CN106328926B - High-safety long-life ternary material battery - Google Patents
High-safety long-life ternary material battery Download PDFInfo
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- CN106328926B CN106328926B CN201610908602.6A CN201610908602A CN106328926B CN 106328926 B CN106328926 B CN 106328926B CN 201610908602 A CN201610908602 A CN 201610908602A CN 106328926 B CN106328926 B CN 106328926B
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- 239000000463 material Substances 0.000 title claims abstract description 43
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000002033 PVDF binder Substances 0.000 claims abstract description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 12
- 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 abstract description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 11
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 11
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- -1 lithium hexafluorophosphate Chemical group 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000002608 ionic liquid Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 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 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910012516 LiNi0.4Co0.2Mn0.4O2 Inorganic materials 0.000 claims description 4
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 claims description 3
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000004682 monohydrates Chemical class 0.000 claims description 2
- 239000011267 electrode slurry Substances 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 23
- 238000007790 scraping Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 230000001680 brushing effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004804 winding 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
- H01M4/50—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
- 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
- H01M10/42—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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
A high-safety long-life ternary material battery comprises the following solid matter in percentage by mass of positive electrode slurry: ternary materials: 92.0% -95.5%; polyvinylidene fluoride: 3.0% -7.0%; oily carbon nanofiber: 1.5% -2.5%; the mass percentage of solid matter of the negative electrode slurry is as follows: lithium titanate: 90.0% -93.5%; sodium carboxymethylcellulose: 1.0% -2.4%; adhesive: 3.5% -7.0%; SP type conductive carbon black: 0.3% -1.0%; c45Type conductive carbon black: 0.5 to 1.8 percent; KS-6 type conductive graphite: 1.2 to 2.4 percent. The high-safety long-life ternary material battery provided by the invention has qualified safety performance, can be continuously charged and discharged according to a 1C charging and discharging system under the room temperature condition, has a capacity retention rate higher than 80% after 2000 cycles, and meets the use requirements of small electric tools, aviation, aerospace and new energy automobiles.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a high-safety long-life ternary material battery.
Background
High-efficiency secondary batteries are designed and developed for the purpose of "supplying energy to mobile users" and "storing electricity". For mobile user energy storage, batteries are required to have long life, high safety and differentiated performance. Compared with other types of secondary batteries, the lithium ion battery has the outstanding advantages of higher specific energy, higher specific power, higher voltage, small self-discharge, no memory effect, environmental protection and the like, and is the most ideal battery system.
Under the strategic arrangement of national energy, the new energy industry is rapidly developed under the stimulation of favorable policies. Currently, the mainstream system of lithium ion batteries is divided into lithium iron phosphate and ternary materials. The battery performances of the two systems are different, but the ternary material battery has great advantages and market potential from the aspects of battery cost, energy density, popularization easiness and the like. However, the lattice structure and chemical components of the ternary material determine that the physicochemical property and the electrochemical property of the ternary material are unstable, and compared with a lithium iron phosphate battery, the battery of a corresponding system has poorer safety performance and cycle life. Aiming at the defect, a great deal of research work is carried out by various departments and institutes and material manufacturers, but the problems of low safety and poor cycle life of the ternary material battery cannot be thoroughly solved.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art, solving the problems of low safety and poor cycle life of the conventional ternary material battery and providing a high-safety ternary material battery with long service life.
The technical scheme adopted by the invention for solving the technical problem is that,
the preparation process of the battery comprises lamination and winding, and the types of the battery shell comprise an aluminum shell, a steel shell, a soft package and a plastic shell. The battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and positive and negative electrode conductive agents.
The solvent used in the slurry of the anode of the battery is N-methyl pyrrolidone, and the mass percentage of each solid matter is as follows: ternary materials: 92.0% -95.5%; polyvinylidene fluoride: 3.0% -7.0%; oily carbon nanofiber: 1.5% -2.5%; the sum of the mass percentages of the substances is 100.0%.
The solvent used in the slurry of the negative electrode of the battery is deionized water, and the mass percent of each solid matter is as follows: lithium titanate: 90.0% -93.5%; sodium carboxymethylcellulose: 1.0% -2.4%; adhesive: 3.5% -7.0%; SP type conductive carbon black: 0.3% -1.0%; c45Type conductive carbon black: 0.5 to 1.8 percent; KS-6 type conductive graphite: 1.2% -2.4%; the sum of the mass percentages of the substances is 100.0%.
