CN101740809A - Large-capacity power lithium battery and preparation method thereof - Google Patents
Large-capacity power lithium battery and preparation method thereof Download PDFInfo
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- CN101740809A CN101740809A CN200910214214A CN200910214214A CN101740809A CN 101740809 A CN101740809 A CN 101740809A CN 200910214214 A CN200910214214 A CN 200910214214A CN 200910214214 A CN200910214214 A CN 200910214214A CN 101740809 A CN101740809 A CN 101740809A
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- lithium battery
- positive electrode
- negative electrode
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 27
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 15
- 239000011149 active material Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 27
- 239000011267 electrode slurry Substances 0.000 claims description 24
- -1 modified lithium titanate Chemical class 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000005030 aluminium foil Substances 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000011265 semifinished product Substances 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 150000002632 lipids Chemical class 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 4
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 238000005476 soldering Methods 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 238000012858 packaging process Methods 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims 1
- 229910013075 LiBF Inorganic materials 0.000 claims 1
- 229910013063 LiBF 4 Inorganic materials 0.000 claims 1
- 229910013684 LiClO 4 Inorganic materials 0.000 claims 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000010409 thin film Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 229910013716 LiNi Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 1
- DJZIBVUGARDLOC-UHFFFAOYSA-N [Ni]=O.[Co]=O.[Li] Chemical compound [Ni]=O.[Co]=O.[Li] DJZIBVUGARDLOC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001500 lithium hexafluoroborate Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a large-capacity power lithium battery which can be used in the field of vehicles as a power source and a preparation method thereof. The large-capacity power lithium battery of the invention is prepared by stacking and packaging a positive electrode, the thin film of a gel-state polymer electrolyte and a negative electrode, wherein the active material of the negative electrode is modified lithium titanate, the active material of the positive electrode is one or more of a ternary material, lithium manganate and ferric lithium manganate, and the thin film of the gel-state polymer electrolyte is prepared by mixing and drying a lithium salt, the solution of an organic solvent and a conductive polymer solution. The power lithium battery has the characteristics of environmental friendliness, excellent high magnification performance, excellent heat dispersion and the like. The preparation is simple, environmental pollution and leakage do not exist, the storage service life is long, enlargement is easy and the temperature range for use is wide. The large-capacity power lithium battery can be used as the power source and applied to the fields such as hybrid electric vehicle, electric vehicle and the like.
Description
Technical field
The invention belongs to the lithium battery energy technology field, specially refer to a kind of large-capacity power lithium battery and preparation method thereof.
Background technology
Along with social development and scientific and technological progress, people are increasing to the demand of the energy.Compare traditional lead acid accumulator, Ni-Cd, Ni-MH battery, that lithium-ions battery has is environmentally friendly, specific energy is high (140Wh/kg), the voltage platform height, have extended cycle life, characteristics such as self discharge is little, memory-less effect, be widely used in military, civil area, comprise 3C electronic product, various electric tools etc., and be hopeful to be applied to hybrid vehicle, electric automobile field as power source.
Lithium battery technology is ripe not enough at present, has some problems, and particularly the monomer capacity is little, and this shortcoming has limited the application of lithium ion battery at automotive field greatly.The disclosed a kind of lithium battery of patent CN200810066054.2 for example, its negative electrode adopts the lithium titanate active material that accounts for 90%～93% mass ratio, positive electrode adopts the phosphoric acid vanadium lithium active material that accounts for 88%～90% mass ratio, electrolyte adopts ethylene carbonate (EC), propene carbonate (DMC), methyl ethyl carbonate organic solvents such as (EMC), and its lithium ion single electrokinetic cell capacity has only 335～345mAh; The lithium battery of the disclosed a kind of quickly-chargeable of patent CN200810052728.3 for example again, its positive electrode active substance is LiMn2O4 (LiMn
2O
4), LiFePO4 (LiFePO
4), lithium nickel cobalt dioxide (LiNi
xCo
yM
zO
2) and ternary material (LiNi
xMn
xCo
1-2xO
2) in one or more, or cobalt acid lithium (LiCoO
2) and a kind of mixture wherein; Negative electrode active material is the submicron order lithium titanate; Electrolyte is lithium hexafluoro phosphate (LiPF
6), solvent is the multicomponent mixture of ethene carbonic ether (EC), dimethyl carbonic ether (DMC) and ethyl-methyl carbonic ether (EMC), this lithium cell capacity has only mAh more than 400.Above-mentioned two kinds of lithium batteries all can't be applied to hybrid vehicle, electric automobile field as power source.
