Energy storage device, module thereof and electric vehicle using the same

• US 20060124973A1
• Filed: 12/13/2005
• Published: 06/15/2006
• Est. Priority Date: 12/14/2004
• Status: Abandoned Application

• Current Assignee: Hitachi, Ltd.
• Original Assignee: Hitachi, Ltd.
• Inventors: Kumashiro, Yoshiaki, Yoshikawa, Masanori, Arai, Juichi, Yamaki, Takahiro, Kobayashi, Mituru
• Application Number:
  US11/299,742
• Publication Number:
  US 20060124973A1
• Time in Patent Office: Days
• US Class Current: 257/223
• CPC Class Codes: B60K 6/28 characterised by the electric energy storing means, e.g. batteries or capacitors
• CPC Class Codes: B60K 6/32 characterised by the fuel cells
• CPC Class Codes: B60K 6/48 Parallel type
• CPC Class Codes: B60L 2210/40 DC to AC converters
• CPC Class Codes: B60L 2240/12 Speed
• CPC Class Codes: B60L 2240/545 Temperature
• CPC Class Codes: B60L 2240/547 Voltage
• CPC Class Codes: B60L 2240/549 Current
• CPC Class Codes: B60L 50/16 with provision for separate direct mechanical propulsion
• CPC Class Codes: B60L 50/64 Constructional details of batteries specially adapted for electric vehicles
• CPC Class Codes: B60L 50/66 Arrangements of batteries
• CPC Class Codes: B60L 58/18 of two or more battery modules
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• 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 11/10 Multiple hybrid or EDL capacitors, e.g. arrays or modules housings, cases, encapsulations or mountings thereof H01G11/78
• CPC Class Codes: H01G 11/46 Metal oxides
• CPC Class Codes: H01G 11/60 characterised by the solvent
• CPC Class Codes: H01G 9/035 Liquid electrolytes, e.g. impregnating materials H01G11/54 takes precedence
• CPC Class Codes: H01G 9/22 Devices using combined reduction and oxidation, e.g. redox arrangement or solion
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0567 : characterised by the additives
• CPC Class Codes: H01M 10/0569 : characterised by the solvents
• CPC Class Codes: H01M 2300/0042 : Four or more solvents
• 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: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/62 : Hybrid vehicles
• CPC Class Codes: Y02T 10/70 : Energy storage systems for electromobility, e.g. batteries
• CPC Class Codes: Y02T 10/7072 : Electromobility specific charging systems or methods for batteries, ultracapacitors, supercapacitors or double-layer capacitors
• CPC Class Codes: Y02T 10/72 : Electric energy management in electromobility
• CPC Class Codes: Y02T 90/40 : Application of hydrogen technology to transportation, e.g. using fuel cells

Abstract

An object of the present invention is to provide an energy storage device excellent in input/output characteristics at low temperatures, a module thereof and a vehicle using the module. The present invention provides an energy storage device comprising: a positive electrode having a region where a reaction accompanied by charge exchange occurs; a negative electrode having a region where a reaction accompanied by charge exchange occurs; a separator electrically separating the positive and negative electrodes and allowing mobile ions to pass therethrough; an electrolytic solution having an aprotic nonaqueous solvent comprising the mobile ions; and a region in at least one of the positive and negative electrodes where a charge adsorbing/desorbing reaction occurs.

Claims

1. An energy storage device comprising:

a positive electrode having a region where a reaction accompanied by charge exchange occurs;

a negative electrode having a region where a reaction accompanied by charge exchange occurs;

a separator electrically separating said positive and negative electrodes from each other and allowing mobile ions to pass therethrough;

an electrolytic solution having an aprotic nonaqueous solvent comprising said mobile ions; and

a region in at least one of said positive and negative electrodes where a charge adsorbing/desorbing reaction occurs.

2. The energy storage device according to claim 1, wherein:

said regions where the reaction accompanied by charge exchange occurs are formed in a laminated manner in current collectors; and

said region where the charge adsorbing/desorbing reaction occurs is formed in a laminated manner on the surface of said region where the reaction accompanied by charge exchange occurs.

3. The energy storage device according to claim 1, wherein said region where the reaction accompanied by charge exchange occurs and said region where the charge adsorbing/desorbing reaction occurs are formed on the surfaces of the current collectors in a mixed manner or in an alternate manner.

