CN106328935A - High-safety long-life composite material system power battery and preparation method thereof - Google Patents
High-safety long-life composite material system power battery and preparation method thereof Download PDFInfo
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- CN106328935A CN106328935A CN201610780828.2A CN201610780828A CN106328935A CN 106328935 A CN106328935 A CN 106328935A CN 201610780828 A CN201610780828 A CN 201610780828A CN 106328935 A CN106328935 A CN 106328935A
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- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 239000006230 acetylene black Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 239000004698 Polyethylene Substances 0.000 claims abstract description 11
- 229920000573 polyethylene Polymers 0.000 claims abstract description 11
- -1 polyethylene Polymers 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 29
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000005030 aluminium foil Substances 0.000 claims description 11
- 239000011889 copper foil Substances 0.000 claims description 11
- 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 10
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910013872 LiPF Inorganic materials 0.000 claims description 2
- 101150058243 Lipf gene Proteins 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- UCVQOIPQDBZRMG-UHFFFAOYSA-N [C].COC(C=1C(C(=O)OC)=CC=CC1)=O Chemical compound [C].COC(C=1C(C(=O)OC)=CC=CC1)=O UCVQOIPQDBZRMG-UHFFFAOYSA-N 0.000 claims 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000002033 PVDF binder Substances 0.000 abstract description 21
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 21
- 239000002041 carbon nanotube Substances 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 238000012827 research and development Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract 2
- 238000005096 rolling process Methods 0.000 abstract 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 abstract 1
- 229910021383 artificial graphite Inorganic materials 0.000 abstract 1
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract 1
- 238000005524 ceramic coating Methods 0.000 abstract 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 239000011224 oxide ceramic Substances 0.000 abstract 1
- 229910052574 oxide ceramic Inorganic materials 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 7
- 229910001290 LiPF6 Inorganic materials 0.000 description 7
- 102100023116 Sodium/nucleoside cotransporter 1 Human genes 0.000 description 7
- 101710123675 Sodium/nucleoside cotransporter 1 Proteins 0.000 description 7
- 238000001467 acupuncture Methods 0.000 description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010998 test method 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
- 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
- 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
- H01M10/42—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of research and development and preparation of lithium batteries, in particular to a composite material system power battery with high safety and long service life and a preparation method thereof. The manufacturing method of the power battery comprises the following steps: mixing 70-90% of nickel cobalt lithium manganate and 10-30% of lithium manganese phosphate, fully mixing with a high-conductivity carbon nano tube, then, rolling and slitting a coating to prepare a positive plate, fully mixing a negative electrode with artificial graphite and acetylene black, then, rolling and slitting to prepare a negative plate, preparing a battery core by a diaphragm by adopting a wet polyethylene substrate, an aluminum oxide ceramic coating and a binder PVDF according to a required size, and then, injecting liquid to form a partial volume to prepare the battery, wherein the electrolyte is a high-molar-concentration mixed solvent system of various composite additives. The prepared battery has a retention rate of 88 percent after being cycled at normal temperature for 1200 weeks and a retention rate of 87 percent after being cycled at high temperature of 45 ℃ for 680 weeks, has good thermal stability, energy density, normal temperature and high temperature cycle performance and excellent safety, and can be widely applied to electric automobiles and related products.
Description
Technical field
The present invention relates to the research and development preparation field of lithium battery, be specifically related to the composite system of a kind of high-safety long-life
Electrokinetic cell and preparation method thereof.
Background technology
Reach under the target of 300Wh/kg orders about in the energy density of the year two thousand twenty battery module to be realized, nickelic ternary material
Become the focus of research and development, but domestic nickelic ternary battery in use safety be without shortcomings such as guarantee, high temperature cyclic performance differences,
At the beginning of 2016, Ministry of Industry and Information promulgate postpone in commercial car use ternary material power lithium-ion battery, cause ternary lithium from
Sub-battery enterprise in commotion, my department, as power lithium-ion battery leading enterprise, takes the lead in strengthening ternary lithium ion battery
The R&D intensity of security performance.Patent CN104300123A uses the method that nickel-cobalt-manganese ternary material is mixed with iron manganese phosphate for lithium,
The method is given prominence to the key points being mixed into of iron manganese phosphate for lithium, ternary battery safety nickelic to all types and the shadow of cycle performance
Ringing, the present invention is then just for high-nickel material LiNi0.6Co0.2Mn0.2O2With LiMn0.8Fe0.2PO4Many-sided both different blended of investigation
Composition and division in a proportion example and the combination of the auxiliary material impact on battery combination property, provides more safe and reliable foundation for reality application.