Summary of the invention
First purpose of the present invention is to propose a kind of large-capacity power lithium battery that power source is applied to automotive field that can be used as.
Large-capacity power lithium battery of the present invention is formed by piling up, encapsulating by the film and the negative electrode of positive electrode, gel polymer electrolyte, wherein negative electrode and positive electrode are isolated by the film of gel polymer electrolyte, and key is that the active material of described negative electrode is a modified lithium titanate; The active material of described positive electrode is one or more in ternary material, LiMn2O4 and the LiFePO4; The film of described gel polymer electrolyte by the solution of lithium salts, organic solvent mix with conductive polymer solution, drying forms.
Large-capacity power lithium battery of the present invention is owing to adopted modified lithium titanate (Li
4Ti
5O
12/ C) as the active material of negative electrode, with ternary material (LiNi
xMn
y Co
1-x-yO2 or LiNi
xCo
yAl
1-x-yO
2), LiMn2O4 (LiMn
2O
4) and LiFePO4 (LiFePO
4) in one or more as active positive electrode material, its thermal stability and structural stability are better, the cell capacity has higher safety performance about 20Ah～50Ah, good high rate capability, excellent cycle performance and long circulation life.
The granularity of described modified lithium titanate is less than 1 μ m, and specific surface is greater than 2.0m2/g.
The solute of described conductive polymer solution is one or more mixtures in the homopolymers of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, oxireme-propylene oxide or copolymer, polymethyl methacrylate, polyacrylonitrile, the polyurethane, and the solvent in the conductive polymer solution is one or more mixed solvents in ketones solvent, lipid solvent and the jeterocyclic chemistry solvent.
Described ketones solvent is one or both mixed solvents in acetone, the methylethylketone, described lipid solvent is one or more mixed solvents in carbonic acid diethyl ester, carbonic acid dipropyl fat, ethyl acetate, methyl acetate, glycol sulfite, the inferior propyl ester of sulfurous acid, and described jeterocyclic chemistry solvent is one or both mixed solvents in r-butyrolactone, the oxolane.
Described lithium salts is one or more mixtures among LiPF6, LiClO4, LiBOB, LiBF4, LiBF6, LiAsF6, LiCF3SO3, LiN (SO2C2F5) 2 and the LiN (SO2C2F5) 2.
Described organic solvent can adopt ketone or lipid organic solvent, does not have special requirement.
Second purpose of the present invention is the preparation method who proposes above-mentioned large-capacity power lithium battery, and this preparation method may further comprise the steps:
A: the binding agent that will contain the conductive agent of modified lithium titanate, 1%～15% weight of 75%～98% weight and 1%～10% weight is dissolved in makes the negative electrode slurry in the solvent, with the Copper Foil that 9 μ m～13 μ m are thick is collector, be coated on the Copper Foil positive and negative negative electrode slurry and drying, make pole piece, then pole piece is rolled, shears, make negative electrode;
B: the binding agent that will contain the conductive agent of active positive electrode material, 1%～10% weight of 80%～98% weight and 1%～10% weight is dissolved in makes the positive electrode slurry in the solvent, with the aluminium foil that 15 μ m～20 μ m are thick is collector, be coated on the aluminium foil positive and negative positive electrode slurry and drying, make pole piece, then pole piece is rolled, shears, make positive electrode;
C: lithium salts is dissolved in makes potassium salt soln in the organic solvent, and be applied on the surface of polyethylene porous membrane or electrode after conductive polymer solution mixes, obtain the film of gel polymer electrolyte after the drying;
D: successively by piling up, obtaining the dynamic lithium battery semi-finished product behind the coating, soldering polar ear, packaging process, wherein negative electrode and positive electrode are isolated by the film of gel polymer electrolyte with the film of above-mentioned negative electrode, positive electrode and gel polymer electrolyte;
E: with the dynamic lithium battery semi-finished product that obtain in the D step change into, partial volume, detection, obtain the dynamic lithium battery finished product.
