CN114203985B - Wide-temperature-range lithium ion battery and preparation method thereof - Google Patents
Wide-temperature-range lithium ion battery and preparation method thereof Download PDFInfo
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- CN114203985B CN114203985B CN202111314159.7A CN202111314159A CN114203985B CN 114203985 B CN114203985 B CN 114203985B CN 202111314159 A CN202111314159 A CN 202111314159A CN 114203985 B CN114203985 B CN 114203985B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910021383 artificial graphite Inorganic materials 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 35
- 230000004913 activation Effects 0.000 claims abstract description 30
- 238000001994 activation Methods 0.000 claims abstract description 30
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011267 electrode slurry Substances 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000004806 packaging method and process Methods 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 4
- 238000009517 secondary packaging Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 19
- 239000011163 secondary particle Substances 0.000 claims description 18
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 13
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 13
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 12
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 11
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000011265 semifinished product Substances 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002985 plastic film Substances 0.000 claims description 6
- 229920006255 plastic film Polymers 0.000 claims description 6
- 229940090181 propyl acetate Drugs 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 238000003466 welding Methods 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 238000002347 injection Methods 0.000 abstract description 7
- 239000007924 injection Substances 0.000 abstract description 7
- 230000035939 shock Effects 0.000 abstract description 6
- 238000005755 formation reaction Methods 0.000 abstract description 2
- 238000005259 measurement Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 21
- 239000004698 Polyethylene Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 239000002033 PVDF binder Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 239000006256 anode slurry Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 238000005524 ceramic coating Methods 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000011224 oxide ceramic Substances 0.000 description 5
- 229910052574 oxide ceramic Inorganic materials 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 4
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
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- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
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- 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
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
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- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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- 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
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- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium ion battery with a wide temperature range and a preparation method thereof, and belongs to the technical field of lithium ion batteries, wherein a positive plate, a negative plate and a diaphragm are laminated to form a laminated body, and positive lugs and negative lugs are fixed on the laminated body, and then the laminated body is prepared by packaging, short circuit measurement, corner pressing, baking, electrolyte injection, pre-sealing, activation, formation, secondary packaging and capacity division; the positive plate comprises positive slurry prepared from a mixed material of lithium cobaltate and lithium iron phosphate; the negative plate comprises negative electrode slurry prepared from artificial graphite. The lithium ion battery can be used under the wide temperature range condition of-40-70 ℃, the normal temperature power of the lithium ion battery can reach 5.0 ℃, the lithium ion battery has the characteristic of high multiplying power density, and meanwhile, the overcharge performance, overdischarge performance, high-temperature short circuit, thermal shock and needling safety performance of the lithium ion battery are ensured.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, in particular to a lithium ion battery, and relates to a lithium ion battery with a wide temperature range and a preparation method thereof.
Background
The lithium ion battery is used as a secondary battery, has the characteristics of high capacity, small volume, light weight, long cycle life, no memory effect, no pollution and the like, and is widely applied to various fields of mobile phones, notebook computers, electric bicycles, electric tools, digital cameras and the like, and the application range of the lithium ion battery is wider and wider along with the development of the high-speed lithium ion battery.
In recent years, the demand of the global market for low-temperature lithium ion batteries is increased by more than 20%, the lithium ion batteries are rapidly reduced in discharge at low temperature due to the chemical characteristics of the lithium ion batteries, the discharge current and the discharge time are greatly limited, the batteries fail, the low-temperature lithium ion batteries can improve the discharge characteristics at low temperature to a certain extent, but the problem is that, on one hand, if the low-temperature performance of the lithium ion batteries with high power density is improved, the high-temperature performance is poor, the safety performance of the batteries is greatly influenced, the needling resistance is not realized, on the other hand, if the safety performance of the batteries including the needling resistance performance is met, the correspondingly high-temperature performance is improved, the realization of high-power discharge at low temperature is very difficult, and the capacity recovery problem of the lithium ion batteries after being stored at the wide temperature range (-40 to 70 ℃) condition and the storage condition of the lithium ion batteries with high safety at the temperature range of minus 55 ℃ is difficult to study on the high-power density lithium ion batteries and the preparation method thereof.
Disclosure of Invention
The invention aims to provide a wide-temperature-range lithium ion battery and a preparation method thereof, and aims to solve the existing problems.
In order to achieve the above purpose, the invention adopts the following technical scheme: the lithium ion battery with the wide temperature range comprises a positive plate, a negative plate, a diaphragm, electrolyte, a positive lug, a negative lug and an aluminum plastic packaging film; the positive plate comprises positive slurry prepared from a mixed material of lithium cobaltate and lithium iron phosphate and aluminum foil used for coating the positive slurry; the negative plate comprises negative electrode slurry prepared from artificial graphite as a raw material and copper foil used for coating the negative electrode slurry.
