfate (SO 4 ) 2− polyanion and/or (SiO 4 ) 4− polyanion.

19 . The method of claim 15 , wherein the at least one cation comprises a barium (Ba 2+ ) ion, a potassium (K + ) ion, a rubidium (Rb + ) ion, and/or a cesium (Cs + ) ion.

20 . The method of claim 15 , wherein the stable hydroxide polyanion comprises (Ba(OH) x ) 2-x , (K(OH) x ) 1-x , Rb(OH) x ) 1-x and/or (Cs(OH) x ) 1-x .

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

• H01M8/1016 Primary

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

• C01B25/306

  from phosphates · CPC title

• H01M10/36

  Accumulators not provided for in groups H01M10/05-H01M10/34 · CPC title

• C01F11/462

  Sulfates of Sr or Ba · CPC title

• C01B33/32 Primary

  Alkali metal silicates ({C01B33/24} , C01B33/26 take precedence) · CPC title