CN114566717B - Preparation method of lithium iron phosphate battery suitable for wide temperature range - Google Patents
Preparation method of lithium iron phosphate battery suitable for wide temperature range Download PDFInfo
- Publication number
- CN114566717B CN114566717B CN202210210652.2A CN202210210652A CN114566717B CN 114566717 B CN114566717 B CN 114566717B CN 202210210652 A CN202210210652 A CN 202210210652A CN 114566717 B CN114566717 B CN 114566717B
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- lithium iron
- lithium
- temperature range
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 239000006258 conductive agent Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 57
- 239000007788 liquid Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 28
- 239000002041 carbon nanotube Substances 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 238000002347 injection Methods 0.000 claims description 25
- 239000007924 injection Substances 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000011267 electrode slurry Substances 0.000 claims description 16
- 239000011888 foil Substances 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 11
- 239000006256 anode slurry Substances 0.000 claims description 10
- 238000005056 compaction Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000003475 lamination Methods 0.000 claims description 10
- 238000003698 laser cutting Methods 0.000 claims description 10
- 238000004080 punching Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000005524 ceramic coating Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 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 7
- 230000032683 aging Effects 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 claims description 4
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- WXBWKMLIVXELSF-UHFFFAOYSA-N 2,2,2-trifluoro-n,n-dimethylacetamide Chemical compound CN(C)C(=O)C(F)(F)F WXBWKMLIVXELSF-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 11
- 239000011149 active material Substances 0.000 abstract description 5
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000006182 cathode active material Substances 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 42
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 17
- 235000006408 oxalic acid Nutrition 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 238000003466 welding Methods 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000003487 electrochemical reaction Methods 0.000 description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/056—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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of lithium ion battery manufacturing, in particular to a preparation method of a lithium iron phosphate battery which is suitable for being used in a wide temperature range of-40-55 ℃ and has excellent performance and stable reliability, and solves the problems of poor low-temperature performance and poor multiplying power performance of a lithium iron phosphate positive electrode material for a lithium ion battery. On the basis of the traditional preparation process of the lithium iron phosphate battery, the optimal surface loading capacity is designed by adjusting the types and the proportions of the anode and the cathode, the conductive agent and the binder in the battery, the high-quality conductive agent type is selected, a three-dimensional space conductive network is formed on the anode and the cathode material layers, the electronic conductivity among active material particles is improved, and the capacity of the anode and the cathode active materials can be exerted to the greatest extent. The specially prepared low-temperature electrolyte is selected, and the lithium salt concentration and the proportion of each main solvent additive in the electrolyte are adjusted, so that the electrolyte has good stability in a wide temperature range, the variation of ionic conductivity in a use temperature range is small, and the use safety and performance exertion of the battery at different temperatures are met.
Description
Technical Field
The invention relates to the field of lithium ion battery manufacturing, in particular to a preparation method of a lithium iron phosphate battery which is suitable for being used in a wide temperature range of-40 ℃ to 55 ℃ and has excellent performance and stable reliability.
Background
Since Goodenough et al first proposed that lithium iron phosphate (LiFePO 4) is used as a positive electrode active material of a lithium ion battery in 1997, liFePO 4 is considered to be a positive electrode active material for a lithium ion power battery, which has the most development prospect at present, because of its advantages of high safety, long cycle life, low price, environmental friendliness and the like. Lithium ions migrate in the LiFePO 4 lattice along one-dimensional channels, so that the diffusion rate of the lithium ions is greatly limited, and the one-dimensional channels are easily blocked due to the occurrence of impurity defects, so that the ion conductivity of the lithium ions is further reduced. The inherent poor conductivity of LiFePO 4 materials compared to other positive electrode active materials greatly limits their kinetic properties at room temperature. Thus, the initial research around LiFePO 4 has focused mainly on improving both the lithium ion diffusion rate and the electron conductivity. By improving the specific surface area of LiFePO 4 and coating or doping LiFePO 4, the ionic and electronic conductivity of the material is obviously improved, the room temperature dynamic characteristics of the material are obviously improved, the requirement of using is met, but the low-temperature characteristics of LiFePO 4 are still poor, and the use requirement of a power supply at low temperature cannot be met. Therefore, how to improve the low temperature characteristics of LiFePO 4 batteries has become a major concern for lithium ion battery researchers.
Currently, researchers have conducted extensive and intensive studies on the low-temperature characteristics of LiFePO 4 batteries. Such as: the electrochemical reaction scale is reduced by reducing the particle size of LiFePO 4 particles, so that the electrochemical activity of the LiFePO 4 material and the lithium ion migration rate at low temperature are improved; by coating a layer of conductive amorphous carbon net on the surface of LiFePO 4 particles, the electron conductivity of the material can be improved, abnormal growth of the particles of LiFePO 4 in the sintering process can be inhibited, and finally the electrochemical reaction rate of LiFePO 4 at low temperature is accelerated; the lithium or Fe site in the LiFePO 4 lattice is doped with high-valence cations to form a p-type semiconductor, so that holes with corresponding potential in the LiFePO 4 lattice are convenient for migration of Li ions, the ionic conductivity of the material is improved, and the electrochemical reaction rate of LiFePO 4 at low temperature is improved.
In recent years, the popularization and popularization of new energy automobiles are greatly improved in the environmental management level of China, and the living environment of residents in China is better in the future under the national measure of limiting carbon emission. In the north of China, the temperature is generally lower than 0 ℃ in autumn and winter, so that the dynamic performance of a new energy automobile battery, particularly a lithium iron phosphate battery, is difficult or impossible to perform at the temperature below 0 ℃. Such as: at-20 ℃, the capacity is not as high as 70% of the room temperature capacity; at-40 ℃, the capacity plays a role of 30% or less of the capacity of the direct-driven room temperature, even can not discharge. Thus, there is a need for a reasonably efficient method of preparing lithium iron phosphate batteries at low temperatures.
Disclosure of Invention
Aiming at the defect of poor low-temperature performance of the existing lithium iron phosphate, the invention aims to provide a preparation method of a lithium iron phosphate battery suitable for a wide temperature range, and solves the problems of poor low-temperature performance and rate performance of a lithium iron phosphate anode material for a lithium ion battery in the prior art by preparing the three-dimensional network structure composite carbon-coated nano lithium iron phosphate with excellent low-temperature performance and rate performance.