As another embodiment of the present application, the positive electrode slurry includes 65 to 69wt% of a positive electrode solid material and the remaining amide-based solvent;
The amide solvent is N-methyl pyrrolidone;
The positive electrode solid substance comprises the following components in parts by weight: 94-96.5 parts of lithium cobaltate and lithium iron phosphate mixed material, 1.3-2.5 parts of conductive agent, 0.7-1.2 parts of conductive carbon black and 1.5-2.3 parts of binder;
the viscosity of the positive electrode slurry is 6000+/-2000 mPa.s;
The binder is polyvinylidene fluoride.
As another embodiment of the present application, the lithium cobaltate and lithium iron phosphate mixed material comprises the following components in weight ratio of 7-8: 2-3 of lithium cobalt oxide and lithium iron phosphate.
As another embodiment of the present application, the negative electrode slurry includes 48 to 50wt% of a negative electrode solid substance and the remaining polar solvent;
The polar solvent is water;
The negative electrode solid substance comprises the following components in parts by weight: 94-96 parts of artificial graphite, 1.2-2.0 parts of conductive agent, 1.3-2.0 parts of sodium carboxymethylcellulose and 1.5-2.0 parts of adhesive;
The viscosity of the negative electrode slurry is 2000+/-1000 mPa.s;
the aqueous binder is styrene butadiene latex binder, namely SBR binder.
As another embodiment of the application, the artificial graphite is prepared from the following components in percentage by weight: 4-6, and mixing the secondary particle artificial graphite with small particle size;
the particle size of the secondary particle artificial graphite is 13-17 mu m;
The particle size of the small-particle-size secondary particle artificial graphite is 5.5-9.5 mu m.
As another embodiment of the application, the membrane is formed by respectively coating aluminum oxide ceramic layers with the thickness of 3-4 mu m on two sides of a base membrane with the thickness of 9-12 mu m, and respectively coating plastic materials with the thickness of 2-3 mu m on the ceramic layers;
the plastic material is polyvinylidene fluoride;
The base film is made of polyethylene material;
the diaphragm is made of polyethylene material with ceramic glue coated on both sides;
the porosity of the diaphragm is 47-50%.
As another embodiment of the present application, the electrolyte includes, in parts by weight:
① Lithium salt: 12-15 parts of lithium hexafluorophosphate (LiPF 6) and 1-5 parts of lithium bistrifluoromethylsulfonyl imide (LiTFSI);
② Organic solvent: 50-55 parts of methyl ethyl carbonate (EMC), 8-12 parts of propyl acetate (EP), 10-15 parts of Ethylene Carbonate (EC) and 3-5 parts of Propylene Carbonate (PC);
③ Additive: 0.5 to 3 parts of Vinylene Carbonate (VC), 0.5 to 3 parts of Propane Sultone (PS) and 0.5 to 2 parts of vinyl sulfate (DTD).
The invention also provides a preparation method of the lithium ion battery with the wide temperature range, which comprises the steps of taking a positive plate, a negative plate and a diaphragm to form a lamination body, fixing a positive lug and a negative lug on the obtained lamination body, then filling an aluminum plastic film, and obtaining the lithium ion battery with the wide temperature range through packaging, short circuit measurement, angle pressing, baking, electrolyte injection, pre-packaging, activation, formation, secondary packaging and capacity division.
As another embodiment of the application, the activation temperature is 40-45 ℃ and the activation time is 48-60 hours;
The activation is that firstly, the vertical air bag end of the pre-sealed battery obtained by pre-sealing is upwards, the pre-sealed battery is put into a liquid injection tray for activation for 20-24 h, then the battery is horizontally placed in the tray with the vertical air bag end facing the right side of the battery, activation is carried out for 14-18 h, then the battery is horizontally placed in the tray with the turnover surface of the battery and the vertical air bag end facing the left side of the battery, and activation is carried out for 14-18 h.
As another embodiment of the application, the surface pressure of the formation is 0.2-0.3 mPa, and the temperature is 55+ -2 ℃;
the activated battery obtained after the formation and activation is kept stand for 3min under the conditions that the surface pressure is 0.2-0.3 mPa and the temperature is 53-57 ℃, then is charged for 60min by constant current with the current of 0.2C and the voltage of less than or equal to 4.05V, is kept stand for 1min, and is charged for 50min by constant current with the current of 0.6C and the voltage of less than or equal to 4.2V.