Summary of the invention
Present invention aim to address above-mentioned the deficiencies in the prior art, improve high-nickel material LiNi0.6Co0.2Mn0.2O2Combine
Close performance, it is provided that composite system electrokinetic cell of a kind of high-safety long-life and preparation method thereof.
The present invention is achieved by the following technical solutions:
The composite system electrokinetic cell of a kind of high-safety long-life, including positive pole, barrier film, negative pole, electrolyte and outer
Shell, described
Positive pole includes the component of following mass percent: 93～the polyethylene pyrrole of the positive active material of 97%, 1～2%
Pyrrolidone (PVP), 1～3.5% CNT (CNTs) and 1～the Kynoar (PVDF) of 3.5%；Slurry viscosity: 6000
～9000mPa.S；
Wherein, positive active material is high-nickel material LiNi0.6Co0.2Mn0.2O2And LiMn (NCM)0.8Fe0.2PO4 (LMFP)
Mixture, and LiNi0.6Co0.2Mn0.2O2Account for the 70～90% of positive active material gross mass, LiMn0.8Fe0.2PO4Account for positive pole
The 10～30% of active substance gross mass；
Negative pole includes the component of following mass percent: 93～the graphite of 96%, 1～the acetylene black of 3%, 1～the carboxylic of 3%
Sodium carboxymethylcellulose pyce and 1.5～the butadiene-styrene rubber of 3%；Slurry viscosity: 3000～5000mPa S；
Barrier film is coated separator, and described diaphragm matrix is wet method polyethylene (PE), and coating is pottery (Al2O3Or SiO2), viscous
Knot agent is Kynoar-hexafluoropropene (PVDF-HFP), Kynoar (PVDF) or polymethyl methacrylate (PMMA),
Barrier film gross thickness is 12～20 μm；
Electrolyte includes the electrolyte LiPF that concentration is 0.9mol/L～1.2mol/L6, vinyl carbonate (EC), carbonic acid first
Ethyl ester (EMC) and dimethyl carbonate (DMC) press the organic solvent of the volume ratio mixing of 1:1:1, and include 1～2% carbonic acid sub-
Vinyl acetate (VC), 1～2% propylene sulfite (PS), 0～1% biphenyl (BP) and 0～1% cyclohexyl benzene (CHB) add at interior
Add agent.
Preferably, the aluminium foil that described positive pole uses collector thickness to be 12～18 μm.
Preferably, the Copper Foil that described negative pole uses collector thickness to be 8～12 μm.
Preferably, described anode pole piece applies 1～5mm ceramic sol with lug adjoining border, and ceramic sol is by Al2O3With
N-Methyl pyrrolidone (NMP) forms, and Al2O3Account for the 15～30% of ceramic sol gross mass.
Preferably, the caliber of described CNT is 10～30nm.
Preferably, described positive pole double-coated surface density is 340～430kg/m2, negative pole double-coated surface density is 190
～240kg/m2。
Preferably, described shell is aluminum hull, box hat or moulds shell.
The method preparing the composite system electrokinetic cell of a kind of high-safety long-life, comprises the following steps:
(1), with NMP as solvent, after being completely dissolved PVDF (molecular weight 90～1,000,000), CNTs high speed dispersion is added, then
It is mixed into LiNi0.6Co0.2Mn0.2O2And LiMn0.8Fe0.2PO4Positive active material, uses coating machine even application to exist after fully closing slurry
On aluminium foil, drying, roll-in, cut after, make anode pole piece；
(2), with deionized water as solvent, after being completely dispersed dissolving sodium carboxymethyl cellulose, it is mixed into conductive agent acetylene black and bears
Pole active substance Delanium, the most again with binding agent butadiene-styrene rubber mixed pulp, is then coated on Copper Foil, baking, roll-in,
Cathode pole piece is made after cutting；
(3) according to required positive/negative plate size, use coated separator, be wound into battery core, then two battery cores link shell
Rear Laser Welding, fluid injection, chemical conversion, make battery.