The technical scheme of the invention is as follows:
The preparation method of the lithium iron phosphate battery suitable for being used in a wide temperature range comprises the following steps:
(1) Firstly, lithium iron phosphate is prepared according to the weight proportion: conductive agent: binder=91 to 94:2 to 4: 2-4, adding the mixture into a stirring barrel; then adding N-methyl pyrrolidone for fine kneading to ensure that the solid content of slurry in a stirring barrel is 60-70 wt%, and simultaneously starting stirring rotation speed is 40-45 rad/min and dispersing rotation speed is 2800-3500 rad/min for 2-4 hours; then continuously adding N-methyl pyrrolidone for three times, and simultaneously starting stirring rotation speed of 40-50 rad/min and dispersing rotation speed of 3000-4000 rad/min, wherein each time lasts for 0.5-2 hours; finally, the anode slurry with uniform dispersion and viscosity of 4500-8000 N.m is obtained;
(2) Filtering the positive electrode slurry through a 120-150 mesh screen, and uniformly coating the positive electrode slurry on a carbon-coated aluminum foil with the thickness of 12-18 mu m by using a continuous coater according to the surface density of 25-38 mg/cm 2;
(3) The positive electrode roll is rolled by a roll squeezer according to the compaction density of 2.2-2.4 g/cm 3, and then a laser cutting die is used for completing punching of the positive electrode small sheet, so that the positive electrode small sheet with proper size is prepared;
(4) Firstly, artificial graphite is prepared according to the weight proportion: conductive agent: binder=94 to 95.5:1.2 to 1.8:3.3 to 4.2, and adding the mixture into a stirring barrel; adding deionized water for fine kneading to ensure that the solid content of the slurry in the stirring barrel is 60-70 wt%, and simultaneously starting the stirring rotation speed of 40-45 rad/min and the dispersing rotation speed of 2800-3500 rad/min for 2-4 hours; then adding deionized water continuously for three times, and simultaneously starting stirring rotation speed of 40-50 rad/min and dispersing rotation speed of 3000-4000 rad/min, wherein each time lasts for 0.5-2 hours; finally, anode slurry with uniform dispersion and viscosity of 3500-4800 N.m is obtained;
(5) Filtering the negative electrode slurry through a 100-120 mesh screen, and uniformly coating the negative electrode slurry on copper foil with the thickness of 6-8 mu m by using a continuous coater according to the surface density of 14.4-16.8 mg/cm 2;
(6) The negative electrode roll is rolled by a roll squeezer according to the compaction density of 1.3-1.5 g/cm 3, and then a laser cutting die is used for completing punching of a negative small piece, so that the negative small piece with proper size is prepared;
(7) Matching the positive and negative small pieces with a diaphragm with a single-sided Al 2O3 ceramic coating, finishing core package manufacturing by a lamination machine in a Z-shaped lamination type structure, and assembling to form an assembly without liquid injection;
(8) After the non-injected assembly is subjected to vacuum baking at 80-90 ℃ for 24-36 hours, injecting electrolyte of the lithium iron phosphate battery into the non-injected assembly by using a liquid injector according to the coefficient of 4.5-6.5 g/Ah, and aging for 12-24 hours at 30-40 ℃ to form a battery cell;
(9) Placing the battery cell on a formation device, charging the battery cell with an opening formation system of the battery cell in three sections at 0.02-0.05C, 0.05-0.1C and 0.1-0.2C for 3.33 hours respectively, sealing after the battery cell is completed, and then transferring the battery cell to an environment of 30-40 ℃ for open circuit aging for 3-7 days;
(10) And carrying out capacity-dividing operation on the aged battery, and obtaining the lithium iron phosphate battery which is stably used in a wide temperature area after finishing.
According to the preparation method of the lithium iron phosphate battery suitable for the wide temperature range, the granularity D50 of the lithium iron phosphate used for the anode is 0.5-1.5 mu m, the carbon content is 1.5-1.9 wt%, and the specific surface area is 15-22 m 2/g; the granularity D50 of the artificial graphite used for the negative electrode is 7.5-12 mu m, and the specific surface area is 1.3-1.8 m 2/g.
According to the preparation method of the lithium iron phosphate battery suitable for being used in a wide temperature range, preferably, the granularity D50 of lithium iron phosphate used in the anode is 0.7 mu m, the carbon content is 1.85wt%, the specific surface area is 20m 2/g, and the lithium iron phosphate battery has good low-temperature rate performance; the artificial graphite used for the negative electrode has the granularity D50 of 11 mu m, the specific surface area of 1.5m 2/g and good electrochemical performance in a wide temperature area.
In the preparation method of the lithium iron phosphate battery suitable for wide temperature range, the conductive agent used by the anode and the cathode is one or more than two of superconductive carbon black, conductive graphite, carbon nano tube, ketjen black and graphene; the binder used for the positive electrode and the negative electrode is one or more than two of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, sodium alginate, sodium carboxymethyl cellulose and styrene butadiene rubber.
According to the preparation method of the lithium iron phosphate battery suitable for being used in a wide temperature range, the conductive agent used for the anode is added in the form of conductive liquid, the concentration of the conductive agent in the conductive liquid is 4-6wt%, and the balance is N-methylpyrrolidone; the conductive agent used in the negative electrode is added in the form of conductive liquid, the concentration of the conductive agent in the conductive liquid is 4-6wt% and the balance is water.
In the step (1), weighing lithium iron phosphate, a conductive agent and a binder, adding the materials into a stirring barrel, and starting stirring to perform primary mixing of dry powder at a rotating speed of 10-15 rad/min for 1-3 hours; in the step (4), the artificial graphite, the conductive agent and the adhesive are weighed and added into a stirring barrel, stirring is started, and dry powder is primarily mixed for 1-3 hours at the rotating speed of 10-15 rad/min.
In the preparation method of the lithium iron phosphate battery suitable for being used in a wide temperature range, in the step (1), 61-63 wt% of the total amount of N-methyl pyrrolidone is added for fine kneading, and when the N-methyl pyrrolidone is continuously added for three times, 11-13 wt% of the total amount of the N-methyl pyrrolidone is added each time; in the step (4), 57.5 to 60 weight percent of the total amount of deionized water is added for fine kneading, and when the deionized water is continuously added in three times, 13.5 to 14.5 weight percent of the total amount of the deionized water is added each time.
In the preparation method of the lithium iron phosphate battery suitable for wide temperature range, in the carbon-coated aluminum foil used for coating the positive electrode, the thickness of the carbon-coated layers on the two sides of the aluminum foil is respectively 1-3 mu m, and the carbon-coated layer material is one or more than two selected from superconducting carbon black, superconducting graphite, carbon nano tubes and superconducting silver adhesive.
According to the preparation method of the lithium iron phosphate battery suitable for the wide temperature area, the membrane used in lamination is a wet high-porosity membrane, the thickness of the membrane is 15-25 mu m, the porosity of the membrane is 35-45%, the average pore diameter is 0.05-0.15 mu m, the membrane is made of one or two of polypropylene and polyethylene, and the thickness of a ceramic coating of Al 2O3 is coated on one side of the membrane and is 1-3 mu m.