4. The energy storage device according to claim 1, wherein said nonaqueous solvent comprises at least one solvent selected from the group consisting of solvents represented by the following formulas (1) to (20):

a cyclic carbonate solvent represented by;

wherein R₁, R₂, R₃ and R₄ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group, an allyl group or an acyl group;

or alternatively a fluorinated alkyl, allyl or acyl group; and

R₁, R₂, R₃ and R₄ may be the same or different from each other;

a chain carbonate solvent represented by;

wherein R₅ and R₆ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group; and

R₅ and R₆ may be the same or different from each other;

a chain ester solvent represented by;

wherein R₇ and R₈ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group; and

R₇ and R₈ may be the same or different from each other;

a lactone derivative represented by;

wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group;

or alternatively a fluorinated alkyl, allyl or acyl group; and

R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ may be the same or different from each other;

a dioxolane derivative represented by;

wherein R₁₅, R₁₆, R₁₇, R₁₈, R₁₉ and R₂₀ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group; and

R₁₅, R₁₆, R₁₇, R₁₈, R₁₉ and R₂₀ may be the same or different from each other;

a chain ether derivative represented by;

wherein n is an integer of 1 to 10, R₂₁ is methylene, and R₂₂ is a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group;

a dioxolane derivative represented by;

wherein R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈, R₂₉ and R₃₀ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group; and

R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈, R₂₉ and R₃₀ may be the same or different from each other;

a chain ether derivative represented by;

wherein n is an integer of 1 to 10, R₃₁ and R₃₂ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group; and

R₃₁ and R₃₂ may be the same or different from each other;

a cyclopentane derivative represented by;

wherein R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group; and

R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ may be the same or different from each other;

an alkane represented by;

R₄₁—

R₄₂ 

 

(Formula

     10)

wherein R₄₁ and R₄₂ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group; and

R₄₁ and R₄₂ may be the same or different from each other;

a 1,3-dioxo-4,5-1en-2-one derivative represented by;

wherein R₄₃ and R₄₄ each represent a hydrogen, fluorine, chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group; and

R₄₃ and R₄₄ may be the same or different from each other;

a phenyl derivative represented by;

wherein R₄₅, R₄₆, R₄₇, R₄₈, R₄₉, R₅₀, R₅₁, R₅₂, R₅₃ and R₅₄ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group or a fluorinated alkyl group; and

R₄₅, R₄₆, R₄₇, R₄₈, R₄₉, R₅₀, R₅₁, R₅₂, R₅₃ and R₅₄ may be the same or different from each other;

an ethylene sulfite derivative represented by;

wherein R₅₅, R₅₆, R₅₇ and R₅₈ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group, an allyl group or an acyl group;

or alternatively a fluorinated alkyl, allyl or acyl group; and

R₅₅, R₅₆, R₅₇ and R₅₈ may be the same or different from each other;

a propane sultone derivative represented by

wherein R₅₉, R₆₀, R₆₁, R₆₂, R₆₃ and R₆₄ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group, an allyl group or an acyl group;

or alternatively a fluorinated alkyl, allyl or acyl group; and

R₅₉, R₆₀, R₆₁, R₆₂, R₆₃ and R₆₄ may be the same or different from each other;

a disulfide derivative represented by

R₆₅—

S—

S—

R₆₆ 

 

(Formula

     15)

wherein R₆₅ and R66 each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group, an allyl group or an acyl group;

or alternatively a fluorinated alkyl, allyl, acyl, phenyl, benzyl, diphenyl or terphenyl group;

or alternatively a partially fluorinated phenyl, benzyl, diphenyl or terphenyl group;

or alternatively a partially alkylated, allylated or acylated phenyl, benzyl, diphenyl or terphenyl group; and

R₆₅ and R₆₆ may be the same or different from each other;

a benzene derivative represented by;

wherein R₆₇, R₆₈, R₆₉, R₇₀, R₇₁ and R₇₂ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group, an allyl group, an acyl group or an alkoxy group;

or alternatively a fluorinated alkyl, allyl, acyl or alkoxy group; and

R₆₇, R₆₈, R₆₉, R₇₀, R₇₁, and R₇₂ may be the same or different from each other;

a pyridine derivative represented by;

wherein R₇₃, R₇₄, R₇₅, R₇₆ and R₇₇ each represent a hydrogen, fluorine or chlorine atom;

or alternatively a C_1-3 alkyl group, an allyl group, an acyl group or an alkoxy group;

or alternatively a fluorinated alkyl, allyl, acyl or alkoxy group; and

R₇₃, R₇₄, R₇₅, R₇₆ and R₇₇ may be the same or different from each other;

a chain phosphazene derivative represented by;

wherein R₇₈, R₇₉, R₈₀ and R₈₁ each represent a C_1-3 alkyl group, an allyl group, an acyl group or an alkoxy group;

or alternatively a fluorinated alkyl, allyl, acyl or alkoxy group; and

R₇₈, R₇₉, R₈₀ and R₈₁ may be the same or different from each other;

a cyclic phosphazene derivative represented by;

wherein R₈₂, R₈₃, R₈₄, R₈₅, R₈₆ and R₈₇ each represent a C_1-3 alkyl group, an allyl group, an acyl group or an alkoxy group;

or alternatively a fluorinated alkyl, allyl, acyl or alkoxy group; and

R₈₂, R₈₃, R₈₄, R₈₅, R₈₆ and R₈₇ may be the same or different from each other;

and a phosphate derivative represented by;

wherein R₈₈, R₈₉ and R₉₀ each represent a C_1-3 alkyl group or a fluorinated alkyl group; and

R₈₈, R₈₉ and R₉₀ may be the same or different from each other.