In the above-mentioned A step, the coated weight of negative electrode slurry on negative electrode is less than 40mg/cm2.
In the above-mentioned B step, the coated weight of positive electrode slurry on positive electrode is less than 40mg/cm2.
Conductive agent described in above-mentioned A, the B step is one or more the mixture in super conductive black, electrically conductive graphite or the electrical-conductive nanometer carbon pipe; Described binding agent is one or more the mixture in polytetrafluoroethylene, Kynoar or the polymer resin; Solvent in positive electrode slurry and the negative electrode slurry is N-methyl pyrrolidone or dimethylformamide or dimethylacetylamide.
Dynamic lithium battery of the present invention has characteristics such as environmentally friendly, good high rate capability, good performance of heat dissipation, and preparation is simple, there is not environmental pollution, do not have and leak, storage life is long, be easy to maximize, the serviceability temperature wide ranges can be used as power source and is applied in fields such as hybrid-electric car, electric automobile.
Description of drawings
Fig. 1 is preparation method's flow chart of large-capacity power lithium battery of the present invention;
Fig. 2 is the stack manner figure of film of positive electrode, negative electrode and the gel polymer electrolyte of large-capacity power lithium battery of the present invention.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiments and the drawings.
Embodiment 1:
The large-capacity power lithium battery of present embodiment, press cell rated capacity 10Ah design, film and negative electrode by positive electrode, gel polymer electrolyte form by piling up, encapsulating, wherein negative electrode and positive electrode are isolated by the film of gel polymer electrolyte, key is that the active material of described negative electrode is that particle diameter is 0.165 μ m, and specific area is 9.2m
2The modified lithium titanate of/g; The active material of described positive electrode is a ternary material; The film of described gel polymer electrolyte by the solution of lithium salts, organic solvent mix with conductive polymer solution, drying forms, as shown in Figure 1, its concrete preparation method is as follows:
A: with the modified lithium titanate of 84% weight, the conductive carbon black of 7% weight and the Kynoar of 9% weight is solute, with the N-methyl pyrrolidone is the negative electrode slurry of solvent furnishing paste, make collector with the thick Copper Foil of 10 μ m, the negative electrode slurry is coated onto on the positive and negative of Copper Foil and after under 120 ℃ of conditions dry 6 hours and makes pole piece, then pole piece is rolled, shears, make negative electrode, the density of negative electrode is 4.6g/cm3;
B: will contain the ternary material of 95% weight, the acetylene black of 1.5% weight, the conductive carbon black of 1.5% weight, the Kynoar of 4% weight is solute, with the N-methyl pyrrolidone is the positive electrode slurry of solvent furnishing paste, with the thick aluminium foil of 15 μ m as collector, the positive electrode slurry is coated on the positive and negative of aluminium foil and under 120 ℃ of conditions dry 8 hours, make pole piece, then pole piece rolled, shear and make positive electrode, the density of positive electrode is 3.8g/cm3;
C: with lithium salts LiPF
6Be dissolved in and make potassium salt soln in the organic solvent, and be applied on the surface of polyethylene porous membrane after conductive polymer solution mixes, obtain the film of gel polymer electrolyte after the drying, wherein the solute of conductive polymer solution is a vinylidene fluoride-hexafluoropropylene copolymer, and solvent is the mixture of carbonic acid diethyl ester, carbonic acid dipropyl fat;
D: with the film of above-mentioned negative electrode, positive electrode and gel polymer electrolyte successively by pile up, coating, soldering polar ear, with obtaining the dynamic lithium battery semi-finished product after the operations such as aluminum-plastic composite membrane encapsulation, negative electrode 1 and positive electrode 2 are isolated by the film 3 of gel polymer electrolyte when piling up as shown in Figure 2;
E: with the dynamic lithium battery semi-finished product that obtain in the D step change into, partial volume, detection, obtain the dynamic lithium battery finished product.