The wide-temperature-range lithium ion battery and the preparation method thereof provided by the invention have the beneficial effects that: compared with the prior art, the lithium ion battery can be used under the wide temperature range condition of-40-70 ℃, wherein the discharge capacity of 2.0C under the condition of-40 ℃ can reach more than 50% of the nominal capacity, the recovery capacity of the lithium ion battery after being stored for 48 hours under the condition of 70 ℃ is more than 90%, the recovery capacity of the lithium ion battery after being stored for 24 hours under the condition of-55 ℃ is more than 90%, the normal temperature power of the lithium ion battery can reach 5.0C, the lithium ion battery has the characteristic of high multiplying power density, and meanwhile, the overcharge performance, the overdischarge performance, the high temperature short circuit, the thermal shock and the needling safety performance of the lithium ion battery are also ensured;
the lithium cobalt oxide and lithium iron phosphate mixed material is adopted in the positive electrode slurry, so that the passing rate of the overcharge performance, the overdischarge performance, the high-temperature short circuit, the thermal shock and the needling safety performance of the lithium ion battery can be effectively improved;
The negative electrode slurry adopts a material system prepared by mixing and doping secondary particle artificial graphite and small-particle-size secondary particle artificial graphite, and adopts a lamination type structure, so that the obtained lithium ion battery has better normal-temperature rate performance and low-temperature rate performance of-40 ℃ and has high rate density characteristic;
According to the invention, the polyethylene material with double-sided ceramic coating is used as the diaphragm and is prepared in a hierarchical coating mode, so that on one hand, the passing rate of overcharge performance, overdischarge performance, high-temperature short circuit, thermal shock and needling safety performance of the lithium ion battery can be improved, and on the other hand, the coating layer formed by the plastic material is arranged outside the diaphragm and can be in close contact with positive and negative pole pieces, and the deformation rate of the lithium ion battery is small, so that the multiplying power performance of the lithium ion battery can be improved;
According to the electrolyte adopted by the invention, a certain amount of lithium bistrifluoromethane sulfonyl imide is added into the lithium salt, so that the resistance of an SEI layer formed on the surface of a pole piece at low temperature can be effectively reduced, and the low-temperature rate performance of a lithium ion battery is improved; meanwhile, the additive is prepared from vinylene carbonate, propane sultone and vinyl sulfate, so that the obtained lithium ion battery has good high-low temperature performance, prevents the lithium ion battery from expanding after being stored and placed at high temperature, improves the charge-discharge performance and the cycle life of the lithium ion battery, and enables the lithium ion battery to be used under a wide temperature range condition (-40-70 ℃) and to recover more than 90% of the capacity of the lithium ion battery after being stored at-55 ℃.
The positive electrode slurry, the polyethylene material coated with ceramic glue on the two sides and the specific electrolyte are matched with each other, so that the passing rate of the overcharge performance, the overdischarge performance, the high-temperature short circuit and the thermal shock safety performance of the lithium ion battery is ensured to be 100%, the needling passing rate of the lithium ion battery is obviously improved, and the lithium ion battery has high safety characteristics;
in the preparation process of the lithium ion battery, the wettability of the electrolyte is effectively improved by optimizing the activation mode, the activation temperature and the activation time, the liquid retention amount of the electrolyte is improved, and the cycle performance of the lithium ion battery is obviously improved;
in the preparation process of the lithium ion battery, the formation temperature and time are optimized, so that the lithium ion battery is ensured to form a compact and uniform SEI film on the surface of negative graphite, and the low-temperature performance of the lithium ion battery under the high-power condition is effectively improved.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clearly apparent, the invention is further described in detail. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of a lithium ion battery with a wide temperature range, which comprises the following specific steps:
preparation of a positive plate:
mixing 7.52kg of lithium cobalt oxide and 1.88kg of lithium iron phosphate (the weight ratio of the lithium cobalt oxide to the lithium iron phosphate is 8:2) to obtain a lithium cobalt oxide and lithium iron phosphate mixed material;
9.4kg of a mixed material of lithium cobalt oxide and lithium iron phosphate, 0.25kg of a conductive agent SP, 0.12kg of conductive carbon black ECP and 0.23kg of polyvinylidene fluoride binder are taken, and the positive electrode solid substance is obtained by dry powder mixing, mud stirring, high-viscosity stirring and viscosity adjustment to 5600 mpa.s;
then at 65:35, stirring and uniformly mixing the anode solid substance and N-methyl pyrrolidone (NMP) to obtain anode slurry;
and then the positive electrode slurry is coated on the surface of the aluminum foil to obtain the positive electrode plate.