The beneficial effects of the present invention is:
In the present invention, the aluminum-shell battery of making uses anode composite system, improves the general safety stability of battery system.
Lithium ion battery running voltage is 3.0～4.2V, uses this scope running voltage, can substantially reduce the electricity that high voltage system is brought
Solve matter resolution problem, and then battery table reveals good cycle performance；Anode pole piece and lug adjoining border coating 1～5mm pottery
Porcelain cement body, on the one hand can improve pole piece and cut the burr being occur, on the other hand can improve the heat stability of battery；Positive conductive
Agent CNT, fluid behaviour can limited improvement stir uneven, and CNT also has the highest electric conductivity simultaneously；Electrolysis
In liquid, the addition of additive can be obviously improved security performance and the cycle performance of battery, particularly high temperature cyclic performance.The present invention
Making battery room temperature 1200 weeks conservation rates 88% of circulation, high temperature 45 DEG C circulates 680 weeks conservation rates 87%, has good thermally-stabilised
Property, energy density, room temperature, high temperature cyclic performance and excellent safety, can be widely used for electric automobile and Related product.
Accompanying drawing explanation
Fig. 1 is LiNi of the present invention0.6Co0.2Mn0.2O2:LiMn0.8Fe0.2PO4Composite scanning electron microscope (SEM) photograph during=8:2；
Fig. 2 is the room temperature circulation figure of the battery that the embodiment of the present invention is prepared with comparative example；
Fig. 3 is the high temperature circulation figure of the battery that the embodiment of the present invention is prepared with comparative example；
Fig. 4 is acupuncture effect figure of the present invention；
Fig. 5 is that in acupuncture course of the present invention, voltage changes over curve.
Detailed description of the invention
For being best understood from the present invention, below in conjunction with embodiment and accompanying drawing, the invention will be further described, following example
It is only that the present invention will be described rather than is limited it.
Embodiment one
The present embodiment use coated separator use 14 μm PE to be base material, 4 μm Al2O3Coating (i.e. 14+4).
1), with NMP as solvent, after being completely dissolved PVDF, add CNT high speed dispersion, be then mixed into anode composite and live
Property material (LiNi0.6Co0.2Mn0.2O2:LiMn0.8Fe0.2PO4=8:2), use coating machine even application at aluminium foil after fully closing slurry
On, drying, roll-in, cut after, make anode pole piece, PVP 1～2%, PVDF 1～3.5%, CNT 1～3.5%, slurry
Material viscosity: 6000～9000mPa.S, positive pole applicator surface density 370kg/m2, slurry edge coating 2mm Al2O3Ceramic sol.Negative
Pole is with deionized water as solvent, after being completely dispersed CMC, is mixed into acetylene black and negative electrode active material Delanium, the most again with SBR
Mixed pulp, is then coated on Copper Foil, baking, roll-in, cut after make cathode pole piece.Mixed proportion: graphite 93～
96%, acetylene black 1～3%, sodium carboxymethyl cellulose 1～3%, butadiene-styrene rubber 1.5～3.5%.Slurry viscosity: 3000～
5000mPa S, negative pole applicator surface density 205kg/m2；
2), according to required positive/negative plate size, use 14+4 coated separator, be wound into battery core, then two battery core parallel connections
Enter Laser Welding after shell, inject containing 1.1mol/L LiPF6/ (EC+EMC+DMC, volume ratio 1:1:1), 2%VC, 2%PS, 1%
The electrolyte of BP, is melted into, makes battery.
