Electrochemical cells with a high voltage cathode

• US 10,109,859 B1
• Filed: 04/03/2018
• Issued: 10/23/2018
• Est. Priority Date: 04/03/2017
• Status: Active Grant

• Current Assignee: Hydro-Quebec (Province of Québec)
• Original Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Inventors: Goodenough, John B., De Oliveira Braga, Maria Helena Sousa Soares
• Primary Examiner(s): Conley, Helen Oi K
• Application Number:
  US15/944,354
• Publication Number:
  US 20180287150A1
• Time in Patent Office: 203 Days
• CPC Class Codes: H01G 11/28 arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
• CPC Class Codes: H01G 11/32 Carbon-based
• CPC Class Codes: H01G 11/48 Conductive polymers
• CPC Class Codes: H01G 11/50 specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• 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 10/0562 Solid materials
• CPC Class Codes: H01M 10/0585 of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

The present disclosure provides a rechargeable electrochemical cell including an electrolyte side, a cathode side, and a polymer/plasticizer. The electrolyte side includes a solid glass electrolyte including an electrolyte mobile cation and electric dipoles, as well as an anode including a metal of the electrolyte mobile cation and contacting the solid glass electrolyte at an anode:solid glass electrolyte interface. The cathode side includes a cathode including a cathode active material into which a cathode guest cation is reversibly extracted/inserted. The cathode active material has a voltage versus lithium (Li) metal of between 3V and 15V. The polymer/plasticizer contacts the solid glass electrolyte at a solid glass electrolyte:polymer/plasticizer interface and the cathode at a polymer/plasticizer:cathode interface such that the cathode guest cation is confined to the cathode side and the electrolyte mobile cation is confined to the anode side during charge and discharge of the electrochemical cell.

Claims

1. A rechargeable electrochemical cell comprising:

an electrolyte side comprising;

a solid glass electrolyte comprising an electrolyte mobile cation and electric dipoles; and

an anode comprising a metal of the electrolyte mobile cation and contacting the solid glass electrolyte at an anode;

solid glass electrolyte interface;

a cathode side comprising a cathode comprising a cathode active material into which a cathode guest cation is reversibly extracted/inserted, the cathode active material having a voltage versus lithium (Li) metal of between 3V and 15V; and

a polymer/plasticizer contacting the solid glass electrolyte at a solid glass electrolyte;

polymer/plasticizer interface and the cathode at a polymer/plasticizer;

cathode interface such that the cathode guest cation is confined to the cathode side and the electrolyte mobile cation is confined to the anode side during charge and discharge of the electrochemical cell.

2. The rechargeable electrochemical cell of claim 1, wherein the electrolyte mobile cation and the cathode guest cation are the same type of cation.

3. The rechargeable electrochemical cell of claim 1, wherein the electrolyte mobile cation and the cathode guest cation are different types of cations.

4. The rechargeable electrochemical cell of claim 1, wherein the polymer/plasticizer comprises a mobile cation.

5. The rechargeable electrochemical cell of claim 4, wherein the mobile cation in the polymer/plasticizer is the same type of cation as the electrolyte mobile cation, the cathode guest cation, or both.

6. The rechargeable electrochemical cell of claim 4, wherein the mobile cation in the polymer/plasticizer is a different type of cation than the electrolyte mobile cation, the cathode guest cation, or both.

7. The rechargeable electrochemical cell of claim 1, wherein the polymer/plasticizer comprises a material having a dielectric constant between 50 and 24,000.

8. The rechargeable electrochemical cell of claim 4, wherein the polymer/polymer plasticizer comprises a polymer or plasticizer and the molar ratio of polymer or plasticizer to mobile cation is between 10:

1 and 50;

1.

9. The rechargeable electrochemical cell of claim 4, wherein the mobile cation is supplied by LiClO₄ in the polymer/plasticizer.

10. The rechargeable electrochemical cell of claim 1, wherein the polymer/plasticizer comprises a —

C≡

N terminal group.

11. The rechargeable electrochemical cell of claim 10, wherein the polymer/plasticizer comprises succinonitrile.

12. The rechargeable electrochemical cell of claim 1, wherein the polymer/plasticizer comprises electric dipoles.

13. The rechargeable electrochemical cell of claim 1, further comprising a cathode current collector contacting the cathode at a cathode:

cathode current collector interface.

14. The rechargeable electrochemical cell of claim 1, wherein the electrolyte mobile cation, the cathode guest cation, or both moves in the direction of the anode or the cathode current collector on average no more than 1/10,000^th of the distance between the anode:

sold glass electrolyte interface and the cathode;

cathode current collector interface during a charge/discharge cycle of the electrochemical cell.

15. The rechargeable electrochemical cell of claim 1, wherein the metal in the anode comprises Li metal, sodium (Na) metal, potassium (K) metal, aluminum metal (Al), magnesium (Mg) metal, or alloys thereof.

16. The rechargeable electrochemical cell of claim 1, wherein the electrolyte mobile cation comprises lithium ion (Li ), sodium ion (Na ), potassium ion (K ), aluminum ion (Al³ ), or magnesium ion (Mg² ).

17. The rechargeable electrochemical cell of claim 1, wherein the cathode active material comprises a layered oxide, a spinel, or an olivine.

18. The rechargeable electrochemical cell of claim 1, wherein the cathode guest cation comprises lithium ion (Li ), sodium ion (Na ), potassium ion (K ), aluminum ion (Al³ ), or magnesium ion (Mg² ).

19. The rechargeable electrochemical cell of claim 1, wherein the cathode further comprises elemental carbon (C).

20. The rechargeable electrochemical cell of claim 1, wherein the electric dipoles of the solid glass electrolyte comprise material of the general formulas A₂X or AX⁻

, or MgX or Al₂X₃ where A is Li, Na, or K and X is oxygen (O), sulfur (S) or combinations thereof.