Preparing a negative plate:
Mixing 3.76kg of secondary particle artificial graphite with the particle size of 13-17 mu m and 5.64kg of small-particle artificial graphite with the particle size of 5.5-9.5 mu m (the weight ratio of the secondary particle artificial graphite to the small-particle artificial graphite is 4:6) to obtain artificial graphite;
taking 9.4kg of artificial graphite, 0.20kg of conductive agent SP, 0.20kg of carboxymethylcellulose sodium and 0.20kg of SBR binder (styrene butadiene latex binder), and obtaining a negative electrode solid substance by dry powder mixing, mud stirring, CMC stirring and high-viscosity stirring, and adjusting the viscosity to 2000 mpa.s;
Then at 48:52, uniformly stirring and mixing the cathode solid substance and water to obtain cathode slurry;
and then the negative electrode slurry is coated on the surface of the copper foil to obtain the negative electrode plate.
Preparation of the separator:
The polyethylene material with the thickness of 9 mu m is used as a base film, aluminum oxide ceramic layers with the thickness of 4 mu m are respectively coated on two sides of the base film, polyvinylidene fluoride with the thickness of 2 mu m is respectively coated on the ceramic layers, and the polyethylene material with the double-sided ceramic coating glue is obtained, wherein the thickness of 21 mu m and the porosity of 47%.
Preparation of electrolyte:
1.3kg of lithium hexafluorophosphate (LiPF 6) and 0.2kg of lithium bistrifluoromethylsulfonylimide (LiTFSI) were taken as lithium salts for use;
Taking 5.4kg of methyl ethyl carbonate (EMC), 1.2kg of propyl acetate (EP), 1.3kg of Ethylene Carbonate (EC) and 0.4kg of Propylene Carbonate (PC) as organic solvents for standby;
taking 0.05kg of Vinylene Carbonate (VC), 0.05kg of Propane Sultone (PS) and 0.1kg of vinyl sulfate (DTD) as additives for standby;
And uniformly mixing lithium salt, an organic solvent and an additive to obtain the electrolyte.
Preparation of a wide-temperature-range lithium ion battery:
And (3) forming a laminated body after the positive plate and the negative plate after die cutting are laminated by a baffle and a diaphragm, welding a positive electrode lug and a negative electrode lug on the laminated body, filling an aluminum plastic film, packaging, short circuit testing, angle pressing and baking to form a semi-finished product cell, injecting electrolyte into the obtained semi-finished product cell, and pre-sealing, activating, forming, secondarily packaging and separating to obtain the laminated flexible-package wide-temperature-range lithium ion battery.
The method comprises the steps of firstly, placing a vertical air bag end of a pre-sealed battery, which is obtained by pre-sealing, upwards in a liquid injection tray for activation for 20 hours, placing the battery in the tray horizontally with the vertical air bag end facing the right side of the battery for activation for 14 hours, placing the battery in the tray horizontally with the vertical air bag end facing the left side of the battery, and activating for 14 hours;
The formation is carried out by adopting a high-temperature pressure formation mode, specifically, the activated battery obtained after activation is subjected to standing for 3min under the conditions that the surface pressure is 0.2mPa and the temperature is 55 ℃, then is charged for 60min by constant current with the current of 0.2C and the voltage of less than or equal to 4.05V, then is subjected to standing for 1min, and then is charged for 50min by constant current with the current of 0.6C and the voltage of less than or equal to 4.2V.
Example 2
The embodiment provides a preparation method of a lithium ion battery with a wide temperature range, which comprises the following specific steps:
preparation of a positive plate:
Mixing 7.125kg of lithium cobalt oxide and 2.375kg of lithium iron phosphate (the weight ratio of the lithium cobalt oxide to the lithium iron phosphate is 7.5:2.5) to obtain a lithium cobalt oxide and lithium iron phosphate mixed material;
9.5kg of a mixed material of lithium cobalt oxide and lithium iron phosphate, 0.18kg of a conductive agent SP, 0.10kg of conductive carbon black ECP and 0.22kg of polyvinylidene fluoride binder are taken, and the positive electrode solid substance is obtained by dry powder mixing, mud stirring, high-viscosity stirring and viscosity adjustment to 600 mpa.s;
then at 67:33, stirring and uniformly mixing the anode solid substance and N-methyl pyrrolidone (NMP) to obtain anode slurry;
and then the positive electrode slurry is coated on the surface of the aluminum foil to obtain the positive electrode plate.