The ternary material is LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.15Al0.05O2One or more of them.
The binder is one or more of styrene butadiene rubber emulsion, LA132 type water-based binder and LA133 type water-based binder.
The diaphragm of the battery is coated with a coating material, and the coating material is one or more of aluminum oxide, alumina monohydrate, barium sulfate and palygorskite.
The electrolyte of the battery is a five-element system functional material added with ionic liquid, and the concentration of the ionic liquid is 0.5-1.0 mol/L; the lithium salt in the electrolyte is lithium hexafluorophosphate, the concentration in the electrolyte is 0.8-1.3 mol/L, and the volume ratio of the solvent in the electrolyte is ethylene carbonate: ethyl methyl carbonate: vinylene carbonate: ethylene sulfite: heptamethyldisiminoalkane is 1.5-2.5: 3.5-4.5: 0.5-1.5: 1.5-2.5: 0.5 to 1.5.
The chemical structure of the anion of the ionic liquid is shown as the formula (I):
the cation of the ionic liquid comprises one or more of quaternary ammonium ion, piperidine ion, pyrrole ion, quaternary phosphonium ion, pyrazole ion and imidazole ion. The chemical structures of the quaternary ammonium ions, the piperidine ions, the pyrrole ions, the quaternary phosphonium ions, the pyrazole ions and the imidazole ions are shown as the formula (II):
wherein R is1-R4And R18-R21Independently selecting alkyl or substituted alkyl with 1-8 carbon atoms; r5、R6、R12、R13、R26、R31Independently selecting alkyl with 1-6 carbon atoms; r7-R11、R14-R17、R22-R25、R27-R30Each independently selected from a hydrogen atom, a halogen atom, or an alkyl group or substituted alkyl group having 1 to 6 carbon atoms.
The invention has the beneficial effects that:
the anode material uses the ternary material LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.15Al0.05O2One or more of the components, high voltage platform, high gram volume, uniform particle size distribution, moderate specific surface area, high tap density, simple preparation process of the slurry and strong operability; the negative electrode material is lithium titanate, a zero-strain material is adopted, the cycle performance is good, the discharge voltage is stable, side reaction with the electrolyte is avoided, and the safety performance of the battery can be improved; the electrolyte is a five-element system functional material added with ionic liquid, has flame retardance, can overcome the problems of oxygen release due to decomposition of the electrolyte in a high-temperature environment, unstable interfacial film of a solid electrolyte and the like, and improves the high-temperature safety performance of the battery; the isolating membrane is a coating membrane, has high strength and flame retardance, high electrolyte liquid retention and good safety, high temperature property and cyclicity; the positive electrode conductive agent is oily carbon nanofiber, and the negative electrode conductive agent is SP type conductive carbon black or C45The combination of the conductive carbon black and the KS-6 conductive graphite can improve the cycle life of the battery due to the synergistic effect of the conductive agents.
The high-safety long-life ternary material battery provided by the invention is qualified in safety performance through testing of new national standards GB/T31484 and GB/T31485, and is continuously charged and discharged according to a 1C charging and discharging system under the room temperature condition, the capacity retention rate is higher than 80% after 2000 cycles, and the battery can meet the use requirements of small electric tools, aviation, aerospace and new energy automobiles.
Detailed Description
The invention will be further illustrated with reference to specific examples:
in the following examples, the ratio of substances is a mass ratio or a mass percentage unless otherwise specified.