In the preparation method of the lithium iron phosphate battery suitable for being used in a wide temperature range, in electrolyte used by the uninjected assembly, lithium salt is one or more than two of lithium hexafluorophosphate, lithium difluorosulfimide, lithium tetrafluoroborate, lithium dioxalate borate, lithium bistrifluoromethylsulfonimide and lithium difluorophosphate, and the content of the lithium salt is 10-13 wt%; the additive is one or more than two of propylene sulfite, triallyl phosphate, dimethyl trifluoroacetamide, phosphorus pentoxide, trimethyl phosphate and vinylene carbonate, and the content of the additive is 1-8wt%; the solvent is one or more of methyl ethyl carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate and ethyl acrylate, and the balance is solvent.
The design idea of the invention is as follows: the electrochemical reaction scale is reduced by selecting the nanoscale lithium iron phosphate with small particle size, which is beneficial to the diffusion and migration of Li ions; the multiple conductive agents are selected for cooperation, so that charge conduction among active material particles is improved, and the carbon coating aluminum foil is combined, so that contact between the active material layer and the current collector is enhanced, contact surface impedance is reduced, and electrons are conducted on the current collector more rapidly. By combining the using schemes, the performance of the lithium iron phosphate battery at low temperature can be improved.
The lithium hexafluorophosphate and the lithium difluorosulfimide are used as lithium salts together by selecting a low-temperature special electrolyte with high compounding degree, and various low-temperature additives and film forming auxiliaries are contained. The components and the dosage of the solvent are adjusted to ensure that the electrolyte has good stability and higher ionic conductivity in a wide temperature range of-40 ℃ to 55 ℃.
By using the preparation method of the low-temperature lithium iron phosphate battery, the lithium iron phosphate battery also has good usability at low temperature, and can meet the daily use of most areas in China.
The invention has the advantages and beneficial effects that:
1. The method provided by the invention has high compatibility with the traditional preparation method of the lithium iron phosphate battery, and only part of component raw materials are required to be adjusted, so that the lithium iron phosphate battery which has excellent low-temperature performance and is suitable for being used in a wide temperature area can be produced, and excessive equipment replacement and capital investment are not required.
2. The lithium iron phosphate battery prepared by the method can meet the normal performance exertion of normal temperature and high temperature areas at 0-55 ℃, gives consideration to performance exertion in a low temperature area of minus 40-0 ℃ and has excellent low temperature performance.
3. The lithium iron phosphate battery prepared by the method has high consistency and stable performance. The low-temperature performance is improved, meanwhile, the cyclic service life and the multiplying power performance are improved to different degrees, and the use safety is high.
4. The invention selects the specially prepared low-temperature electrolyte, and the lithium salt concentration and the proportion of each main solvent additive in the electrolyte are adjusted to ensure that the electrolyte has good stability in a wide temperature range, the ion conductivity has small fluctuation in a use temperature range, and the use safety and performance exertion of the battery at different temperatures are satisfied.
Drawings
FIG. 1 is a plot of percent discharge capacity versus discharge voltage for the sample of example 1 at temperatures of-20 ℃, -40 ℃ and 55 ℃. In the figure, the abscissa CAPACITY PERCENT represents the discharge capacity (%), and the ordinate Voltage represents the Voltage (V).
FIG. 2 is a plot of percent discharge capacity versus discharge voltage for the sample of example 2 at temperatures of-20 ℃, -40 ℃ and 55 ℃. In the figure, the abscissa CAPACITY PERCENT represents the discharge capacity (%), and the ordinate Voltage represents the Voltage (V).
FIG. 3 is a plot of the percentage discharge capacity versus discharge voltage for samples of example 3 at-20 ℃, -40 ℃ and 55 ℃. In the figure, the abscissa CAPACITY PERCENT represents the discharge capacity (%), and the ordinate Voltage represents the Voltage (V).
Detailed Description
In the specific implementation process, the nano-carbon coated lithium iron phosphate, the multi-component conductive material, the oil-based adhesive and the N-methyl pyrrolidone are uniformly mixed according to a certain proportion, uniformly coated on the surface of a current collector, and baked, rolled and sliced to prepare the positive electrode chip; uniformly mixing modified artificial graphite with uniform granularity, a multi-component conductive material, a low-temperature water-based adhesive, sodium carboxymethyl cellulose and deionized water according to a certain proportion, uniformly coating the mixture on the surface of a negative electrode current collector, and baking, rolling and slicing the mixture to obtain a negative electrode small piece; and (3) preparing a core bag by matching proper positive and negative micro sheets with an Al 2O3 ceramic coating diaphragm in a lamination structure, then performing cold and hot pressing, ultrasonic welding, tab folding and laser welding to prepare an assembly without liquid injection, and placing the assembly without liquid injection in a vacuum oven for baking, and waiting for electrolyte injection.
According to the performance requirements, preparing a proper low-temperature electrolyte, injecting the electrolyte into the un-injected assembly body by using a liquid injection device, continuously transferring the electrolyte to an oven, aging for a certain time, and waiting for formation.
And by combining the characteristics of the anode material, the cathode material and the electrolyte, determining the potential of side reaction in the formation process, setting the formation process step, and reasonably controlling the gas production rate in the cell formation process. And (3) finishing the process of converting the formed battery core into an aging process, and finishing the preparation of the wide-temperature-zone lithium iron phosphate battery after the aging process is finished.
In the present invention, a stirring vessel may employ a powerful stirring apparatus having both high-speed dispersion and low-speed stirring (e.g., patent publication No. CN 208583282U or the like or other conventional apparatuses).
The invention is further elucidated below by means of examples and figures.
Example 1:
in this embodiment, a preparation method of a lithium iron phosphate battery suitable for use in a wide temperature range is as follows:
(1) Firstly, 9470g of nanoscale carbon-coated lithium iron phosphate, 250g of superconducting carbon black and 200g of polyvinylidene fluoride are weighed and sequentially added into a 20L stirring barrel, and the mixture is slowly stirred for 2 hours at a speed of 12rad/min, so that solid particles are primarily and uniformly mixed; then 1333.33g of carbon nanotube conductive liquid (5 wt% of carbon nanotubes and the balance of N-methyl pyrrolidone) is added, the N-methyl pyrrolidone is continuously added to ensure that the solid content of the slurry in the stirring barrel reaches 63wt%, the stirring rotation speed is started to 40rad/min and the dispersing rotation speed is 3000rad/min while the N-methyl pyrrolidone is added, and the slurry is continuously and finely kneaded for 3 hours through high shearing force to ensure that all components are uniformly dispersed; then adding N-methyl pyrrolidone for three times, simultaneously starting stirring rotation speed 40rad/min and dispersing rotation speed 3000rad/min for high-speed dispersion while adding N-methyl pyrrolidone, stirring for 1 hour each time until the slurry viscosity is 3000-4800 N.m and the fineness is below 25 mu m, taking the slurry as positive electrode slurry, starting vacuum to-95 kPa (gauge pressure), and maintaining the pressure for 0.5 hour; filtering the anode slurry into a container through a 150-mesh stainless steel screen, uniformly coating the anode slurry on carbon-coated aluminum foil with the thickness of 16 mu m at the surface density of 35mg/cm 2 by using a continuous coater, wherein the thickness of carbon-coated layers on the two sides of the aluminum foil is 2 mu m respectively, and the carbon-coated layers are made of superconducting carbon black to prepare an anode coil; and rolling the positive electrode roll according to the compaction density of 2.37g/cm 3, punching the positive electrode small sheet with a fixed shape by using a laser cutting die of die cutting equipment to obtain the positive electrode small sheet with proper size, and finally transferring the positive electrode small sheet into a vacuum oven for temporary storage.