Preparing a negative plate:
Mixing 4.75kg of secondary particle artificial graphite with the particle size of 13-17 mu m and 4.75kg of small-particle artificial graphite with the particle size of 5.5-9.5 mu m (the weight ratio of the secondary particle artificial graphite to the small-particle artificial graphite is 5:5) to obtain artificial graphite;
9.5kg of artificial graphite, 0.15kg of conductive agent SP, 0.17kg of carboxymethylcellulose sodium and 0.18kg of SBR binder are taken, and the negative electrode solid substance is obtained through dry powder mixing, mud stirring, CMC stirring and high-viscosity stirring, and the viscosity is adjusted to 2000 mpa.s;
Then at 49:51, uniformly stirring and mixing the anode solid substance and water to obtain anode slurry;
and then the negative electrode slurry is coated on the surface of the copper foil to obtain the negative electrode plate.
Preparation of the separator:
the polyethylene material with the thickness of 10 mu m is used as a base film, aluminum oxide ceramic layers with the thickness of 3 mu m are respectively coated on two sides of the base film, polyvinylidene fluoride with the thickness of 3 mu m is respectively coated on the ceramic layers, and the polyethylene material with the double-sided ceramic coating glue is obtained, wherein the thickness of 22 mu m and the porosity of 48%.
Preparation of electrolyte:
1.2kg of lithium hexafluorophosphate (LiPF 6) and 0.4kg of lithium bistrifluoromethylsulfonylimide (LiTFSI) were taken as lithium salts for use;
taking 5.5kg of methyl ethyl carbonate (EMC), 1.0kg of propyl acetate (EP), 1.2kg of Ethylene Carbonate (EC) and 0.3kg of Propylene Carbonate (PC) as organic solvents for standby;
Taking 0.1kg of Vinylene Carbonate (VC), 0.2kg of Propane Sultone (PS) and 0.1kg of vinyl sulfate (DTD) as additives for standby;
And uniformly mixing lithium salt, an organic solvent and an additive to obtain the electrolyte.
Preparation of a wide-temperature-range lithium ion battery:
And (3) forming a laminated body after the positive plate and the negative plate after die cutting are laminated by a baffle and a diaphragm, welding a positive electrode lug and a negative electrode lug on the laminated body, filling an aluminum plastic film, packaging, short circuit testing, angle pressing and baking to form a semi-finished product cell, injecting electrolyte into the obtained semi-finished product cell, and pre-sealing, activating, forming, secondarily packaging and separating to obtain the laminated flexible-package wide-temperature-range lithium ion battery.
The method comprises the steps of firstly, placing a vertical air bag end of a pre-sealed battery, which is obtained by pre-sealing, upwards in a liquid injection tray for activation for 20 hours, placing the battery in the tray horizontally with the vertical air bag end facing the right side of the battery for activation for 18 hours, placing the battery in the tray horizontally with the vertical air bag end facing the left side of the battery, and activating for 18 hours;
The formation is carried out by adopting a high-temperature pressure formation mode, specifically, the activated battery obtained after activation is subjected to standing for 3min under the conditions that the surface pressure is 0.3mPa and the temperature is 55 ℃, then is charged for 60min by constant current with the current of 0.2C and the voltage of less than or equal to 4.05V, then is subjected to standing for 1min, and then is charged for 50min by constant current with the current of 0.6C and the voltage of less than or equal to 4.2V.
Example 3
The embodiment provides a preparation method of a lithium ion battery with a wide temperature range, which comprises the following specific steps:
preparation of a positive plate:
Mixing 6.755kg of lithium cobaltate and 2.895kg of lithium iron phosphate (the weight ratio of the lithium cobaltate to the lithium iron phosphate is 7:3) to obtain a lithium cobaltate and lithium iron phosphate mixed material;
9.65kg of mixed material of lithium cobalt oxide and lithium iron phosphate, 0.13kg of conductive agent SP, 0.07kg of conductive carbon black ECP and 0.15kg of polyvinylidene fluoride binder are taken, and the positive electrode solid substance is obtained by dry powder mixing, mud stirring, high viscosity stirring and viscosity adjustment to 6500 mpa.s;
Then at 69:31, stirring and uniformly mixing the anode solid substance and N-methyl pyrrolidone (NMP) to obtain anode slurry;
and then the positive electrode slurry is coated on the surface of the aluminum foil to obtain the positive electrode plate.