Embodiment two
The present embodiment use coated separator use 12 μm PE to be base material, 4 μm Al2O3With 2 μm PVDF coating (i.e. 12+4
+2)。
1), with NMP as solvent, after being completely dissolved PVDF, add CNT high speed dispersion, be then mixed into anode composite and live
Property material (LiNi0.6Co0.2Mn0.2O2:LiMn0.8Fe0.2PO4=8:2), use coating machine even application at aluminium foil after fully closing slurry
On, drying, roll-in, cut after, make anode pole piece, PVP 1～2%, PVDF 1～3.5%, CNT 1～3.5%, slurry
Material viscosity: 6000～9000mPa.S, positive pole applicator surface density 370kg/m2, slurry edge coating 2mm Al2O3Ceramic sol.Negative
Pole is with deionized water as solvent, after being completely dispersed CMC, is mixed into acetylene black and negative electrode active material Delanium, the most again with SBR
Mixed pulp, is then coated on Copper Foil, baking, roll-in, cut after make cathode pole piece.Mixed proportion: graphite 93～96%,
Acetylene black 1～3%, sodium carboxymethyl cellulose 1～3%, butadiene-styrene rubber 1.5～3.5%.Slurry viscosity: 3000～5000mPa
S, negative pole applicator surface density 205kg/m2；
2), according to required positive/negative plate size, using 12+4+2 coated separator, be wound into battery core, then two battery cores are also
Link Laser Welding after shell, inject containing 1.1mol/L LiPF6/ (EC+EMC+DMC, volume ratio 1:1:1), 2%VC, 2%PS,
The electrolyte of 1%BP, is melted into, makes battery.
Embodiment three
The present embodiment use coated separator use 12 μm PE to be base material, 4 μm Al2O31 μm PVDF coating each with two sides
(i.e. 12+4+1+1).
1), with NMP as solvent, after being completely dissolved PVDF, add CNT high speed dispersion, be then mixed into anode composite and live
Property material (LiNi0.6Co0.2Mn0.2O2:LiMn0.8Fe0.2PO4=8:2), use coating machine even application at aluminium foil after fully closing slurry
On, drying, roll-in, cut after, make anode pole piece, PVP 1～2%, PVDF 1～3.5%, CNT 1～3.5%, slurry
Material viscosity: 6000～9000mPa.S, positive pole applicator surface density 370kg/m2, slurry edge coating 2mm Al2O3Ceramic sol.Negative
Pole is with deionized water as solvent, after being completely dispersed CMC, is mixed into acetylene black and negative electrode active material Delanium, the most again with
SBR mixed pulp, is then coated on Copper Foil, baking, roll-in, cut after make cathode pole piece.Mixed proportion: graphite 93～
96%, acetylene black 1～3%, sodium carboxymethyl cellulose 1～3%, butadiene-styrene rubber 1.5～3.5%.Slurry viscosity: 3000～
5000mPa S, negative pole applicator surface density 205kg/m2；
2), according to required positive/negative plate size, use 12+4+1+1 coated separator, be wound into battery core, then two battery cores
And link Laser Welding after shell, inject containing 1.1mol/L LiPF6/ (EC+EMC+DMC, volume ratio 1:1:1), 2%VC, 2%PS,
The electrolyte of 1%BP, is melted into, makes battery.
Embodiment four
The present embodiment use coated separator use 14 μm PE to be base material, each 2 μm PVDF coatings of one side (i.e. 14+2+2).
1), with NMP as solvent, after being completely dissolved PVDF, add CNT high speed dispersion, be then mixed into anode composite and live
Property material (LiNi0.6Co0.2Mn0.2O2:LiMn0.8Fe0.2PO4=8:2), use coating machine even application at aluminium foil after fully closing slurry
On, drying, roll-in, cut after, make anode pole piece, PVP 1～2%, PVDF 1～3.5%, CNT 1～3.5%, slurry
Material viscosity: 6000～9000mPa.S, positive pole applicator surface density 370kg/m2, slurry edge coating 2mm Al2O3Ceramic sol.Negative
Pole is with deionized water as solvent, after being completely dispersed CMC, is mixed into acetylene black and negative electrode active material Delanium, the most again with SBR
Mixed pulp, is then coated on Copper Foil, baking, roll-in, cut after make cathode pole piece.Mixed proportion: graphite 93～96%,
Acetylene black 1～3%, sodium carboxymethyl cellulose 1～3%, butadiene-styrene rubber 1.5～3.5%.Slurry viscosity: 3000～5000mPa
S, negative pole applicator surface density 205kg/m2；
2), according to required positive/negative plate size, using 14+2+2 coated separator, be wound into battery core, then two battery cores are also
Link Laser Welding after shell, inject containing 1.1mol/L LiPF6/ (EC+EMC+DMC, volume ratio 1:1:1), 2%VC, 2%PS,
The electrolyte of 1%BP, is melted into, makes battery.