(2) Firstly, weighing 9525g of hard carbon coated artificial graphite, 130g of superconducting carbon black, 120g of sodium carboxymethylcellulose and 3g of oxalic acid (the oxalic acid has the effect that the low acidity of the oxalic acid slightly corrodes the surface of copper foil, the bonding property of a coating is improved, the hydrolysis temperature of the oxalic acid is very low, the oxalic acid can be further dried and removed, and the performance of a battery is not influenced), sequentially adding the materials into a stirring barrel, and stirring at a slow speed of 12rad/min for 2 hours to ensure that solid particles are primarily and uniformly mixed; then adding 333.33g of oxalic acid, 333.33g of carbon nanotube conductive liquid (5 wt% of carbon nanotubes in the carbon nanotube conductive liquid and the balance of water), 1333.33g of water-based binder (16 wt% of polyacrylic acid in the water-based binder and the balance of water) and deionized water, so that the solid content of slurry in a stirring barrel reaches 66.5wt%, and starting stirring rotation speed of 40rad/min and dispersing rotation speed of 3000rad/min while adding the deionized water, and continuously and finely kneading the slurry for 3 hours by high shear force to uniformly disperse each component; adding deionized water for three times, simultaneously starting stirring rotation speed 40rad/min and dispersing rotation speed 3000rad/min for high-speed dispersion, stirring for 1 hour each time until slurry viscosity is 3000-3500 N.m and fineness is below 40 mu m, taking the slurry as negative electrode slurry, starting vacuum to-95 kPa (gauge pressure), and maintaining pressure for 0.5 hour; filtering the cathode slurry into a container through a 150-mesh stainless steel screen, and uniformly coating the slurry on a copper foil with the thickness of 8 mu m at the surface density of 16.4mg/cm 2 by using a continuous coater to prepare a cathode coil; and rolling the negative electrode roll according to the compaction density of 1.37g/cm 3, punching the negative electrode small sheet with a fixed shape by using a laser cutting die of die cutting equipment to obtain the negative electrode small sheet with proper size, and finally transferring into a vacuum oven for temporary storage.
(3) And (3) processing the positive electrode small piece, the negative electrode small piece and the wet high-porosity PP diaphragm (the PP diaphragm porosity is 44%, the average pore diameter of the PP diaphragm is 0.08 mu m, the thickness of the PP diaphragm is 20 mu m, and the thickness of the Al 2O3 ceramic coating is 2 mu m) in the steps (1) and (2) into a core bag with the capacity of 13Ah by using a Z-shaped lamination type structure, and then sequentially completing the working procedures of hot and cold pressing, short circuit testing, cover plate ultrasonic welding, lug bending, shell entering, shell laser welding and the like, thereby completing the 13Ah non-injected aluminum shell assembly.
(4) And (3) baking the assembly without liquid injection in the step (3) for 36 hours by a vacuum oven at 85 ℃, recovering to room temperature, taking out, injecting low-temperature special electrolyte containing lithium dioxalate borate and lithium bis (trifluoromethyl) sulfonyl imide into the assembly without liquid injection by using a liquid injection machine according to the liquid injection coefficient of 4.9g/Ah, using an adhesive tape to enable a liquid injection port to be simply packaged, taking out, placing the liquid injection machine in the oven at 35 ℃, baking for 18 hours, recovering to room temperature, and taking out to form the battery cell.
In the electrolyte, the concentration of lithium dioxalate borate is 6.1wt%, the concentration of lithium bistrifluoromethylsulfonyl imide is 2.8wt%, the concentration of lithium tetrafluoroborate is 1.3wt%, the concentration of triallyl phosphate is 3.4wt%, the concentration of vinylene carbonate is 2.22wt%, the concentration of propylene sulfite is 2.38 wt%, the concentration of ethylene carbonate is 15wt%, the concentration of propylene carbonate is 15wt%, and the balance is ethyl acrylate.
(5) And placing the battery cell after liquid injection on formation equipment, connecting positive and negative poles of the battery cell with a channel test line, and charging to a voltage of 3.65V for 3.33 hours at 0.05C, 0.1C and 0.15C in stages. And after the battery cell is finished, taking the battery cell out of the formation equipment, and placing the battery cell in a 35 ℃ oven again for 5 days. And finally, taking out the battery core, placing the battery core on a capacity-dividing test cabinet, connecting the battery core with a binding post, respectively carrying out 3 times (6 times in total) of charge and discharge cycles at 0.5C and 1C, wherein the upper and lower limit cut-off voltages are 3.65V and 2.5V, and finally charging the battery for 0.5 hour at 1C current to finish the test. Thus, a lithium iron phosphate battery suitable for use in a wide temperature range is produced.
The normal-temperature capacity positive electrode of the lithium iron phosphate battery is 141mAh/g, and the internal resistance average value is within 1mΩ after 12 hours of capacity division. As shown in fig. 1, the lithium iron battery prepared by the preparation method has excellent low-temperature discharge performance, the 1C discharge capacity is 90.35% of the room temperature capacity in the environment of-20 ℃, the 1C discharge capacity is 73.46% of the room temperature capacity in the environment of-40 ℃, and the 1C discharge capacity is 96.33% of the room temperature capacity in the environment of 55 ℃.