Preparing a negative plate:
Mixing 5.76kg of secondary particle artificial graphite with the particle size of 13-17 mu m and 3.84kg of small-particle artificial graphite with the particle size of 5.5-9.5 mu m (the weight ratio of the secondary particle artificial graphite to the small-particle artificial graphite is 6:4) to obtain artificial graphite;
9.6kg of artificial graphite, 0.12kg of conductive agent SP, 0.13kg of carboxymethylcellulose sodium and 0.15kg of SBR binder are taken, and the negative electrode solid substance is obtained through dry powder mixing, mud stirring, CMC stirring and high-viscosity stirring, and the viscosity is adjusted to 2600 mpa.s;
then at 50:50, uniformly stirring and mixing the anode solid substance and water to obtain anode slurry;
and then the negative electrode slurry is coated on the surface of the copper foil to obtain the negative electrode plate.
Preparation of the separator:
The polyethylene material with the thickness of 12 mu m is used as a base film, aluminum oxide ceramic layers with the thickness of 4 mu m are respectively coated on two sides of the base film, polyvinylidene fluoride with the thickness of 3 mu m is respectively coated on the ceramic layers, and the polyethylene material with the double-sided ceramic coating glue is obtained, wherein the thickness of 26 mu m and the porosity of 50%.
Preparation of electrolyte:
1.4kg of lithium hexafluorophosphate (LiPF 6) and 0.1kg of lithium bistrifluoromethylsulfonylimide (LiTFSI) were taken as lithium salts for use;
taking 5.0kg of methyl ethyl carbonate (EMC), 0.8kg of propyl acetate (EP), 1.5kg of Ethylene Carbonate (EC) and 0.5kg of Propylene Carbonate (PC) as organic solvents for standby;
taking 0.25kg of Vinylene Carbonate (VC), 0.25kg of Propane Sultone (PS) and 0.2kg of vinyl sulfate (DTD) as additives for standby;
And uniformly mixing lithium salt, an organic solvent and an additive to obtain the electrolyte.
Preparation of a wide-temperature-range lithium ion battery:
And (3) forming a laminated body after the positive plate and the negative plate after die cutting are laminated by a baffle and a diaphragm, welding a positive electrode lug and a negative electrode lug on the laminated body, filling an aluminum plastic film, packaging, short circuit testing, angle pressing and baking to form a semi-finished product cell, injecting electrolyte into the obtained semi-finished product cell, and pre-sealing, activating, forming, secondarily packaging and separating to obtain the laminated flexible-package wide-temperature-range lithium ion battery.
The method comprises the steps of firstly, placing a vertical air bag end of a pre-sealed battery, which is obtained by pre-sealing, upwards in a liquid injection tray for activation for 24 hours, placing the battery in the tray horizontally with the vertical air bag end facing the right side of the battery for activation for 18 hours, placing the battery in the tray horizontally with the vertical air bag end facing the left side of the battery, and activating for 18 hours;
The formation is carried out by adopting a high-temperature pressure formation mode, specifically, the activated battery obtained after activation is subjected to standing for 3min under the conditions that the surface pressure is 0.3mPa and the temperature is 55 ℃, then is charged for 60min by constant current with the current of 0.2C and the voltage of less than or equal to 4.05V, then is subjected to standing for 1min, and then is charged for 50min by constant current with the current of 0.6C and the voltage of less than or equal to 4.2V.
Example 4
The embodiment provides a preparation method of a lithium ion battery with a wide temperature range, which comprises the following specific steps:
preparation of a positive plate:
Mixing 6.755kg of lithium cobaltate and 2.895kg of lithium iron phosphate (the weight ratio of the lithium cobaltate to the lithium iron phosphate is 7:3) to obtain a lithium cobaltate and lithium iron phosphate mixed material;
9.65kg of mixed material of lithium cobalt oxide and lithium iron phosphate, 0.13kg of conductive agent SP, 0.07kg of conductive carbon black ECP and 0.15kg of polyvinylidene fluoride binder are taken, and the positive electrode solid substance is obtained by dry powder mixing, mud stirring, high viscosity stirring and viscosity adjustment to 6500 mpa.s;
Then at 69:31, stirring and uniformly mixing the anode solid substance and N-methyl pyrrolidone (NMP) to obtain anode slurry;
and then the positive electrode slurry is coated on the surface of the aluminum foil to obtain the positive electrode plate.
Preparing a negative plate:
Mixing 5.76kg of secondary particle artificial graphite with the particle size of 13-17 mu m and 3.84kg of small-particle artificial graphite with the particle size of 5.5-9.5 mu m (the weight ratio of the secondary particle artificial graphite to the small-particle artificial graphite is 6:4) to obtain artificial graphite;
9.6kg of artificial graphite, 0.12kg of conductive agent SP, 0.13kg of carboxymethylcellulose sodium and 0.15kg of SBR binder are taken, and the negative electrode solid substance is obtained through dry powder mixing, mud stirring, CMC stirring and high-viscosity stirring, and the viscosity is adjusted to 2600 mpa.s;
then at 50:50, uniformly stirring and mixing the anode solid substance and water to obtain anode slurry;
and then the negative electrode slurry is coated on the surface of the copper foil to obtain the negative electrode plate.
Preparation of the separator:
The polyethylene material with the thickness of 12 mu m is used as a base film, aluminum oxide ceramic layers with the thickness of 4 mu m are respectively coated on two sides of the base film, polyvinylidene fluoride with the thickness of 3 mu m is respectively coated on the ceramic layers, and the polyethylene material with the double-sided ceramic coating glue is obtained, wherein the thickness of 26 mu m and the porosity of 50%.
Preparation of electrolyte:
Taking 1.5kg of lithium hexafluorophosphate (LiPF 6) and 0.5kg of lithium bistrifluoromethylsulfonyl imide (LiTFSI) as lithium salts for standby;
Taking 5.0kg of methyl ethyl carbonate (EMC), 0.85kg of propyl acetate (EP), 1.0kg of Ethylene Carbonate (EC) and 0.5kg of Propylene Carbonate (PC) as organic solvents for standby;
Taking 0.3kg of Vinylene Carbonate (VC), 0.3kg of Propane Sultone (PS) and 0.05kg of vinyl sulfate (DTD) as additives for standby;
And uniformly mixing lithium salt, an organic solvent and an additive to obtain the electrolyte.
Preparation of a wide-temperature-range lithium ion battery:
And (3) forming a laminated body after the positive plate and the negative plate after die cutting are laminated by a baffle and a diaphragm, welding a positive electrode lug and a negative electrode lug on the laminated body, filling an aluminum plastic film, packaging, short circuit testing, angle pressing and baking to form a semi-finished product cell, injecting electrolyte into the obtained semi-finished product cell, and pre-sealing, activating, forming, secondarily packaging and separating to obtain the laminated flexible-package wide-temperature-range lithium ion battery.
The method comprises the steps of firstly, placing a vertical air bag end of a pre-sealed battery, which is obtained by pre-sealing, upwards in a liquid injection tray for activation for 24 hours, placing the battery in the tray horizontally with the vertical air bag end facing the right side of the battery for activation for 18 hours, placing the battery in the tray horizontally with the vertical air bag end facing the left side of the battery, and activating for 18 hours;
The formation is carried out by adopting a high-temperature pressure formation mode, specifically, the activated battery obtained after activation is subjected to standing for 3min under the conditions that the surface pressure is 0.3mPa and the temperature is 55 ℃, then is charged for 60min by constant current with the current of 0.2C and the voltage of less than or equal to 4.05V, then is subjected to standing for 1min, and then is charged for 50min by constant current with the current of 0.6C and the voltage of less than or equal to 4.2V.
Comparative example 1
Comparative example 1 is a comparative experiment of example 1, differing only in that: comparative example 1 lithium cobaltate was used entirely instead of the lithium cobaltate and lithium iron phosphate mixed material (i.e., lithium iron phosphate was not used) in the preparation of the positive electrode solid substance.
Comparative example 2
Comparative example 2 is a comparative experiment of example 1, differing only in: comparative example 2 in the preparation of the negative electrode solid matter, the secondary particle artificial graphite having a particle size of 13 to 17 μm was entirely used instead of artificial graphite (i.e., small-particle secondary particle artificial graphite was not used).
Comparative example 3
Comparative example 3 is a comparative experiment of example 1, differing only in: in comparative example 3, a double-sided ceramic separator was used as a separator instead of a double-sided ceramic-coated polyethylene material (i.e., polyvinylidene fluoride was not coated during the separator preparation).
Comparative example 4
Comparative example 4 is a comparative experiment of example 1, differing only in: comparative example 4 in the preparation of a wide temperature range lithium ion battery, conventional activation was used instead of staged activation.
Comparative example 5
Comparative example 5 is a comparative experiment of example 1, differing only in: comparative example 5 in the preparation of a wide temperature range lithium ion battery, conventional formation was used instead of high temperature pressure formation.
