Solid electrolyte glass for lithium or sodium ions conduction

• US 10,411,293 B2
• Filed: 02/26/2015
• Issued: 09/10/2019
• Est. Priority Date: 02/26/2014
• Status: Active Grant

• Current Assignee: Laboratorio Nacional De Energia E Geologia, Universidade D.O. Porto
• Original Assignee: Universidade D.O. Porto
• Inventors: Sousa Soares De Oliveira Braga, Maria Helena, Do Amaral Ferreira, Jose Jorge
• Primary Examiner(s): McConnell, Wyatt P
• Application Number:
  US15/121,678
• Publication Number:
  US 20160365602A1
• Time in Patent Office: 1,657 Days
• Field of Search: None
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01G 11/84 Processes for the manufacture of hybrid or EDL capacitors, or components thereof
• CPC Class Codes: H01G 9/15 Solid electrolytic capacitors H01G11/00 takes precedence
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/054 Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 16/00 Structural combinations of different types of electrochemical generators
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

Glassy electrolyte for lithium or sodium ions conduction The present disclosure relates to the development and improvement of sodium or lithium-ion electrochemical devices, in particular to the development of a new glassy electrolyte comprising high ionic conductivity for batteries, capacitors, and other electrochemical devices comprising a solid electrolyte glass comprising the formula R_3-2xM_xHalO wherein R is selected from the group consisting of lithium or sodium; M is selected from the group consisting of magnesium, calcium, strontium or barium; Hal is selected from the group consisting of fluorine, chlorine, bromine, iodine or mixtures thereof; X is the number of moles of M and 0≤x≤0.01 and the solid electrolyte glass has a glass transition point.

Claims

1. A solid electrolyte glass comprising compound of formula R3_3-2xM_xHalO wherein

R is selected from the group consisting of lithium and sodium;

M is selected from the group consisting of magnesium, calcium, strontium, barium, and mixtures thereof;

Hal is selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures thereof;

X is the number of moles of M and 0<

x<

0.01;

and the solid electrolyte glass has a glass transition point and an ionic conductivity of at least 13 mScm<sup>−

1</sup> at 25°

C.

2. The electrolyte glass according to claim 1, wherein R is lithium.

3. The electrolyte glass according to claim 1, wherein R is sodium.

4. The electrolyte glass according to claim 1, comprising an ionic conductivity of 13-60 mScm⁻

1 at 25°

C.

5. The electrolyte glass according to claim 1, comprising an ionic conductivity of at least 25 mScm⁻

1 at 25°

C.

6. The electrolyte glass according to claim 1, comprising an ionic conductivity of at least 17 mScm⁻

1 at 25°

C.

7. The electrolyte glass according to claim 1, comprising an ionic conductivity of 17-105 mScm⁻

1 at 25°

C.

8. The electrolyte glass according to claim 1, comprising an ionic conductivity of at least 31 mScm⁻

1 at 25°

C.

9. The electrolyte glass according to claim 1, wherein X is 0.002, 0.005, 0.007 or 0.01.

10. The electrolyte glass according to claim 1, wherein Hal is a mixture of chlorine and iodine.

11. The electrolyte glass according to claim 1, wherein Hal is Hal=0.5Cl+0.5I.

12. The electrolyte glass according to claim 1, wherein Hal is a mixture of fluorine and iodine.

13. The electrolyte glass according to claim 1, wherein R is lithium, M is barium, Hal is chlorine and x is 0.005.

14. The electrolyte glass according to claim 1, wherein R is lithium, M is barium, Hal is a mixture of chlorine and iodine, x is 0.005.

15. The electrolyte glass according to claim 1, wherein R is sodium, M is barium, Hal is chlorine and x is 0.005.

16. A method for synthetizing a glass electrolyte comprising a compound of formula Li_3-2xM_xHalO wherein

M is selected from the group consisting of magnesium, calcium, strontium, and barium;

Hal is selected from the group consisting of fluorine, chlorine, bromine, iodine, and mixtures thereof;

X is the number of moles of M and 0 <

x<

0.01;

the method comprising the following steps;

mixing a stoichiometric quantity of LiHal, LiOH, and one of the following compounds;

Mg(OH)₂, Ca(OH)₂, Sr(OH)₂ or Ba(OH)₂, and mixtures thereof;

adding to said mixture deionized water and mixing to form a solution in a closed container;

heating said solution to a temperature of less than 250°

C. for 2-8 h to form a heated product;

evaporating water in the heated product to form a synthesized electrolyte.

17. The method according to claim 16, further comprising:

introducing the synthetized glass electrolyte between electrodes of an electrochemical device;

heating the glass electrolyte up to a temperature between 170°

C. and 240° and

cooling the glass electrolyte.

18. A method for synthetizing a glass electrolyte comprising a compound of formula Na_3-2xM_xHalO wherein

M is selected from the group consisting of magnesium, calcium, strontium, barium, and mixtures thereof;

Hal is selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures thereof; and

X is the number of moles of M and 0 <

x<

0.01;

the method comprising the following steps;

mixing a stoichiometric quantity of NaHal, NaOH, and one of the following compounds;

Mg(OH)2, Ca(OH)2, Sr(OH)2 or Ba(OH)2, and mixtures thereof;

adding to said mixture deionized water and mixing to form a solution in a closed container;

heating said solution to a temperature of 70-90°

C. for 2-8 h, then heating the solution to a temperature of 190°

C.-250°

C. for 2-8 hours to form a heated product; and

evaporating water in the heated product to form a synthesized glass electrolyte.

19. The method of claim 18, further comprising:

introducing the synthesized glass electrolyte between electrodes of an electrochemical device;

heating the glass electrolyte up to a temperature between 190°

C. and 230°

C.; and

cooling the glass electrolyte.