Example 2:
in this embodiment, a preparation method of a lithium iron phosphate battery suitable for use in a wide temperature range is as follows:
(1) Firstly, 9370g of nanoscale carbon-coated lithium iron phosphate, 200g of superconducting carbon black, 2166.67g of carbon nanotube conductive liquid (in the carbon nanotube conductive liquid, 5wt% of carbon nanotube and the balance of N-methylpyrrolidone) and 300g of polyvinylidene fluoride are weighed. 300g of polyvinylidene fluoride and 5000g of N-methyl pyrrolidone are added into a 20L stirring barrel, the mixture is stirred at a low speed of 10rad/min for 2 hours to prepare a glue solution, and the glue solution is vacuumized for standby. Sequentially adding the carbon nanotube conductive liquid, the superconducting carbon black and the lithium iron phosphate into a 20L stirring barrel according to the sequence of the carbon nanotube conductive liquid, the superconducting carbon black and the lithium iron phosphate, simultaneously starting the stirring rotation speed of 45rad/min and the dispersing rotation speed of 3500rad/min, and continuously and finely kneading the slurry for 2 hours through high shearing force to uniformly disperse all the components; then adding N-methyl pyrrolidone for three times, simultaneously starting stirring rotation speed of 45rad/min and dispersing rotation speed of 3500rad/min for dispersing while adding N-methyl pyrrolidone, stirring for 1 hour each time until the viscosity of the slurry is 3000-4800 N.m, the fineness is below 25 mu m, taking the slurry as positive electrode slurry, starting vacuum to-95 kPa (gauge pressure), and maintaining the pressure for 0.5 hour; filtering the anode slurry into a container through a 150-mesh stainless steel screen, uniformly coating the anode slurry on carbon-coated aluminum foil with the thickness of 14 mu m at the surface density of 38mg/cm 2 by using a continuous coater, wherein the thickness of carbon-coated layers on the two sides of the aluminum foil is 1 mu m respectively, and the carbon-coated layers are made of superconductive graphite to prepare an anode coil; and rolling the positive electrode roll according to the compaction density of 2.35g/cm 3, punching the positive electrode small sheet with a fixed shape by using a laser cutting die of die cutting equipment to obtain the positive electrode small sheet with proper size, and finally transferring the positive electrode small sheet into a vacuum oven for temporary storage.
(2) Firstly, weighing 9525g of hard carbon coated artificial graphite, 130g of superconducting carbon black, 120g of sodium carboxymethylcellulose and 3g of oxalic acid (the oxalic acid has the effect that the low acidity of the oxalic acid slightly corrodes the surface of copper foil, the bonding property of a coating is improved, the hydrolysis temperature of the oxalic acid is very low, the oxalic acid can be further dried and removed, and the performance of a battery is not influenced), sequentially adding the materials into a stirring barrel, and stirring at a slow speed of 10rad/min for 2 hours to ensure that solid particles are primarily and uniformly mixed; then adding 333.33g of oxalic acid, 333.33g of carbon nanotube conductive liquid (5 wt% of carbon nanotubes in the carbon nanotube conductive liquid and the balance of water), 1333.33g of water-based binder (16 wt% of polyacrylic acid in the water-based binder and the balance of water) and deionized water, so that the solid content of slurry in a stirring barrel reaches 66.5wt%, adding deionized water, and simultaneously starting stirring rotation speed of 45rad/min and dispersing rotation speed of 3500rad/min, and continuously and finely kneading the slurry for 3 hours by high shear force to uniformly disperse each component; adding deionized water for three times, simultaneously starting stirring rotation speed of 45rad/min and dispersing rotation speed of 3500rad/min for high-speed dispersion, stirring for 1 hour each time until slurry viscosity is 3000-3500 N.m and fineness is below 40 mu m, taking the slurry as negative electrode slurry, starting vacuum to-95 kPa (gauge pressure), and maintaining pressure for 0.5 hour; filtering the cathode slurry into a container through a 150-mesh stainless steel screen, and uniformly coating the slurry on a copper foil with the thickness of 6 mu m at the surface density of 16.2mg/cm 2 by using a continuous coater to prepare a cathode coil; and rolling the cathode coil according to the compaction density of 1.35g/cm 3, then punching the cathode small sheet with a fixed shape by using a laser cutting die of die cutting equipment to obtain the cathode small sheet with proper size, and finally transferring the cathode small sheet into a vacuum oven for temporary storage.
(3) And (3) processing the positive electrode small piece, the negative electrode small piece and the wet high-porosity PP diaphragm with the single side coated with the Al 2O3 ceramic coating in the steps (1) and (2) into a core bag with the capacity of 13Ah by using a Z-shaped lamination type structure, and then sequentially completing the working procedures of hot and cold pressing, short circuit testing, cover plate ultrasonic welding, tab bending, shell entering, shell laser welding and the like to complete the 13Ah non-injected aluminum shell assembly, wherein the porosity of the PP diaphragm is 37%, the average pore diameter of the PP diaphragm is 0.15 mu m, the thickness of the PP diaphragm is 20 mu m, and the thickness of the Al 2O3 ceramic coating is 2 mu m.
(4) And (3) baking the assembly without liquid injection in the step (3) for 36 hours by a vacuum oven at 85 ℃, recovering to room temperature, taking out, injecting low-temperature special electrolyte containing lithium dioxalate borate and lithium bis (trifluoromethyl) sulfonyl imide into the assembly without liquid injection by using a liquid injection machine according to the liquid injection coefficient of 5.1g/Ah, using an adhesive tape to enable a liquid injection port to be simply packaged, taking out, placing the liquid injection machine in the oven at 35 ℃, baking for 24 hours, recovering to room temperature, and taking out to form the battery cell.
In the electrolyte, the concentration of lithium dioxalate borate was 6.1wt%, the concentration of lithium bistrifluoromethylsulfonyl imide was 2.8wt%, the concentration of lithium difluorophosphate was 1.1wt%, the concentration of triallyl phosphate was 3.4wt%, the concentration of vinylene carbonate was 2.22wt%, the concentration of ethylene carbonate was 24wt%, the concentration of propylene carbonate was 14.2wt%, and the balance was ethyl acrylate.
(5) And placing the battery cell after liquid injection on formation equipment, connecting positive and negative poles of the battery cell with a channel test line, and charging to 3.65V for 3.33 hours at 0.05C, 0.1C and 0.15C in stages. And after the battery cell is finished, taking the battery cell out of the formation equipment, and placing the battery cell in a 35 ℃ oven again for 5 days. And finally, taking out the battery core, placing the battery core on a capacity-division testing cabinet, connecting the battery core with a binding post, respectively carrying out 3 times of charge-discharge cycles at 0.5C and 1C, enabling the cut-off voltage of the upper line and the lower line to be 3.65V and 2.5V, and finally charging the battery for 0.5 hour at 1C current to finish the test. Thus, a lithium iron phosphate battery suitable for use in a wide temperature range is produced.
The specific capacity of the normal-temperature capacity positive electrode of the lithium iron phosphate battery is 140.15mAh/g, and the internal resistance average value is within 1mΩ after 12 hours of capacity division. As shown in FIG. 2, the lithium iron battery prepared by the preparation method has a 1C discharge capacity of 76.93% of room temperature capacity in an environment of-20 ℃, a 1C discharge capacity of 37.47% of room temperature capacity in an environment of-40 ℃, and a 1C discharge capacity of 98.17% of room temperature capacity in an environment of 55 ℃.
