Rechargeable hybrid battery/supercapacitor system

• US 6,252,762 B1
• Filed: 04/21/1999
• Issued: 06/26/2001
• Est. Priority Date: 04/21/1999
• Status: Expired due to Term

• Current Assignee: Rutgers University
• Original Assignee: Telcordia Technologies Incorporated (Telefonaktiebolaget LM Ericsson)
• Inventors: Amatucci, Glenn G.
• Primary Examiner(s): Reichard, Dean A.
• Assistant Examiner(s): THOMAS, ERIC W
• Application Number:
  US09/295,537
• Time in Patent Office: 797 Days
• Field of Search: 361/502, 361/503, 361/504, 361/505, 361/506, 361/507, 361/508, 361/509, 361/510, 361/511, 361/512, 361/516, 361/517, 429/231.9, 429/231.95, 429/229, 429/231.1, 429/231.8
• US Class Current: 361/503
• CPC Class Codes: H01G 11/06 with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• CPC Class Codes: H01G 11/32 Carbon-based
• CPC Class Codes: H01G 11/46 Metal oxides
• CPC Class Codes: H01G 11/62 characterised by the solute, e.g. salts, anions or cations 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 10/4264 with capacitors
• CPC Class Codes: H01M 14/00 Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A rechargeable hybrid battery/supercapacitor electrical storage system capable of providing high energy and high power densities comprises an intercalation electrode (17) and a capacitor electrode (13) combined with a separator (15) and electrically-conductive current collector elements (11, 19) to form a unitary cell structure (10). An electrolyte solution of a dissociable salt absorbed into the porous structure of the separator (15) provides complementary ion species which respectively reversibly intercalate into the one electrode (17) and capacitively adsorb at the surface of the other electrode (13) upon the application of charging current. The high density stored electrical energy may be recovered at high power over extended periods upon demand of a utilizing device and may be rapidly restored to stable capacity through numerous charging cycles.

Claims

1. A rechargeable electrical energy storage system comprising in contiguity a positive electrode member, a negative electrode member, and a separator member interposed therebetween containing a fluid electrolyte comprising a cation and an anion of an ion species of a dissociable salt wherein

a) said negative electrode member comprises a first material capable of reversibly intercalating said cation of said ion species in response to the application of an electrical charge of a first polarity, and

b) said positive electrode member comprises a second material capable of reversibly adsorbing said anion of said ion species in response to the application of a contemporaneous electrical charge of opposite polarity.

2. A storage system according to claim 1 wherein said cation is selected from the group consisting of alkalies, alkaline earths, lanthanides, Al, and Zn.

3. A storage system according to claim 1 wherein said anion is selected from the group consisting of PF₆, ClO₄, BF₄, CF₃SO₃, and SbF₆.

4. A storage system according to claim 1 wherein said first material is selected from the group consisting of transition metal oxides, sulfides, phosphates, and fluorides, and alkali and alkaline earth metal-alloying metals and compounds.

5. A storage system according to claim 4 wherein said first material is a transition metal oxide spinel compound.

6. A storage system according to claim 5 wherein said first material is Li₄Ti₅O₁₂.

7. A storage system according to claim 1 wherein said first material is selected from the group consisting of open-structured carbonaceous graphites, hard carbons, and cokes.

8. A storage system according to claim 1 wherein said second material is selected from the group consisting of pseudocapacitor and double-layer capacitor electrode materials.

9. A storage system according to claim 6 wherein said second material is selected from the group consisting of high surface area activated carbon powder, foam, fiber, and fabric materials.

10. A storage system according to claim 1 wherein said electrolyte comprises a 0.5 to 2.0 M solution of at least one said dissociable salt in an organic solvent selected from the group consisting of ethylene carbonate, dimethyl carbonate, propylene carbonate, diethoxyethane, diethyl carbonate, dimethoxyethane, sulfolane, and dipropyl carbonate and mixtures thereof.

11. A storage system according to claim 10 wherein said at least one dissociable salt is selected from the group consisting of LiPF₆, LiClO₄, LiN(CF₃SO₂)₂, LiBF₄, LiCF₃SO₃, and LiSbF₆.

12. A rechargeable hybrid battery/supercapacitor system comprising a positive electrode member, a negative electrode member, and a separator member interposed therebetween containing a fluid electrolyte comprising a cation and an anion of an ion species of a dissociable salt wherein

a) said negative electrode member comprises a layer comprising a first material capable of reversibly intercalating said cation of said ion species in response to the application of an electrical charge of a first polarity, and

b) said positive electrode member comprises a layer comprising a second material capable of reversibly adsorbing said anion of said ion species in response to the application of a contemporaneous electrical charge of opposite polarity,

c) said separator member comprises a microporous layer having dispersed therein a non-aqueous solution of said dissociable salt, and

d) each said member is bonded to its contiguous members at their respective interface to form a unitary laminate structure.

13. A hybrid system according to claim 12 wherein each of said positive electrode member and said negative electrode member is bonded to a respective electrically-conductive current collector element.

14. A hybrid system according to claim 12 wherein

a) each of said electrode member layers comprises a polymeric matrix having dispersed therein the respective ion-intercalating and ion-adsorbing material,

b) said separator member layer comprises a polymeric membrane having dispersed therein a multiplicity of pores or voids, and

c) said members are bonded by thermal adhesion at their polymeric surfaces.

15. A hybrid system according to claim 12 wherein said first material is selected from the group consisting of transition metal oxides, sulfides, phosphates, and fluorides, and alkali and alkaline earth metal-alloying metals and compounds.

16. A hybrid system according to claim 12 wherein said first material is selected from the group consisting of open-structured carbonaceous graphites, hard carbons, and cokes.

17. A hybrid system according to claim 12 wherein said second material is selected from the group consisting of pseudocapacitor and double-layer capacitor electrode materials and high surface area activated carbon powder and fibers.

18. A hybrid system according to claim 12 wherein said electrolyte comprises a 0.5 to 2.0 M solution of at least one said dissociable salt in an organic solvent selected from the group consisting of ethylene carbonate, dimethyl carbonate, propylene carbonate, diethoxyethane, diethyl carbonate, dimethoxyethane, sulfolane, and dipropyl carbonate and mixtures thereof.

19. A hybrid system according to claim 18 wherein said at least one dissociable salt is selected from the group consisting of LiPF₆, LiClO₄, LiN(CF₃SO₂)₂, LiBF₄, LiCF₃SO₃, and LiSbF₆.

20. A hybrid system according to claim 12 wherein

a) said negative electrode member layer comprises Li₄Ti₅O₁₂,

b) said positive electrode member layer comprises a high surface area activated carbon, and

c) said electrolyte comprises a 1 M solution of LiPF₆ in a 2:

1 mixture of ethylene carbonate;

dimethyl carbonate.