Embodiment five
The present embodiment use coated separator use 10 μm PE to be base material, each 1 μm PVDF-HFP coating (the i.e. 12+4 of one side
+1+1)。
1), with NMP as solvent, after being completely dissolved PVDF, add CNT high speed dispersion, be then mixed into anode composite and live
Property material (LiNi0.6Co0.2Mn0.2O2:LiMn0.8Fe0.2PO4=9:1), use coating machine even application at aluminium foil after fully closing slurry
On, drying, roll-in, cut after, make anode pole piece, PVP 1～2%, PVDF 1～3.5%, CNT 1～3.5%, slurry
Material viscosity: 6000～9000mPa.S, positive pole applicator surface density 340kg/m2, slurry edge coating 2mm Al2O3Ceramic sol.
Negative pole is with deionized water as solvent, after being completely dispersed CMC, is mixed into acetylene black and negative electrode active material Delanium, the most again with
SBR mixed pulp, is then coated on Copper Foil, baking, roll-in, cut after make cathode pole piece.Mixed proportion: graphite 93～
96%, acetylene black 1～3%, sodium carboxymethyl cellulose 1～3%, butadiene-styrene rubber 1.5～3.5%.Slurry viscosity: 3000～
5000mPa S, negative pole applicator surface density 190kg/m2；
2), according to required positive/negative plate size, using 10+1+1 coated separator, be wound into battery core, then two battery cores are also
Link Laser Welding after shell, inject containing 0.9mol/L LiPF6/ (EC+EMC+DMC, volume ratio 1:1:1), 1%VC, 1%PS,
The electrolyte of 1%CHB, is melted into, makes battery.
Embodiment six
The present embodiment use coated separator use 12 μm PE to be base material, 4 μm SiO22 μm PMMA coatings each with two sides are (i.e.
12+4+1+1)。
1), with NMP as solvent, after being completely dissolved PVDF, add CNT high speed dispersion, be then mixed into anode composite and live
Property material (LiNi0.6Co0.2Mn0.2O2:LiMn0.8Fe0.2PO4=7:3), use coating machine even application at aluminium foil after fully closing slurry
On, drying, roll-in, cut after, make anode pole piece, PVP 1～2%, PVDF 1～3.5%, CNT 1～3.5%, slurry
Material viscosity: 6000～9000mPa.S, positive pole applicator surface density 430kg/m2, slurry edge coating 2mm Al2O3Ceramic sol.Negative
Pole is with deionized water as solvent, after being completely dispersed CMC, is mixed into acetylene black and negative electrode active material Delanium, the most again with SBR
Mixed pulp, is then coated on Copper Foil, baking, roll-in, cut after make cathode pole piece.Mixed proportion: graphite 93～96%,
Acetylene black 1～3%, sodium carboxymethyl cellulose 1～3%, butadiene-styrene rubber 1.5～3.5%.Slurry viscosity: 3000～5000mPa
S, negative pole applicator surface density 240kg/m2；
2), according to required positive/negative plate size, use 12+4+2+2 coated separator, be wound into battery core, then two battery cores
And link Laser Welding after shell, inject containing 1.2mol/L LiPF6/ (EC+EMC+DMC, volume ratio 1:1:1), 2%VC, 2%PS,
The electrolyte of 1%BP, 1%CHB, is melted into, makes battery.
Comparative example
The present embodiment use coated separator use 14 μm PE to be base material, 4 μm Al2O3Coating (i.e. 14+4).
1), with NMP as solvent, after being completely dissolved PVDF, add CNT high speed dispersion, be then mixed into positive electrode active material
Matter (LiNi0.6Co0.2Mn0.2O2), use after fully closing slurry coating machine even application on aluminium foil, dryings, roll-in, cut after, make
Become anode pole piece, PVP 1～2%, PVDF 1～3.5%, CNT 1～3.5%, slurry viscosity: 6000～
9000mPa.S, positive pole applicator surface density 370kg/m2.Negative pole is with deionized water as solvent, after being completely dispersed CMC, is mixed into acetylene
Black and negative electrode active material Delanium, the most again with SBR mixed pulp, is then coated on Copper Foil, baking, roll-in, cuts
After make cathode pole piece.Mixed proportion: graphite 93～96%, acetylene black 1～3%, sodium carboxymethyl cellulose 1～3%, butylbenzene rubber
Glue 1.5～3.5%.Slurry viscosity: 3000～5000mPa S, negative pole applicator surface density 205kg/m2；
2), according to required positive/negative plate size, use 14+4 coated separator, be wound into battery core, then two battery core parallel connections
Enter Laser Welding after shell, inject containing 1.1mol/L LiPF6/ (EC+EMC+DMC, volume ratio 1:1:1), 2%VC, 2%PS, 1%
The electrolyte of BP, is melted into, makes battery.
1), lithium ion battery uses takeup type structure in experimental example, is fabricated to the square aluminum housing battery of 27Ah.
2), experimental example makes constant voltage to electric current after the circulation of battery room temperature uses 1C to charge to 4.2V and reaches 0.05C eventually
Only, static 1h, constant-current discharge to 3.0V.
3) experimental example makes battery high-temperature cycle battery and be incubated after 5h, 1C charge to 4.2V constant voltage extremely at calorstat
Electric current reaches 0.05C and terminates, static 1h, constant-current discharge to 3.0V.
4) in experimental example, safety experiment all uses GB/T 31485-2015 " power accumulator safety requirements used for electric vehicle
And test method "
5) acupuncture experiment test effect is shown in that Fig. 4, Fig. 5 are that in acupuncture course, voltage changes over curve, it can be seen that real
Test in example that battery is after acupuncture, apparent unchanged, the most on fire do not explode, cell voltage slowly declines and thermal runaway does not occur.
Fig. 1 is experimental example one to four, LiNi0.6Co0.2Mn0.2O2And LiMn0.8Fe0.2PO4Compound proportioning is positive pole during 8:2
Scanning electron microscopic picture, it can be seen that the granule dispersion of composite positive pole is very good, and electrode stability is well ensured,
It is of value to room temperature and high temperature circulation.
Table 1 is the performance test results
Comparative example finds with embodiment comparing result, and such as Fig. 2-3 and table 1, lithium ferric manganese phosphate adds membership and somewhat sacrifices electricity
The room temperature in pond and high temperature cyclic performance, but security performance (acupuncture, overcharge) has and clearly improves.Use the auxiliary material of barrier film with compound
Positive electrode is combined, and the acupuncture of battery, overcharges almost all and is tested by GB.
The above embodiment is only to be described the preferred embodiment of the present invention, the not model to the present invention
Enclose and be defined, on the premise of designing spirit without departing from the present invention, the those of ordinary skill in the art technical side to the present invention
Various deformation that case is made and improvement, all should fall in the protection domain that claims of the present invention determines.
Claims (8)
1. a composite system electrokinetic cell for high-safety long-life, including positive pole, barrier film, negative pole, electrolyte and shell,
It is characterized in that: described
Positive pole includes the component of following mass percent: 93～the polyvinylpyrrolidone of the positive active material of 97%, 1～2%,
1～3.5% CNT and 1～the Kynoar of 3.5%；Slurry viscosity: 6000～9000 mPa.S；
Wherein, positive active material is high-nickel material LiNi0.6Co0.2Mn0.2O2With LiMn0.8Fe0.2PO4Mixture, and
LiNi0.6Co0.2Mn0.2O2Account for the 70～90% of positive active material gross mass, LiMn0.8Fe0.2PO4Account for the total matter of positive active material
The 10～30% of amount；
Negative pole includes the component of following mass percent: 93～the graphite of 96%, 1～the acetylene black of 3%, 1～3% carboxymethyl fine
Dimension element sodium and 1.5～the butadiene-styrene rubber of 3%；Slurry viscosity: 3000～5000 mPa.S；
Barrier film is coated separator, and described diaphragm matrix is wet method polyethylene, and coating is pottery, and binding agent is Kynoar-six
Fluoropropene, Kynoar or polymethyl methacrylate, barrier film gross thickness is 12～20 μm；
Electrolyte includes the electrolyte LiPF that concentration is 0.9mol/L～1.2mol/L6, vinyl carbonate, Ethyl methyl carbonate and carbon
Dimethyl phthalate presses the organic solvent of the volume ratio mixing of 1:1:1, and includes 1～2% vinylene carbonate, 1～2% sulfurous acid third
Alkene ester, 0～1% biphenyl and 0～1% cyclohexyl benzene at interior additive.
The composite system electrokinetic cell of a kind of high-safety long-life the most according to claim 1, it is characterised in that: institute
State the aluminium foil that positive pole uses collector thickness to be 12～18 μm.
The composite system electrokinetic cell of a kind of high-safety long-life the most according to claim 1, it is characterised in that: institute
State the Copper Foil that negative pole uses collector thickness to be 8～12 μm.
The composite system electrokinetic cell of a kind of high-safety long-life the most according to claim 1, it is characterised in that: institute
Stating anode pole piece and apply 1～5mm ceramic sol with lug adjoining border, ceramic sol is by Al2O3With N-Methyl pyrrolidone group
Become, and Al2O3Account for the 15～30% of ceramic sol gross mass.
The composite system electrokinetic cell of a kind of high-safety long-life the most according to claim 1, it is characterised in that: institute
The caliber stating CNT is 10～30nm.
The composite system electrokinetic cell of a kind of high-safety long-life the most according to claim 1, it is characterised in that: institute
Stating positive pole double-coated surface density is 340～430 kg/m2, negative pole double-coated surface density is 190～240 kg/m2。
The composite system electrokinetic cell of a kind of high-safety long-life the most according to claim 1, it is characterised in that: institute
State shell to be aluminum hull, box hat or mould shell.
8. the method for the composite system electrokinetic cell of preparation high-safety long-life described in any one of claim 1-7, its
It is characterised by, comprises the following steps:
(1), with N-Methyl pyrrolidone as solvent, after being completely dissolved Kynoar, CNT high speed dispersion is added, then
It is mixed into LiNi0.6Co0.2Mn0.2O2And LiMn0.8Fe0.2PO4Positive active material, uses coating machine even application to exist after fully closing slurry
On aluminium foil, drying, roll-in, cut after, make anode pole piece；
(2), with deionized water as solvent, after being completely dispersed dissolving sodium carboxymethyl cellulose, it is mixed into conductive agent acetylene black and negative pole is lived
Property material Delanium, the most again with binding agent butadiene-styrene rubber mixed pulp, is then coated on Copper Foil, baking, roll-in, cuts
After make cathode pole piece；
(3) according to required positive/negative plate size, use coated separator, be wound into battery core, then two battery cores swashing after linking shell
Flush weld, fluid injection, chemical conversion, make battery.
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| CN113675401A (en) * | 2021-07-13 | 2021-11-19 | 天能电池集团股份有限公司 | Laminated lithium ion battery and negative pole piece thereof |
| CN114566393A (en) * | 2022-03-23 | 2022-05-31 | 上海奥威科技开发有限公司 | Composite positive electrode material for lithium ion capacitor and application thereof |
| CN114583094A (en) * | 2020-11-30 | 2022-06-03 | 力神（青岛）新能源有限公司 | Lithium ion battery capable of improving low-temperature performance and preparation method thereof |
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Application publication date: 20170111 |