Example 3:
in this embodiment, a method for preparing a commercial lithium iron phosphate power battery includes:
(1) Firstly, 9370g of commercial power lithium iron phosphate, 200g of conductive carbon black, 300g of polyvinylidene fluoride and 2166.67g of carbon nanotube conductive liquid (the concentration of the carbon nanotube in the carbon nanotube conductive liquid is 5wt% and the balance is N-methylpyrrolidone) are weighed. 300g of polyvinylidene fluoride and 5000g of N-methyl pyrrolidone are added into a 20L stirring barrel, the mixture is stirred at a low speed of 15rad/min for 2 hours to prepare a glue solution, and the glue solution is vacuumized for standby. Then sequentially adding the carbon nanotube conductive liquid, the conductive carbon black and the lithium iron phosphate into a 20L stirring barrel according to the sequence of the carbon nanotube conductive liquid, the conductive carbon black and the lithium iron phosphate, stirring for 2 hours each time until the fineness is less than 26 mu m and the viscosity is 4000-6000 N.m, taking the carbon nanotube conductive liquid, the conductive carbon black and the lithium iron phosphate as positive electrode slurry, starting vacuum to-95 kPa (gauge pressure), and maintaining the pressure for 0.5 hour; filtering the anode slurry into a container through a 150-mesh stainless steel screen, uniformly coating the anode slurry on carbon-coated aluminum foil with the thickness of 18 mu m at the surface density of 38mg/cm 2 by using a continuous coater, wherein the thickness of carbon-coated layers on the two sides of the aluminum foil is 3 mu m respectively, and the carbon-coated layers are made of carbon nano tubes to prepare an anode coil; and rolling the positive electrode roll according to the compaction density of 2.34g/cm 3, punching the positive electrode small sheet with a fixed shape by using a laser cutting die of die cutting equipment to obtain the positive electrode small sheet with proper size, and finally transferring the positive electrode small sheet into a vacuum oven for temporary storage.
(2) Firstly, 9525g of artificial graphite, 150g of conductive carbon black, 120g of sodium carboxymethylcellulose, 3g of oxalic acid, 583.33g of carbon nanotube conductive liquid (the concentration of carbon nanotubes in the carbon nanotube conductive liquid is 5wt% and the balance is water) and 425g of styrene-butadiene rubber aqueous emulsion (the concentration of styrene-butadiene rubber in the styrene-butadiene rubber aqueous emulsion is 45wt% and the balance is water) are weighed. 120g of sodium carboxymethylcellulose and 10000g of deionized water are added into a 20L stirring barrel, the mixture is stirred at a low speed of 15rad/min to prepare a glue solution, the glue solution is uniformly dispersed for 2 hours, and vacuum pumping is carried out for standby. Sequentially adding oxalic acid, carbon nanotube conductive liquid, conductive carbon black and artificial graphite into a stirring barrel, and stirring for 2 hours each time to uniformly mix the components; adding deionized water for three times, dispersing at high speed of 3500rad/min, stirring for 1 hour each time until the viscosity of the slurry is 3000-3500 N.m, the fineness is below 40 μm, finally adding 425g of styrene-butadiene rubber water emulsion, stirring for 1 hour at low speed of 15rad/min as negative electrode slurry, starting vacuum to-95 kPa (gauge pressure), and maintaining the pressure for 0.5 hour; filtering the negative electrode slurry into a container through a 150-mesh stainless steel screen, and uniformly coating the negative electrode slurry on a copper foil with the thickness of 8 mu m at the surface density of 16mg/cm 2 by using a continuous coater to prepare a negative electrode coil; and rolling the negative electrode roll according to the compaction density of 1.41g/cm 3, then punching the negative electrode small sheet with a fixed shape by using a laser cutting die of die cutting equipment to obtain the negative electrode small sheet with proper size, and finally transferring the negative electrode small sheet into a vacuum oven for temporary storage.
(3) And (3) processing the positive electrode small piece, the negative electrode small piece and the wet high-porosity PP diaphragm (the PP diaphragm porosity is 37 percent, the average pore diameter of the PP diaphragm is 0.15 mu m, and the thickness of the PP diaphragm is 20 mu m) in the steps (1) and (2) into a core package with the capacity of 13Ah by using a lamination machine, and then sequentially completing the working procedures of cold and hot pressing, short circuit testing, cover plate ultrasonic welding, lug bending, shell entering, shell laser welding and the like, so as to complete the 13Ah non-injected aluminum shell assembly.
(4) And (3) baking the non-injected assembly in the step (3) for 36 hours by a vacuum oven at 85 ℃, recovering to room temperature, taking out, injecting the power electrolyte of the commercial lithium iron phosphate battery into the non-injected assembly by using a liquid injection machine according to the liquid injection coefficient of 4.9g/Ah, simply packaging a liquid injection port by using an adhesive tape, taking out, placing the liquid injection machine in the oven at 35 ℃, baking for 24 hours, recovering to room temperature, and taking out to form the battery core.
The composition and content of the commercial lithium iron phosphate battery power electrolyte are as follows: the concentration of lithium hexafluorophosphate was 12wt%, the concentration of vinylene carbonate was 1wt%, the concentration of propylene sulfite was 1.5wt%, the concentration of lithium difluorophosphate was 0.5wt%, the concentration of ethylene carbonate was 35wt%, and the balance was ethyl methyl carbonate.
(5) And placing the battery cell after liquid injection on formation equipment, connecting positive and negative poles of the battery cell with a channel test line, and charging to 3.65V for 3.33 hours at 0.05C, 0.1C and 0.15C in stages. And after the battery cell is finished, taking the battery cell out of the formation equipment, and placing the battery cell in a 35 ℃ oven again for 5 days. And finally, taking out the battery core, placing the battery core on a capacity-division testing cabinet, connecting the battery core with a binding post, respectively carrying out 3 times of charge-discharge cycles at 0.5C and 1C, enabling the cut-off voltage of the upper line and the lower line to be 3.65V and 2.5V, and finally charging the battery for 0.5 hour at 1C current to finish the test. Thus, a commercial lithium iron phosphate power battery was produced.
The normal-temperature capacity positive electrode of the lithium iron phosphate battery is 143.48mAh/g, and the internal resistance average value is within 3mΩ after 12 hours of capacity division. As shown in fig. 3, the power lithium iron battery prepared by the preparation method has a 1C discharge capacity of 68.71% of the room temperature capacity in an environment of-20 ℃, and a 1C discharge capacity of 99.43% of the room temperature capacity in an environment of-40 ℃ in which the 1C discharge capacity cannot be performed.