Through test, the internal resistance of the dynamic lithium battery of present embodiment is 2.4m Ω, and capacity is 21.93Ah, and open circuit voltage is 2.436V, and the voltage platform of 2.212V appears in battery, and the conservation rate of 500 circulation back battery capacities is 96.86%.
Embodiment 2:
The large-capacity power lithium battery of present embodiment, press cell rated capacity 40Ah design, film and negative electrode by positive electrode, gel polymer electrolyte form by piling up, encapsulating, wherein negative electrode and positive electrode are isolated by the film of gel polymer electrolyte, key is that the active material of described negative electrode is that particle diameter is 0.165 μ m, and specific area is 9.2m
2The modified lithium titanate of/g; The active material of described positive electrode is a ternary material; The film of described gel polymer electrolyte by the solution of lithium salts, organic solvent mix with conductive polymer solution, drying forms, as shown in Figure 1, its concrete preparation method is as follows:
A: with the modified lithium titanate of 84% weight, the conductive carbon black of 7% weight and the Kynoar of 9% weight is solute, with the N-methyl pyrrolidone is the negative electrode slurry of solvent furnishing paste, make collector with the thick Copper Foil of 10 μ m, the negative electrode slurry is coated onto on the positive and negative of Copper Foil and after under 120 ℃ of conditions dry 6 hours and makes pole piece, then pole piece is rolled, shears, make negative electrode, the density of negative electrode is 4.6g/cm3;
B: will contain the LiMn2O4 of 93% weight, the acetylene black of 1.5% weight, the conductive carbon black of 2% weight, the Kynoar of 3.5% weight is solute, with the N-methyl pyrrolidone is the positive electrode slurry of solvent furnishing paste, with the thick aluminium foil of 15 μ m as collector, the positive electrode slurry is coated on the positive and negative of aluminium foil and under 120 ℃ of conditions dry 8 hours, make pole piece, then pole piece rolled, shear and make positive electrode, the density of positive electrode is 3.8g/cm3;
C: with lithium salts LiPF
6Be dissolved in and make potassium salt soln in the organic solvent, and be applied on the surface of polyethylene porous membrane after conductive polymer solution mixes, obtain the film of gel polymer electrolyte after the drying, wherein the solute of conductive polymer solution is a vinylidene fluoride-hexafluoropropylene copolymer, and solvent is the mixture of carbonic acid diethyl ester, carbonic acid dipropyl fat;
D: with the film of above-mentioned negative electrode, positive electrode and gel polymer electrolyte successively by pile up, coating, soldering polar ear, with obtaining the dynamic lithium battery semi-finished product after the operations such as aluminum-plastic composite membrane encapsulation, negative electrode 1 and positive electrode 2 are isolated by the film 3 of gel polymer electrolyte when piling up as shown in Figure 2;
E: with the dynamic lithium battery semi-finished product that obtain in the D step change into, partial volume, detection, obtain the dynamic lithium battery finished product.
Through test, the internal resistance of the dynamic lithium battery of present embodiment is 2.35m Ω, and capacity is 43.74Ah, and open circuit voltage is 2.537V, and the voltage platform of 2.364V appears in battery, and the conservation rate of 500 circulation back battery capacities is 87.68%.
Claims (9)
1. large-capacity power lithium battery, film and negative electrode by positive electrode, gel polymer electrolyte form by piling up, encapsulating, wherein negative electrode and positive electrode are isolated by the film of gel polymer electrolyte, and the active material that it is characterized in that described negative electrode is a modified lithium titanate; The active material of described positive electrode is one or more in ternary material, LiMn2O4 and the LiFePO4; The film of described gel polymer electrolyte by the solution of lithium salts, organic solvent mix with conductive polymer solution, drying forms.
2. large-capacity power lithium battery according to claim 1, the granularity that it is characterized in that described modified lithium titanate is less than 1 μ m, and specific surface is greater than 2.0m
2/ g.
3. large-capacity power lithium battery according to claim 1, the solute that it is characterized in that described conductive polymer solution is one or more mixtures in the homopolymers of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, oxireme-propylene oxide or copolymer, polymethyl methacrylate, polyacrylonitrile, the polyurethane, and the solvent in the conductive polymer solution is one or more mixed solvents in ketones solvent, lipid solvent and the jeterocyclic chemistry solvent.