Experimental example 1
The lithium ion batteries with wide temperature ranges prepared in examples 1 to 3 and comparative examples 1 to 5 were respectively subjected to capacity-division and then cell performance test, and specific test results are as follows
Table 1 list of lithium ion battery Performance test results
As can be seen from table 1, the wide temperature range lithium ion battery prepared by the invention is a wide temperature range high-safety high-power density lithium ion battery, can be used under the wide temperature range condition of-40 ℃ to 70 ℃, wherein the discharge capacity of 2.0C under the condition of-40 ℃ can reach more than 50% of the nominal capacity, the recovery capacity of the battery after being stored for 48 hours under the condition of 70 ℃ is more than 90%, in addition, the recovery capacity after being stored for 24 hours under the condition of-55 ℃ is more than 90%, the normal-temperature power can reach 5.0C, and the lithium ion battery has the characteristic of high multiplying power density; meanwhile, the overcharge performance, the overdischarge performance, the high-temperature short circuit, the thermal shock and the needling safety performance are ensured.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (3)
1. The lithium ion battery with the wide temperature range comprises a positive plate, a negative plate, a diaphragm and electrolyte, and is characterized in that the positive plate comprises positive slurry prepared from a lithium cobaltate and lithium iron phosphate mixed material; the negative plate comprises negative electrode slurry prepared from artificial graphite, wherein:
The positive electrode slurry comprises 65-69 wt% of positive electrode solid matters and the rest amide solvents; the positive electrode solid substance comprises the following components in parts by weight: 94-96.5 parts of lithium cobaltate and lithium iron phosphate mixed material, 1.3-2.5 parts of conductive agent, 0.7-1.2 parts of conductive carbon black and 1.5-2.3 parts of binder; the lithium cobaltate and lithium iron phosphate mixed material comprises the following components in percentage by weight: 2-3 of lithium cobalt oxide and lithium iron phosphate;
The negative electrode slurry comprises 48-50wt% of negative electrode solid matter and the rest of polar solvent; the negative electrode solid substance comprises the following components in parts by weight: 94-96 parts of artificial graphite, 1.2-2.0 parts of conductive agent, 1.3-2.0 parts of sodium carboxymethylcellulose and 1.5-2.0 parts of adhesive; the artificial graphite is prepared from the following components in percentage by weight: 4-6, and mixing the secondary particle artificial graphite with small particle size; the particle size of the secondary particle artificial graphite is 13-17 mu m; the particle size of the small-particle-size secondary particle artificial graphite is 5.5-9.5 mu m;
The preparation method of the lithium ion battery with wide temperature range comprises the following steps: forming a laminated body after the positive plate and the negative plate after die cutting are laminated by a baffle and a diaphragm, welding a positive electrode tab and a negative electrode tab on the laminated body, filling an aluminum plastic film, packaging, short circuit testing, angle pressing and baking to form a semi-finished product cell, injecting electrolyte into the obtained semi-finished product cell, and pre-sealing, activating, forming, secondary packaging and capacity division to obtain a laminated flexible-packaged wide-temperature-range lithium ion battery, wherein the laminated flexible-packaged wide-temperature-range lithium ion battery comprises a plurality of lithium ion batteries;
The activation temperature is 40-45 ℃ and the activation time is 48-60 h, the activation is carried out in three sections, firstly, the vertical air bag end of the pre-sealed battery obtained by pre-sealing is activated for 20-24 h upwards, then the vertical air bag end is activated for 14-18 h towards the right side of the battery, then the battery is turned over, and the vertical air bag end is activated for 14-18 h towards the left side of the battery;
The formation adopts a high-temperature pressure formation mode: taking the activated battery obtained after activation, standing for 3min under the conditions that the surface pressure is 0.2-0.3 mPa and the temperature is 55 ℃, charging for 60min by constant current with the current of 0.2C and the voltage of less than or equal to 4.05V, standing for 1min, and charging for 50min by constant current with the current of 0.6C and the voltage of less than or equal to 4.2V.
2. The broad temperature range lithium ion battery of claim 1, wherein the separator is formed by coating ceramic layers on both sides of a base film, and coating plastic materials on the ceramic layers.
3. The broad temperature range lithium ion battery of claim 1, wherein the electrolyte comprises, in parts by weight:
① Lithium salt: 12-15 parts of lithium hexafluorophosphate and 1-5 parts of lithium bistrifluoromethylsulfonyl imide;
② Organic solvent: 50-55 parts of methyl ethyl carbonate, 8-12 parts of propyl acetate, 10-15 parts of ethylene carbonate and 3-5 parts of propylene carbonate;
③ Additive: 0.5 to 3 parts of vinylene carbonate, 0.5 to 3 parts of propane sultone and 0.5 to 2 parts of vinyl sulfate.
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| CN107851795A (en) * | 2015-12-23 | 2018-03-27 | 株式会社Lg化学 | Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery containing same |
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| CN107851795A (en) * | 2015-12-23 | 2018-03-27 | 株式会社Lg化学 | Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery containing same |
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