The example result shows that on the basis of the traditional preparation process of the lithium iron phosphate battery, the invention designs the optimal surface loading amount by adjusting the types and the proportion of the anode and the cathode in the battery and the conductive agent and the binder, selects the type of the high-quality conductive agent, forms a three-dimensional space conductive network on the anode and the cathode material layers, improves the electron conductivity among active material particles, and ensures that the capacity of the anode and the cathode active materials can be exerted to the greatest extent; on the basis, a high-quality carbon coating foil is selected, so that the bonding between an active material layer and a current collector is enhanced, the transmission of charges between the material layer and the foil is facilitated, and the rate capability of the battery is improved; the multi-layer wet high-porosity diaphragm is selected, and the surface of the diaphragm is covered with a layer of Al 2O3 coating, so that the puncture resistance of the diaphragm is improved while the liquid storage capacity of the diaphragm is improved, not only is the defect of electrolyte caused by excessively high consumption of electrolyte when the battery is used at a high temperature avoided, but also the potential safety hazard caused by lithium precipitation when the battery is used at a low temperature is avoided.
Claims (10)
1. The preparation method of the lithium iron phosphate battery suitable for the wide temperature range is characterized by comprising the following steps of:
(1) Firstly, lithium iron phosphate is prepared according to the weight proportion: conductive agent: binder=91 to 94:2 to 4: 2-4, adding the mixture into a stirring barrel; then adding N-methyl pyrrolidone for fine kneading to ensure that the solid content of slurry in a stirring barrel is 60-70 wt%, and simultaneously starting stirring rotation speed is 40-45 rad/min and dispersing rotation speed is 2800-3500 rad/min for 2-4 hours; then continuously adding N-methyl pyrrolidone for three times, and simultaneously starting stirring rotation speed of 40-50 rad/min and dispersing rotation speed of 3000-4000 rad/min, wherein each time lasts for 0.5-2 hours; finally, the anode slurry with uniform dispersion and viscosity of 4500-8000 N.m is obtained;
(2) Filtering the positive electrode slurry through a 120-150 mesh screen, and uniformly coating the positive electrode slurry on a carbon-coated aluminum foil with the thickness of 12-18 mu m by using a continuous coater according to the surface density of 25-38 mg/cm 2;
(3) The positive electrode roll is rolled by a roll squeezer according to the compaction density of 2.2-2.4 g/cm 3, and then a laser cutting die is used for completing punching of the positive electrode small sheet, so that the positive electrode small sheet with proper size is prepared;
(4) Firstly, artificial graphite is prepared according to the weight proportion: conductive agent: binder=94 to 95.5:1.2 to 1.8:3.3 to 4.2, and adding the mixture into a stirring barrel; adding deionized water for fine kneading to ensure that the solid content of the slurry in the stirring barrel is 60-70 wt%, and simultaneously starting the stirring rotation speed of 40-45 rad/min and the dispersing rotation speed of 2800-3500 rad/min for 2-4 hours; then adding deionized water continuously for three times, and simultaneously starting stirring rotation speed of 40-50 rad/min and dispersing rotation speed of 3000-4000 rad/min, wherein each time lasts for 0.5-2 hours; finally, anode slurry with uniform dispersion and viscosity of 3500-4800 N.m is obtained;
(5) Filtering the negative electrode slurry through a 100-120 mesh screen, and uniformly coating the negative electrode slurry on copper foil with the thickness of 6-8 mu m by using a continuous coater according to the surface density of 14.4-16.8 mg/cm 2;
(6) The negative electrode roll is rolled by a roll squeezer according to the compaction density of 1.3-1.5 g/cm 3, and then a laser cutting die is used for completing punching of a negative small piece, so that the negative small piece with proper size is prepared;
(7) Matching the positive and negative small pieces with a diaphragm with a single-sided Al 2O3 ceramic coating, finishing core package manufacturing by a lamination machine in a Z-shaped lamination type structure, and assembling to form an assembly without liquid injection;
(8) After the non-injected assembly is subjected to vacuum baking at 80-90 ℃ for 24-36 hours, injecting electrolyte of the lithium iron phosphate battery into the non-injected assembly by using a liquid injector according to the coefficient of 4.5-6.5 g/Ah, and aging for 12-24 hours at 30-40 ℃ to form a battery cell;
(9) Placing the battery cell on a formation device, charging the battery cell with an opening formation system of the battery cell in three sections at 0.02-0.05C, 0.05-0.1C and 0.1-0.2C for 3.33 hours respectively, sealing after the battery cell is completed, and then transferring the battery cell to an environment of 30-40 ℃ for open circuit aging for 3-7 days;
(10) And carrying out capacity-dividing operation on the aged battery, and obtaining the lithium iron phosphate battery which is stably used in a wide temperature area after finishing.
2. The method for preparing a lithium iron phosphate battery suitable for a wide temperature range according to claim 1, wherein the granularity D50 of lithium iron phosphate used for the positive electrode is 0.5-1.5 μm, the carbon content is 1.5-1.9 wt%, and the specific surface area is 15-22 m 2/g; the granularity D50 of the artificial graphite used for the negative electrode is 7.5-12 mu m, and the specific surface area is 1.3-1.8 m 2/g.
3. The method for preparing the lithium iron phosphate battery suitable for the wide temperature range according to claim 1, wherein the granularity D50 of the lithium iron phosphate used for the positive electrode is 0.7 mu m, the carbon content is 1.85wt%, the specific surface area is 20m 2/g, and the lithium iron phosphate battery has good low-temperature rate performance; the artificial graphite used for the negative electrode has the granularity D50 of 11 mu m, the specific surface area of 1.5m 2/g and good electrochemical performance in a wide temperature area.
4. The method for preparing a lithium iron phosphate battery suitable for a wide temperature range according to claim 1, wherein the conductive agent used for the positive electrode and the negative electrode is one or more selected from the group consisting of superconductive carbon black, conductive graphite, carbon nanotubes, ketjen black and graphene; the binder used for the positive electrode and the negative electrode is one or more than two of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, sodium alginate, sodium carboxymethyl cellulose and styrene butadiene rubber.
5. The method for preparing a lithium iron phosphate battery suitable for a wide temperature range according to claim 4, wherein the conductive agent used for the positive electrode is added in the form of conductive liquid, the concentration of the conductive agent in the conductive liquid is 4-6wt%, and the balance is N-methylpyrrolidone; the conductive agent used in the negative electrode is added in the form of conductive liquid, the concentration of the conductive agent in the conductive liquid is 4-6wt% and the balance is water.
