High energy density hybrid battery/supercapacitor system

• US 6,517,972 B1
• Filed: 09/29/2000
• Issued: 02/11/2003
• Est. Priority Date: 09/29/2000
• Status: Expired due to Term

• Current Assignee: Rutgers University
• Original Assignee: Telcordia Technologies Incorporated (Telefonaktiebolaget LM Ericsson)
• Inventors: Amatucci, Glenn
• Primary Examiner(s): Chaney, Carol
• Assistant Examiner(s): Martin, Angela J
• Application Number:
  US09/650,364
• Time in Patent Office: 865 Days
• Field of Search: 429/231.8, 429/231.95, 429/231.9, 429/231.1, 429/9, 361/503, 361/502, 361/504-512
• US Class Current: 429/231.1
• 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 11/28 arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
• CPC Class Codes: H01G 11/34 characterised by carbonisation or activation of carbon
• CPC Class Codes: H01G 11/50 specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• CPC Class Codes: H01G 11/62 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 2300/0025 Organic electrolyte
• 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 4/362 Composites
• 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 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• 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 a negative intercalation electrode (17) and a positive capacitor electrode (13) comprising an anion-adsorbing component and a cation-intercalating material 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, supplemented by cations supplied from the positive electrode intercalation material in order to increase the energy density capability of the system, respectively reversibly intercalate into the negative electrode (17) and capacitively adsorb at the surface of the positive electrode (13) upon the application of charging current. The high density stored electrical energy may be rapidly recovered at high power over extended periods upon demand of a utilizing device and may be equally rapidly restored to stable high energy 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 pair of ion species of a dissociable salt characterized in that one of said electrode members comprises a first material capable of intercalating the cation of said species in response to the application of an electrical charge of a first polarity, and the other of said electrode members comprises a combination of

a) a second material capable of adsorbing the anion of said species in response to the application of a contemporaneous electrical charge of opposite polarity, and

b) a third material capable of yielding said cation species in response to the application of said contemporaneous electrical charge of opposite polarity, said third material being selected from the group consisting of lithiated transition metal oxides, sulfides, phosphates, and fluorides.

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

3. A storage system according to claim 1 wherein said anion species is selected from the group consisting of PF₆, ClO₄, BF₄, CF₃SO₃, and AsF₆.

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

5. A storage system according to claim 2 wherein said cation species is lithium and said third electrode member material is a lithiated transition metal oxide intercalation compound.

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

7. A storage system according to claim 4 wherein said third electrode member material is selected from the group consisting of lithiated transition metal oxide spinel compounds.

8. A storage system according to claim 7 wherein said first electrode member material is Li₄Ti₅O₁₂.

9. A storage system according to claim 6 wherein said second electrode member 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 M 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 LiAsF₆.

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 pair of ion species of a dissociable salt characterized in that

a) one of said electrode members comprises a first material capable of reversibly intercalating the cation of said species in response to the application of an electrical charge of a first polarity,

b) the other of said electrode members comprises

a second material capable of reversibly adsorbing the anion of said species in response to the application of a contemporaneous electrical charge of opposite polarity, and a third material capable of reversibly deintercalating said cation species in response to the application of said contemporaneous electrical charge of opposite polarity, said third material being selected from the group consisting of lithiated transition metal oxides, sulfides, phosphates, and fluorides,

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 one or more contiguous members at its respective interface to form a unitary laminate structure.

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

14. A hybrid system according to claim 12 wherein

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

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 electrode member material is selected from the group consisting of transition metal oxides, sulfides, phosphates, and fluorides, alkali and alkaline earth metal-alloying metals and compounds, and open-structured carbonaceous materials.

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

17. A hybrid system according to claim 12 wherein said third electrode member material is selected from the group consisting of lithiated transition metal oxide intercalation compounds.

18. A hybrid system according to claim 12 wherein

a) said first electrode member material comprises Li₄Ti₅O₁₂,

b) said second electrode member material comprises a high surface area activated carbon,

c) said third electrode member material comprises LiMn₂O₄, and

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

1 mixture of ethylene carbonate;

dimethyl carbonate.

19. A method of improving the high energy charge capacity of a hybrid rechargeable electrical energy storage system comprising a separator member containing a fluid electrolyte comprising a pair of ion species of a dissociable salt interposed between a first electrode member comprising a first material capable of reversibly combining a first of said ion species in response to the application of an electrical charge of a first polarity and a second electrode member comprising a second material capable of reversibly adsorbing the second of said ion species in response to the application of a contemporaneous electrical charge of opposite polarity, said method comprising incorporating into said second electrode member a third material capable of reversibly yielding said first ion species in response to the application of said contemporaneous electrical charge of opposite polarity, said third material being selected from the group consisting of lithiated transition metal oxides, sulfides, phosphates, and fluorides.

20. A method according to claim 19 wherein

a) said first ion species comprises lithium,

b) said first electrode member material is selected from the group consisting of lithium intercalating and lithium alloying metals and compounds, and open-structured carbonaceous materials,

c) said second electrode member material comprises a high surface area activated carbon, and

d) said third electrode member material comprises a lithiated transition metal oxide intercalation compound.