5. The energy storage device according to claim 1, wherein said region where the reaction accompanied by charge exchange occurs in said positive electrode comprises at least one electric energy storing/releasing material selected from the group consisting of LiNi_xMn_yCo_zO₂ (with the proviso that x+y+z=1), a composite oxide comprising Li and one or more transition metals such as Co, Ni, Mn and Fe, and an olivine-structured phosphate compound represented by LiMePO₄ (Me being Fe, Co or Cr).

6. The energy storage device according to claim 1, wherein, said region where the reaction accompanied by charge exchange occurs in said negative electrode comprises at least one electric energy storing/releasing material selected from the group consisting of a carbonaceous material capable of occluding/releasing lithium;

lithium metal;

a lithium alloy;

silicon;

silicon oxides;

tin;

tin oxides; and

composite materials composed of the carbonaceous material and one or more of lithium metal, a lithium alloy, silicon, silicon oxides, tin and tin oxides.

7. The energy storage device according to claim 1, wherein said region where the charge adsorbing/desorbing reaction occurs comprises at least one selected from the group consisting of activated carbon, carbon nanotube, expanded graphite, ruthenium oxide, titanium oxide, and composite materials composed of the activated carbon and one or more of carbon nanotube, expanded graphite, ruthenium oxide and titanium oxide.

8. The energy storage device according to claim 1, wherein said electrolytic solution comprises at least one solute selected from the group consisting of LiPF₆, LiAsF₆, LiBF₄, LiSO₂CF₃, LiN[SO₂CF₃]₂, LiN[SO₂CF₂CF₃]₂, LiC[SO₂CF₃]₃, LiC[SO₂CF₂CF₃]₂, LiB[OCOCF₃]₄, LiB[OCOCF₂CF₃]₄, LiI, LiBr, LiCl, NaPF₆, NaAsF₆, NaBF₄, NaSO₂CF₃, NaN[SO₂CF₃]₂, NaN[SO₂CF₂CF₃]₂, NaC[SO₂CF₃]₃, NaC[SO₂CF₂CF₃]₂, NaB[OCOCF₃]₄, NaB[OCOCF₂CF₃]₄, Nal, NaBr and NaCl.

9. The energy storage device according to claim 1, wherein said electrolytic solution comprises at least one selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC), at least one selected from the group consisting of dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC), and at least one selected from the group consisting of LiPF_{6, LiBF4, LiSO2CF3, LiN[SO2}CF₃]₂, LiN[SO₂CF₂CF₃]₂, LiC[SO₂CF₃]₃, LiC[SO₂CF₂CF₃]₂, LiB[OCOCF₃]₄ and LiB[OCOCF₂CF₃]₄.

10. The energy storage device according to claim 9, wherein said electrolytic solution comprises at least one selected from the group consisting of methyl acetate (MA), ethyl acetate (EA), methyl propionate (MP) and ethyl propionate (ME).

11. The energy storage device according to claim 9, wherein said electrolytic solution comprises at least one selected from the group consisting of nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether and heptafluorocyclopentane.

12. The energy storage device according to claim 9, wherein said electrolytic solution comprises at least one selected from the group consisting of vinylene carbonate, ethylene sulfide, propane sultone, diphenyl disulfide, methoxybenzene, methoxypyridine and hexamethylcyclophosphazene.

13. A secondary battery which is a coin-shaped or cylindrical battery comprising the energy device according to claim 1.

14. A redox capacitor comprising the energy device according to claim 1.

15. An energy device module comprising a plurality of the energy storage devices according to claim 1 connected to each other in series, in parallel, or in series-parallel, and a control circuit for controlling at least any one of the current and the voltage of an electric circuit formed by said connection.

16. An electric vehicle comprising the energy storage device module according to claim 15 mounted therein and an electric motor driven by the power supplied by said module.

17. A hybrid vehicle comprising the energy storage device module according to claim 15 mounted therein, and an electric motor driven by the power supplied by said module and an internal combustion engine.