6. The method for preparing a lithium iron phosphate battery suitable for a wide temperature range according to claim 4, wherein in the step (1), the lithium iron phosphate, the conductive agent and the binder are weighed and added into a stirring barrel, and stirring is started to perform primary mixing of dry powder for 1-3 hours at a rotating speed of 10-15 rad/min; in the step (4), the artificial graphite, the conductive agent and the adhesive are weighed and added into a stirring barrel, stirring is started, and dry powder is primarily mixed for 1-3 hours at the rotating speed of 10-15 rad/min.
7. The method for producing a lithium iron phosphate battery suitable for use in a wide temperature range according to claim 1, wherein in the step (1), 61 to 63wt% of the total amount of N-methylpyrrolidone is added for fine kneading, and 11 to 13wt% of the total amount of N-methylpyrrolidone is added each time when N-methylpyrrolidone is continuously added in three times; in the step (4), 57.5 to 60 weight percent of the total amount of deionized water is added for fine kneading, and when the deionized water is continuously added in three times, 13.5 to 14.5 weight percent of the total amount of the deionized water is added each time.
8. The method for preparing the lithium iron phosphate battery suitable for the wide temperature range, which is characterized in that in the carbon-coated aluminum foil used for coating the positive electrode, the thickness of the carbon-coated layers on the two sides of the aluminum foil is respectively 1-3 mu m, and the carbon-coated layer material is one or more than two selected from superconducting carbon black, superconducting graphite, carbon nano tubes and superconducting silver colloid.
9. The method for preparing the lithium iron phosphate battery suitable for the wide temperature range, which is disclosed in claim 1, is characterized in that the membrane used in lamination is a wet high-porosity membrane, the thickness of the membrane is 15-25 μm, the porosity of the membrane is 35-45%, the average pore diameter is 0.05-0.15 μm, the membrane is made of one or two of polypropylene and polyethylene, and the thickness of a ceramic coating of Al 2O3 coated on one side of the membrane is 1-3 μm.
10. The method for preparing a lithium iron phosphate battery suitable for a wide temperature range according to claim 1, wherein in the electrolyte used in the non-injected assembly, the lithium salt is one or more of lithium hexafluorophosphate, lithium difluorosulfimide, lithium tetrafluoroborate, lithium dioxalate borate, lithium bistrifluoromethylsulfonimide and lithium difluorophosphate, and the content thereof is 10-13 wt%; the additive is one or more than two of propylene sulfite, triallyl phosphate, dimethyl trifluoroacetamide, phosphorus pentoxide, trimethyl phosphate and vinylene carbonate, and the content of the additive is 1-8wt%; the solvent is one or more of methyl ethyl carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate and ethyl acrylate, and the balance is solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210210652.2A CN114566717B (en) | 2022-03-04 | 2022-03-04 | Preparation method of lithium iron phosphate battery suitable for wide temperature range |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210210652.2A CN114566717B (en) | 2022-03-04 | 2022-03-04 | Preparation method of lithium iron phosphate battery suitable for wide temperature range |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114566717A CN114566717A (en) | 2022-05-31 |
| CN114566717B true CN114566717B (en) | 2024-04-26 |
Family
ID=81718646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210210652.2A Active CN114566717B (en) | 2022-03-04 | 2022-03-04 | Preparation method of lithium iron phosphate battery suitable for wide temperature range |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114566717B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117895084B (en) * | 2024-03-18 | 2024-08-20 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and power utilization device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122406A (en) * | 2022-01-25 | 2022-03-01 | 成都特隆美储能技术有限公司 | Preparation method of graphene modified lithium iron phosphate and lithium iron phosphate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752561B (en) * | 2009-12-11 | 2012-08-22 | 宁波艾能锂电材料科技股份有限公司 | Graphite alkene iron lithium phosphate positive active material, preparing method thereof, and lithium ion twice battery based on the graphite alkene modified iron lithium phosphate positive active material |
| CN106450328A (en) * | 2016-10-14 | 2017-02-22 | 深圳市沃特玛电池有限公司 | LiFePO4 power battery and preparation method thereof |
-
2022
- 2022-03-04 CN CN202210210652.2A patent/CN114566717B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122406A (en) * | 2022-01-25 | 2022-03-01 | 成都特隆美储能技术有限公司 | Preparation method of graphene modified lithium iron phosphate and lithium iron phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 圆柱LiFePO_4电池低温性能的研究;张小满;杨承昭;华秉杨;张新河;;电源技术;20150420(第04期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114566717A (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107565086B (en) | Preparation method of battery plate | |
| CN110010903B (en) | Positive pole piece and battery | |
| CN108417777B (en) | Porous ternary composite positive plate and preparation method and application thereof | |
| CN108565412B (en) | Carbon fluoride mixed positive pole piece and preparation method thereof | |
| CN113258031B (en) | Battery with a battery cell | |
| CN106711430A (en) | Production method of lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode used for lithium-sulfur battery | |
| CN110233284B (en) | Low-temperature high-energy-density long-cycle lithium iron phosphate battery | |
| CN108134044B (en) | High-safety lithium ion battery negative electrode material and preparation method thereof | |
| CN116014084B (en) | Dry electrode plate of carbon-based solid lithium battery, preparation method and battery core | |
| CN115084433B (en) | Positive pole piece and sodium ion battery | |
| CN113675365A (en) | Negative plate and lithium ion battery | |
| CN117497835A (en) | Solid-state battery cell, preparation method thereof and solid-state battery | |
| CN116387509A (en) | Composite positive electrode for lithium metal battery and preparation method thereof | |
| CN114566717B (en) | Preparation method of lithium iron phosphate battery suitable for wide temperature range | |
| CN113488342B (en) | Solid electrolyte material for tantalum capacitor lithium battery and preparation method thereof | |
| CN113013395A (en) | Positive electrode material and preparation method and application thereof | |
| CN109103492B (en) | Hydroxyapatite nanowire-carbon nanotube film, preparation method thereof and lithium-sulfur battery | |
| CN116706029A (en) | Double-layer coated graphite anode material and preparation method thereof | |
| WO2023174435A1 (en) | Ternary blended positive electrode material, preparation method therefor and battery | |
| CN106803575A (en) | A kind of anode material for lithium-ion batteries and its preparation method and application | |
| CN114122406B (en) | Preparation method of graphene modified lithium iron phosphate and lithium iron phosphate | |
| CN113299919B (en) | Positive pole piece and lithium ion battery comprising same | |
| CN115275168A (en) | High-rate lithium ion battery negative electrode material and preparation method thereof | |
| CN113991243A (en) | FeCoCuZn co-doped Ni-based alloy-carbon nanotube composite material modified diaphragm and preparation method and application thereof | |
| CN114204035A (en) | Cellulose-supported solid electrolyte membrane and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |