CN107819096A - Preparation method of normal-temperature cycle improved ternary lithium ion battery - Google Patents
Preparation method of normal-temperature cycle improved ternary lithium ion battery Download PDFInfo
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- CN107819096A CN107819096A CN201710948649.XA CN201710948649A CN107819096A CN 107819096 A CN107819096 A CN 107819096A CN 201710948649 A CN201710948649 A CN 201710948649A CN 107819096 A CN107819096 A CN 107819096A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011883 electrode binding agent Substances 0.000 claims abstract description 49
- 239000006258 conductive agent Substances 0.000 claims abstract description 40
- 238000005520 cutting process Methods 0.000 claims abstract description 40
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- 239000007773 negative electrode material Substances 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 229910021156 KS 6 Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000011889 copper foil Substances 0.000 claims abstract description 8
- 239000002985 plastic film Substances 0.000 claims abstract description 8
- 229920006255 plastic film Polymers 0.000 claims abstract description 8
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 27
- 230000004087 circulation Effects 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 230000004888 barrier function Effects 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007774 positive electrode material Substances 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005030 aluminium foil Substances 0.000 claims description 7
- 238000003475 lamination Methods 0.000 claims description 7
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005524 ceramic coating Methods 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- -1 methyl ethyl Chemical group 0.000 claims description 3
- 238000007581 slurry coating method Methods 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000011267 electrode slurry Substances 0.000 abstract 3
- 238000002156 mixing Methods 0.000 abstract 2
- 238000005096 rolling process Methods 0.000 abstract 2
- 238000007789 sealing Methods 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- 239000002041 carbon nanotube Substances 0.000 abstract 1
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract 1
- 239000011888 foil Substances 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000007600 charging Methods 0.000 description 4
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000007306 turnover Effects 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
- H01M4/62—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
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention discloses a preparation method of a normal-temperature cycle improved ternary lithium ion battery, which comprises the following steps: s1, mixing the positive electrode binder solution, the positive electrode conductive agent and the positive electrode active substance to obtain positive electrode slurry; coating the positive electrode slurry on an aluminum foil, and sequentially drying, rolling, slitting and die-cutting to obtain a positive electrode plate; s2, mixing the negative binder solution, the negative conductive agent and the negative active material to obtain negative slurry; coating the negative electrode slurry on a copper foil, and sequentially drying, rolling, slitting and die-cutting to obtain a negative electrode sheet; s3, laminating the positive plate and the negative plate into a battery cell through a diaphragm, placing the battery cell in an aluminum-plastic film bag, sequentially performing side top sealing, injecting electrolyte, standing, sealing, forming, and grading to obtain a soft package battery; wherein the positive electrode conductive agent is at least one selected from conductive carbon black, KS-6, carbon nano tube and graphene. The lithium ion battery provided by the invention improves the energy density of the battery and simultaneously improves the cycle life of the battery.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of improved-type ternary lithium ion battery of normal temperature circulation
Preparation method.
Background technology
In current lithium ion battery industry, whether the advanced and backward of battery technology, energy density gets caught up in market
The rhythm of development has a deep effect on the existence of enterprise.Investigation is found, in several hundred lithium battery enterprises at home, majority input
The 6% of the turnover is only that can possess leading battery technology into R＆D team.April in this year, the Ministry of Industry and Information Technology,
National Development and Reform Commission, the Department of Science and Technology, which combine, to print and distribute《Automobile industry Long-and Medium-term Development is planned》, the rank of the new energy field of planning
Section property target is that to the year two thousand twenty, electrokinetic cell monomer reaches more than 300wh/Kg than energy, strives realizing 350wh/Kg, system
Strive reaching 260wh/Kg than energy；By 2025, electrokinetic cell system reached 350wh/Kg than energy.
(application number 201610176709.6, the notification numbers such as Co., Ltd of automobile power cell research institute of League of Nations Li Xiang
The A of CN 105609869) nickelic ternary/Delanium system is used, battery energy density highest only has 252wh/Kg, and is difficult to
Reach 300wh/Kg and more than；Shanghai aerospace industry Group Co., Ltd Du Chun peaks (application number 201620790635.0, notification number
CN 206250304U) positive electrode uses nickle cobalt lithium manganate, rich lithium ternary material or phosphoric acid vanadium lithium, negative material using graphite,
Battery module energy density made of alloy material or silicon materials just only has 150wh/Kg, according to 60% service efficiency, monomer
Battery energy density only has 250wh/Kg.
Therefore, developing the lithium ion battery of high-energy-density has wide market prospects.
The content of the invention
Based on technical problem existing for background technology, the present invention proposes a kind of improved-type ternary lithium-ion electric of normal temperature circulation
The preparation method in pond, lithium ion battery provided by the invention improve the circulation of battery while battery energy density is improved
In the life-span, taken a firm foundation for exploitation and popularization and application next generation high-energy-density, long-life lithium battery.
A kind of preparation method of the improved-type ternary lithium ion battery of normal temperature circulation proposed by the present invention, methods described are included such as
Lower step：
S1, by positive electrode binder solution, positive conductive agent, positive active material mix, obtain positive pole close slurry；Positive pole is closed and starched
It is coated on aluminium foil, is dried successively, roll-in, cut, positive plate is obtained after cross cutting；
S2, by negative electrode binder solution, cathode conductive agent, negative electrode active material mix, obtain negative pole close slurry；Negative pole is closed and starched
It is coated on copper foil, is dried successively, roll-in, cut, negative plate is obtained after cross cutting；
S3, by positive plate with negative plate by barrier film lamination into battery core, battery core is placed in aluminum plastic film bag and carries out side top successively
Envelope, electrolyte is injected, stood, sealed, is melted into, soft-package battery is obtained after partial volume；
Wherein, the positive conductive agent is selected from least one of conductive carbon black, KS-6, CNT, graphene.
Preferably, in S1, positive electrode binder is Kynoar.
Preferably, in S1, the solvent of positive electrode binder solution is 1-METHYLPYRROLIDONE.
Preferably, in S1, positive active material is nickle cobalt lithium manganate.
Preferably, in S2, cathode conductive agent is selected from least one of conductive carbon black, KS-6.
Preferably, in S2, the solvent of negative electrode binder solution is deionized water.
Preferably, in S2, negative electrode binder is selected from least one of sodium carboxymethylcellulose, LA133N2, AB glue.
Preferably, in S2, negative electrode active material is silicon substrate 600D.
Preferably, in S3, barrier film, which is selected from, spins at least one of human relations composite membrane, ceramic coating film.
Preferably, in S3, the solute of electrolyte is lithium hexafluoro phosphate.
Preferably, in S3, the solvent of electrolyte is in ethylene carbonate, methyl ethyl ester, diethyl carbonate
It is at least one.
Preferably, in S3, FEC is also added with electrolyte.
Preferably, FEC addition is the 6-10% of electrolyte volume.
Preferably, in S1, positive active material, positive conductive agent, the weight ratio of positive electrode binder are 93-98：1-3：
1.5-4.5。
Preferably, in S1, the viscosity that positive pole closes slurry is 4000-10000mpas.
Preferably, in S1, the two-sided surface density of coating of positive plate is 400-460g/m2。
Preferably, in S1, the compacted density 3.1-3.4g/cm of roll-in3。
Preferably, in S1, the cutting width of positive plate is 120-130mm.
Preferably, in S1, the cross cutting size of positive plate is 90-100*120-130mm.
Preferably, in S2, negative electrode active material, cathode conductive agent, the weight of negative electrode binder ratio are 88-93：2-4：4-
8。
Preferably, in S2, the viscosity that negative pole closes slurry is 2500-5000mpas.
Preferably, in S2, the two-sided surface density of coating of negative plate is 156-172g/m2。
Preferably, in S2, the compacted density 1.4-1.6g/cm of roll-in3。
Preferably, in S2, the cutting width of negative plate is 120-130mm.
Preferably, in S2, the cross cutting size of negative plate is 90-100*120-130mm.
Preferably, in S3, the thickness of barrier film is 10-20um.
Preferably, in S3, the concentration of electrolyte solution is 1.0-1.2mol/L.
Preferably, cathode conductive agent is conductive carbon black and KS-6 mixture.
Preferably, conductive carbon black and KS-6 weight ratio are 1-3：0.5-2.
Above-mentioned FEC belongs to cathode film formation additive.
The concentration of above-mentioned positive electrode binder solution is not construed as limiting, and is selected as the case may be.
The time of above-mentioned drying and temperature are not construed as limiting, and meet the state of drying.
Beneficial effects of the present invention are：
(1) present invention is by controlling preferably both positive and negative polarity conjunction slurry formula technique, coated face density and compacted density to be added
The pole piece of work excellent performance.
(2) electrical conductance that the superconduction isoelectric substances such as CNT, graphene improve electronics is added in anode sizing agent of the invention,
High-quality binding agent is added in cathode size, phenomenon that suppression silicon-based anode " eats lithium " caused by being expanded in charge and discharge process, is suppressed
The destruction of solid electrolyte membrane, the cycle life of battery is improved, while use high specific energy batteries system electrolyte, and added
FEC promotes the fine and close solid electrolyte membrane of generation, reduces the polarization phenomena of battery discharge, improves battery coulombic efficiency.
(3) barrier film of the invention enhances the electrolysis of battery from thick 10-20um spinning human relations composite membrane or ceramic coating film
Liquid imbibition and liquid-keeping property, stable passage is provided for the migration of lithium ion.
(4) lithium ion battery provided by the invention improves the circulation longevity of battery while battery energy density is improved
Life, taken a firm foundation for exploitation and popularization and application next generation high-energy-density, long-life lithium battery.
Embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of the improved-type ternary lithium ion battery of normal temperature circulation, methods described comprise the following steps：
S1, by positive electrode binder solution, positive conductive agent, positive active material mix, obtain positive pole close slurry；Positive pole is closed and starched
It is coated on aluminium foil, is dried successively, roll-in, cut, positive plate is obtained after cross cutting；
S2, by negative electrode binder solution, cathode conductive agent, negative electrode active material, adhesive mix, obtain negative pole close slurry；Will
Negative pole closes slurry and is coated on copper foil, is dried successively, roll-in, cuts, and negative plate is obtained after cross cutting；
S3, by positive plate with negative plate by barrier film lamination into battery core, battery core is placed in aluminum plastic film bag and carries out side top successively
Envelope, electrolyte is injected, stood, sealed, is melted into, soft-package battery is obtained after partial volume；
Wherein, the positive conductive agent is selected from least one of conductive carbon black, KS-6, CNT, graphene.
Embodiment 2
A kind of preparation method of the improved-type ternary lithium ion battery of normal temperature circulation, methods described comprise the following steps：
S1, by positive electrode binder solution, positive conductive agent, positive active material mix, obtain positive pole close slurry；Positive pole is closed and starched
It is coated on aluminium foil, is dried successively, roll-in, cut, positive plate is obtained after cross cutting；
S2, by negative electrode binder solution, cathode conductive agent, negative electrode active material, adhesive mix, obtain negative pole close slurry；Will
Negative pole closes slurry and is coated on copper foil, is dried successively, roll-in, cuts, and negative plate is obtained after cross cutting；
S3, by positive plate with negative plate by barrier film lamination into battery core, battery core is placed in aluminum plastic film bag and carries out side top successively
Envelope, electrolyte is injected, stood, sealed, is melted into, soft-package battery is obtained after partial volume；
Wherein, the positive conductive agent is conductive carbon black；
In S1, positive electrode binder is Kynoar；
In S1, the solvent of positive electrode binder solution is 1-METHYLPYRROLIDONE；
In S1, positive active material is nickle cobalt lithium manganate；
In S2, cathode conductive agent is conductive carbon black；
In S2, the solvent of negative electrode binder solution is deionized water；
In S2, negative electrode binder LA133N2；
In S2, negative electrode active material is silicon substrate 600D；
In S3, barrier film is spinning human relations composite membrane；
In S3, the solute of electrolyte is lithium hexafluoro phosphate；
In S3, the solvent of electrolyte is ethylene carbonate；
In S3, FEC is also added with electrolyte；
FEC addition is the 7% of electrolyte volume；
In S1, positive active material, positive conductive agent, the weight ratio of positive electrode binder are 93：1：4.5；
In S1, the viscosity that positive pole closes slurry is 4000mpas；
In S1, the two-sided surface density of coating of positive plate is 420g/m2；
In S1, the compacted density 3.1g/cm of roll-in3；
In S1, the cutting width of positive plate is 120mm；
In S1, the cross cutting size of positive plate is 100*120mm；
In S2, negative electrode active material, cathode conductive agent, the weight of negative electrode binder ratio are 93：2：8；
In S2, the viscosity that negative pole closes slurry is 2500mpas；
In S2, the two-sided surface density of coating of negative plate is 172g/m2；
In S2, the compacted density 1.5g/cm of roll-in3；
In S2, the cutting width of negative plate is 130mm；
In S2, the cross cutting size of negative plate is 90*130mm；
In S3, the thickness of barrier film is 10um；
In S3, the concentration of electrolyte solution is 1.2mol/L.
Embodiment 3
A kind of preparation method of the improved-type ternary lithium ion battery of normal temperature circulation, methods described comprise the following steps：
S1, by positive electrode binder solution, positive conductive agent, positive active material mix, obtain positive pole close slurry；Positive pole is closed and starched
It is coated on aluminium foil, is dried successively, roll-in, cut, positive plate is obtained after cross cutting；
S2, by negative electrode binder solution, cathode conductive agent, negative electrode active material, adhesive mix, obtain negative pole close slurry；Will
Negative pole closes slurry and is coated on copper foil, is dried successively, roll-in, cuts, and negative plate is obtained after cross cutting；
S3, by positive plate with negative plate by barrier film lamination into battery core, battery core is placed in aluminum plastic film bag and carries out side top successively
Envelope, electrolyte is injected, stood, sealed, is melted into, soft-package battery is obtained after partial volume；
Wherein, the positive conductive agent is CNT；
In S1, positive electrode binder is Kynoar；
In S1, the solvent of positive electrode binder solution is 1-METHYLPYRROLIDONE；
In S1, positive active material is nickle cobalt lithium manganate；
In S2, cathode conductive agent KS-6；
In S2, the solvent of negative electrode binder solution is deionized water；
In S2, negative electrode binder LA133N2；
In S2, negative electrode active material is silicon substrate 600D；
In S3, barrier film is spinning human relations composite membrane；
In S3, the solute of electrolyte is lithium hexafluoro phosphate；
In S3, the solvent of electrolyte is methyl ethyl ester；
In S3, FEC is also added with electrolyte；
FEC addition is the 9% of electrolyte volume；
In S1, positive active material, positive conductive agent, the weight ratio of positive electrode binder are 98：3：1.5；
In S1, the viscosity that positive pole closes slurry is 10000mpas；
In S1, the two-sided surface density of coating of positive plate is 450g/m2；
In S1, the compacted density 3.3g/cm of roll-in3；
In S1, the cutting width of positive plate is 130mm；
In S1, the cross cutting size of positive plate is 90*130mm；
In S2, negative electrode active material, cathode conductive agent, the weight of negative electrode binder ratio are 22：1：1；
In S2, the viscosity that negative pole closes slurry is 5000mpas；
In S2, the two-sided surface density of coating of negative plate is 156g/m2；
In S2, the compacted density 1.6g/cm of roll-in3；
In S2, the cutting width of negative plate is 120mm；
In S2, the cross cutting size of negative plate is 100*120mm；
In S3, the thickness of barrier film is 20um；
In S3, the concentration of electrolyte solution is 1.0mol/L.
Embodiment 4
A kind of preparation method of the improved-type ternary lithium ion battery of normal temperature circulation, methods described comprise the following steps：
S1, by 2.74g positive electrode binders, the agent of 45.70g positive conductives, 178.40g positive active materials, 35.11g positive poles
The solvent of binder solution mixes 5h, and vacuum stands defoaming 2h, crosses 200 mesh sieves, obtains positive pole and closes slurry；Positive pole is closed into slurry coating
On aluminium foil, dried, roll-in, cut successively, positive plate is obtained after cross cutting；
S2,5.15g negative electrode binders, 1.88g cathode conductive agents, 86.58g negative electrode active materials, 240.68g negative poles glued
The solvent for tying agent solution mixes 4h, obtains negative pole and closes slurry；Negative pole conjunction slurry is coated on copper foil, dried successively, roll-in,
Cut, negative plate is obtained after cross cutting；
S3, by positive plate with negative plate by barrier film lamination into battery core, battery core is placed in aluminum plastic film bag and carries out side top successively
Envelope, electrolyte is injected, stood, sealed, is melted into, soft-package battery is obtained after partial volume；
Wherein, the positive conductive agent is the mixture of conductive carbon black and graphene, and both weight ratios are 2：1, and
The solid content of positive conductive agent is 5wt%；
In S1, positive electrode binder is Kynoar；
In S1, the solvent of positive electrode binder solution is 1-METHYLPYRROLIDONE；
In S1, positive active material is nickle cobalt lithium manganate；
In S2, cathode conductive agent is conductive carbon black and KS-6 mixture, and both weight ratios are 1.25：0.63；
In S2, the solvent of negative electrode binder solution is deionized water；
In S2, negative electrode binder is AB glue；
In S2, negative electrode active material is silicon substrate 600D；
In S3, barrier film is spinning human relations composite membrane；
In S3, the solute of electrolyte is lithium hexafluoro phosphate；
In S3, the solvent of electrolyte is diethyl carbonate；
In S3, FEC is also added with electrolyte；
FEC addition is the 6% of electrolyte volume；
In S1, the viscosity that positive pole closes slurry is 6500mpas；
In S1, the two-sided surface density of coating of positive plate is 460g/m2；
In S1, the compacted density 3.4g/cm of roll-in3, and positive pole ear is located at pole piece homonymy, the specification of lug is 26*
24mm；
In S1, the cutting width of positive plate is 123mm；
In S1, the cross cutting size of positive plate is 93*123mm；
In S2, the viscosity that negative pole closes slurry is 6500mpas；
In S2, the two-sided surface density of coating of negative plate is 164g/m2；
In S2, the compacted density 1.6g/cm of roll-in3, and negative lug is located at pole piece homonymy, the specification of lug is 26*
24mm；
In S2, the cutting width of negative plate is 126mm；
In S2, the cross cutting size of negative plate is 96*126mm；
In S3, the thickness of barrier film is 16um；
In S3, the concentration of electrolyte solution is 1.15mol/L；
In S3, the concrete operations of chemical conversion are：0.02C multiplying powers charging 2h；0.04C multiplying powers charging 2h；0.33C multiplying powers charge
1h；
In S3, the concrete operations of partial volume are：Constant-current constant-voltage charging voltage is to 4.2V, 1C electric current, 0.05C cut-off currents；It is permanent
Piezoelectric voltage is banished to 2.5V, 1C electric current；Circulation 2 times；Constant-current constant-voltage charging voltage is to 4.2V, 1C electric current, 0.05C cut-off currents.
Embodiment 5
A kind of preparation method of the improved-type ternary lithium ion battery of normal temperature circulation, methods described comprise the following steps：
It is S1,3.03g positive electrode binders, the agent of 3.71g positive conductives, 161.56g positive active materials, 65.45g is just very viscous
The solvent for tying agent solution mixes 5h, and vacuum stands defoaming 2h, crosses 200 mesh sieves, obtains positive pole and closes slurry；Positive pole conjunction slurry is coated on
On aluminium foil, dried, roll-in, cut successively, positive plate is obtained after cross cutting；
S2,4.62g negative electrode binders, 1.34g cathode conductive agents, 60.02g negative electrode active materials, 153.45g negative poles glued
The solvent for tying agent solution mixes 4h, obtains negative pole and closes slurry；Negative pole conjunction slurry is coated on copper foil, dried successively, roll-in,
Cut, negative plate is obtained after cross cutting；
S3, by positive plate with negative plate by barrier film lamination into battery core, battery core is placed in aluminum plastic film bag and carries out side top successively
Envelope, electrolyte is injected, stood, sealed, is melted into, soft-package battery is obtained after partial volume；
Wherein, the positive conductive agent is the mixture of conductive carbon black and graphene, and both weight ratios are 2.52：
1.19；
In S1, positive electrode binder is Kynoar；
In S1, the solvent of positive electrode binder solution is 1-METHYLPYRROLIDONE；
In S1, positive active material is nickle cobalt lithium manganate；
In S2, cathode conductive agent is conductive carbon black and KS-6 mixture, and both weight ratios are 0.88：0.46；
In S2, the solvent of negative electrode binder solution is deionized water；
In S2, negative electrode binder is sodium carboxymethylcellulose and LA133N2 mixture, and both weight ratios are
0.66：3.96；
In S2, negative electrode active material is silicon substrate 600D；
In S3, barrier film is ceramic coating film；
In S3, the solute of electrolyte is lithium hexafluoro phosphate；
In S3, the solvent of electrolyte is ethylene carbonate；
In S3, FEC is also added with electrolyte；
FEC addition is the 10% of electrolyte volume；
In S1, the viscosity that positive pole closes slurry is 5500mpas；
In S1, the two-sided surface density of coating of positive plate is 400g/m2；
In S1, the compacted density 3.2g/cm of roll-in3, and positive pole ear is located at pole piece homonymy, the specification of lug is 26*
24mm；
In S1, the cutting width of positive plate is 123mm；
In S1, the cross cutting size of positive plate is 93*123mm；
In S2, negative electrode active material, cathode conductive agent, the weight of negative electrode binder ratio are 88-93：2-4：4-8；
In S2, the viscosity that negative pole closes slurry is 5500mpas；
In S2, the two-sided surface density of coating of negative plate is 162g/m2；
In S2, the compacted density 1.4g/cm of roll-in3, and negative lug is located at pole piece homonymy, the specification of lug is 26*
24mm；
In S2, the cutting width of negative plate is 126mm；
In S2, the cross cutting size of negative plate is 96*126mm；
In S3, the thickness of barrier film is 16um；
In S3, the concentration of electrolyte solution is 1.2mol/L；
In S3, the concrete operations of chemical conversion are：0.02C multiplying powers charging 2h；0.04C multiplying powers charging 2h；0.33C multiplying powers charge
1h；
In S3, the concrete operations of partial volume are：Constant-current constant-voltage charging voltage is to 4.2V, 1C electric current, 0.05C cut-off currents；It is permanent
Piezoelectric voltage is banished to 2.5V, 1C electric current；Circulation 2 times；Constant-current constant-voltage charging voltage is to 4.2V, 1C electric current, 0.05C cut-off currents.
Test example 1
Normal temperature circulation test is carried out respectively to embodiment 4 and embodiment 5, specific test operation is：Make embodiment 4 and implement
Example 5 is respectively with 1C current ratio discharge and recharges, voltage range 2.5-4.2V, as a result such as following table at a temperature of 25 DEG C：
| Project | Embodiment 4 | Embodiment 5 |
| Circulate the discharge capacity (Ah) after 0 week | 30.0 | 29.0 |
| Circulate the discharge capacity (Ah) after 50 weeks | 28.8 | 26.0 |
| Circulate the discharge capacity (Ah) after 100 weeks | 28.0 | 25.0 |
| Circulate the discharge capacity (Ah) after 150 weeks | 27.5 | 23.6 |
| Circulate the discharge capacity (Ah) after 200 weeks | 27.0 | 0 |
| Circulate the discharge capacity (Ah) after 250 weeks | 26.5 | 0 |
| Circulate the discharge capacity (Ah) after 300 weeks | 26.0 | 0 |
Wherein, the internal circulating load of embodiment 4 is 300 weeks, capability retention 85%, energy density 310Wh/kg；Implement
The internal circulating load of example 5 is 180 weeks, capability retention 80%, energy density 280Wh/kg.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the improved-type ternary lithium ion battery of normal temperature circulation, it is characterised in that methods described includes as follows
Step：
S1, by positive electrode binder solution, positive conductive agent, positive active material mix, obtain positive pole close slurry；Positive pole is closed into slurry coating
On aluminium foil, dried, roll-in, cut successively, positive plate is obtained after cross cutting；
S2, by negative electrode binder solution, cathode conductive agent, negative electrode active material mix, obtain negative pole close slurry；Negative pole is closed into slurry coating
On copper foil, dried, roll-in, cut successively, negative plate is obtained after cross cutting；
S3, by positive plate and negative plate by barrier film lamination into battery core, battery core is placed in aluminum plastic film bag and carries out side closedtop successively, is noted
Enter electrolyte, stand, seal, be melted into, soft-package battery is obtained after partial volume；
Wherein, the positive conductive agent is selected from least one of conductive carbon black, KS-6, CNT, graphene.
2. the preparation method of the improved-type ternary lithium ion battery of normal temperature circulation according to claim 1, it is characterised in that S1
In, positive electrode binder is Kynoar；Preferably, in S1, the solvent of positive electrode binder solution is 1-METHYLPYRROLIDONE；It is excellent
Selection of land, in S1, positive active material is nickle cobalt lithium manganate.
3. the preparation method of the improved-type ternary lithium ion battery of normal temperature circulation according to claim 1 or claim 2, it is characterised in that
In S2, cathode conductive agent is selected from least one of conductive carbon black, KS-6；Preferably, in S2, the solvent of negative electrode binder solution
For deionized water；Preferably, in S2, negative electrode binder is selected from least one of sodium carboxymethylcellulose, LA133N2, AB glue；
Preferably, in S2, negative electrode active material is silicon substrate 600D.
4. according to the preparation method of the improved-type ternary lithium ion battery of any one of the claim 1-3 normal temperature circulations, its feature
It is, in S3, barrier film, which is selected from, spins at least one of human relations composite membrane, ceramic coating film；Preferably, in S3, the solute of electrolyte
For lithium hexafluoro phosphate；Preferably, in S3, the solvent of electrolyte is selected from ethylene carbonate, methyl ethyl ester, diethyl carbonate
At least one of；Preferably, in S3, FEC is also added with electrolyte；Preferably, FEC addition is electrolyte volume
6-10%.
5. according to the preparation method of the improved-type ternary lithium ion battery of any one of the claim 1-4 normal temperature circulations, its feature
It is, in S1, positive active material, positive conductive agent, the weight ratio of positive electrode binder are 93-98：1-3：1.5-4.5；It is preferred that
Ground, in S1, the viscosity that positive pole closes slurry is 4000-10000mpas；Preferably, in S1, the two-sided surface density of coating of positive plate is
400-460g/m2；Preferably, in S1, the compacted density 3.1-3.4g/cm of roll-in3；Preferably, in S1, the cutting of positive plate is wide
Spend for 120-130mm；Preferably, in S1, the cross cutting size of positive plate is 90-100*120-130mm.
6. according to the preparation method of the improved-type ternary lithium ion battery of any one of the claim 1-5 normal temperature circulations, its feature
It is, in S2, negative electrode active material, cathode conductive agent, the weight of negative electrode binder ratio are 88-93：2-4：4-8；Preferably, S2
In, the viscosity that negative pole closes slurry is 2500-5000mpas；Preferably, in S2, the two-sided surface density of coating of negative plate is 156-
172g/m2；Preferably, in S2, the compacted density 1.4-1.6g/cm of roll-in3；Preferably, in S2, the cutting width of negative plate is
120-130mm；Preferably, in S2, the cross cutting size of negative plate is 90-100*120-130mm.
7. according to the preparation method of the improved-type ternary lithium ion battery of any one of the claim 1-6 normal temperature circulations, its feature
It is, in S3, the thickness of barrier film is 10-20um.
8. according to the preparation method of the improved-type ternary lithium ion battery of any one of the claim 1-7 normal temperature circulations, its feature
It is, in S3, the concentration of electrolyte solution is 1.0-1.2mol/L.
9. the preparation method of the improved-type ternary lithium ion battery of normal temperature circulation according to claim 3, it is characterised in that negative pole
Conductive agent is conductive carbon black and KS-6 mixture.
10. the preparation method of the improved-type ternary lithium ion battery of normal temperature circulation according to claim 9, it is characterised in that lead
Electrical carbon is black and KS-6 weight ratio is 1-3：0.5-2.
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| CN114551808A (en) * | 2022-02-24 | 2022-05-27 | 上海兰钧新能源科技有限公司 | Lithium battery pole piece, lithium battery cell and preparation method of lithium battery pole piece |
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| CN114695968A (en) * | 2022-06-01 | 2022-07-01 | 四川新能源汽车创新中心有限公司 | Lithium ion battery with NP ratio less than 1 and preparation method thereof |
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