4. large-capacity power lithium battery according to claim 3, it is characterized in that described ketones solvent is one or both mixed solvents in acetone, the methylethylketone, described lipid solvent is one or more mixed solvents in carbonic acid diethyl ester, carbonic acid dipropyl fat, ethyl acetate, methyl acetate, glycol sulfite, the inferior propyl ester of sulfurous acid, and described jeterocyclic chemistry solvent is one or both mixed solvents in r-butyrolactone, the oxolane.
5. according to claim 1 or 2 or 3 or 4 described large-capacity power lithium batteries, it is characterized in that described lithium salts is LiPF
6, LiClO
4, LiBOB, LiBF
4, LiBF
6, LiAsF
6, LiCF
3SO
3, LiN (SO
2C
2F
5)
2And LiN (SO
2C
2F
5)
2In one or more mixtures.
6. the preparation method of a large-capacity power lithium battery is characterized in that may further comprise the steps:
A: the binding agent that will contain the conductive agent of modified lithium titanate, 1%～15% weight of 75%～98% weight and 1%～10% weight is dissolved in makes the negative electrode slurry in the solvent, with the Copper Foil that 9 μ m～13 μ m are thick is collector, be coated on the Copper Foil positive and negative negative electrode slurry and drying, make pole piece, then pole piece is rolled, shears, make negative electrode;
B: the binding agent that will contain the conductive agent of active positive electrode material, 1%～10% weight of 80%～98% weight and 1%～10% weight is dissolved in makes the positive electrode slurry in the solvent, with the aluminium foil that 15 μ m～20 μ m are thick is collector, be coated on the aluminium foil positive and negative positive electrode slurry and drying, make pole piece, then pole piece is rolled, shears, make positive electrode;
C: lithium salts is dissolved in makes potassium salt soln in the organic solvent, and be applied on the surface of polyethylene porous membrane or electrode after conductive polymer solution mixes, obtain the film of gel polymer electrolyte after the drying;
D: successively by piling up, obtaining the dynamic lithium battery semi-finished product behind the coating, soldering polar ear, packaging process, wherein negative electrode and positive electrode are isolated by the film of gel polymer electrolyte with the film of above-mentioned negative electrode, positive electrode and gel polymer electrolyte;
E: with the dynamic lithium battery semi-finished product that obtain in the D step change into, partial volume, detection, obtain the dynamic lithium battery finished product.
7. the preparation method of large-capacity power lithium battery according to claim 6 is characterized in that in the A step, and the coated weight of negative electrode slurry on negative electrode is less than 40mg/cm
2
8. the preparation method of large-capacity power lithium battery according to claim 6 is characterized in that in the B step, and the coated weight of positive electrode slurry on positive electrode is less than 40mg/cm
2
9. the preparation method of large-capacity power lithium battery according to claim 6 is characterized in that the conductive agent described in A, the B step is one or more the mixture in super conductive black, electrically conductive graphite or the electrical-conductive nanometer carbon pipe; Described binding agent is one or more the mixture in polytetrafluoroethylene, Kynoar or the polymer resin; Solvent in positive electrode slurry and the negative electrode slurry is N-methyl pyrrolidone or dimethylformamide or dimethylacetylamide.
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| CN200910214214A CN101740809A (en) | 2009-12-29 | 2009-12-29 | Large-capacity power lithium battery and preparation method thereof |
| PCT/CN2010/080001 WO2011079735A1 (en) | 2009-12-29 | 2010-12-20 | High capacity power lithium ion battery and preparation method thereof |
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| US6881515B2 (en) * | 2001-05-08 | 2005-04-19 | Celgard Inc. | Separator for polymer battery |
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| CN101740809A (en) * | 2009-12-29 | 2010-06-16 | 奇瑞汽车股份有限公司 | Large-capacity power lithium battery and preparation method thereof |
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2009
- 2009-12-29 CN CN200910214214A patent/CN101740809A/en active Pending
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