Example 1
Positive electrode slurry:
ternary material LiNi0.5Co0.2Mn0.3O2: polyvinylidene fluoride: oily carbon nanofiber 94.0%: 4.5%: 1.5 percent. Adding polyvinylidene fluoride according to a metering ratio, preparing the polyvinylidene fluoride and an anode slurry solvent N-methyl pyrrolidone according to the metering ratio, adding the N-methyl pyrrolidone firstly, and then adding the polyvinylidene fluoride to enable the concentration of the polyvinylidene fluoride to be 4.0 wt%; stirring at revolution speed of 35rpm and rotation speed of 200rpm for 10min, scraping, and performing normal stirring, and performing vacuum stirring at revolution speed of 35rpm and rotation speed of 2200rpm for 4 h; adding oily carbon nanofibers according to the weight ratio, stirring at 55rpm for revolution and 600rpm for 20min, scraping, then revolving at 65rpm and 2600rpm for rotation, and stirring for 2h in vacuum; adding a ternary material LiNi according to a metering ratio0.5Co0.2Mn0.3O2Stirring at 45rpm and 2300rpm for 15min, scraping, and stirring at 65rpm and 2700rpm for 150 min. After the slurry is stirred, adjusting the viscosity, and adjusting the viscosity in sequence from high to low according to the solid content, wherein the adjusting time is 30min each time, the revolution is 25rpm, and the rotation is 1600 rpm; the viscosity is required to be 7000-9000 cp; and the reference solid content is 45-53 wt%. And transferring the qualified slurry to a feeding system, and preparing the positive pole piece meeting the technical requirements through the procedures of coating, drying, rolling, die cutting, brushing and the like.
And (3) negative electrode slurry:
lithium titanate: sodium carboxymethylcellulose: styrene-butadiene rubber emulsion: SP type conductive carbon black: c45Type conductive carbon black: KS-6 type conductive graphite 92.0%: 1.3%: 4.0%: 0.7%: 0.5%: 1.5 percent. Preparing sodium carboxymethylcellulose and deionized water according to a metering ratio, adding deionized water and then adding sodium carboxymethylcellulose to make the concentration of sodium carboxymethylcellulose be 5 wt%; stirring at revolution speed of 35rpm and rotation speed of 400rpm for 10min, scraping, and then performing normal stirring at revolution speed of 35rpm and rotation speed of 2600rpm for 120 min; adding styrene butadiene rubber emulsion, revolving at 45rpm and rotating at 500rpm, and stirring for 90 minutes; adding SP type conductive carbon black and C according to the metering ratio45Conducting carbon black, KS-6 conducting graphite and lithium titanate, revolving at 65rpm and rotating at 700rStirring with a stirrer for 30min, scraping, and stirring at 60rpm for 180 min. After the slurry is stirred, adjusting the viscosity, and adjusting the viscosity in sequence from high to low according to the solid content, wherein the adjusting time is 30min each time, the revolution is 20rpm, and the rotation is 1200 rpm; the viscosity is required to be 3000-4500 cp; and the reference solid content is 40-45 wt%. And transferring the qualified slurry to a feeding system, and preparing the negative pole piece meeting the technical requirements through the procedures of coating, drying, rolling, die cutting, brushing and the like.
The diaphragm of the battery is coated with a coating material, and the coating material is aluminum oxide.
The electrolyte of the battery is a five-element system functional material added with ionic liquid, and the concentration of the ionic liquid is 0.6 mol/L; the lithium salt in the electrolyte is lithium hexafluorophosphate, the concentration in the electrolyte is 0.9mol/L, and the volume ratio of the solvent in the electrolyte is ethylene carbonate: ethyl methyl carbonate: vinylene carbonate: ethylene sulfite: heptamethyldisiminoalkane ═ 2.0: 4.0: 1.0: 2.0: 0.8. wherein the chemical structures of the anions and the cations are respectively shown as a formula (three) and a formula (four):
and (3) preparing the qualified positive pole piece, the qualified negative pole piece and the aluminum oxide coating diaphragm into the battery cell with the rated capacity of 10.0AH by using a laminating machine, and performing procedures of assembling, injecting, laying aside, forming, grading and the like. And detecting various indexes of the battery cell, and warehousing after the indexes are qualified. The battery performance was measured, and the measurement results are shown in the following table. The battery related performance test method is required to be executed according to GB/T31484-.
| Voltage of | Internal resistance of | Capacity of | Puncture, squeeze, etc. test | 2000 cycle rear volume (1C) |
| 3.82V | 0.65mΩ | 10.65AH | Smoke and non-combustion | 8.6AH |
Example 2
Positive electrode slurry:
ternary material LiNi0.4Co0.2Mn0.4O2: polyvinylidene fluoride: oily carbon nanofiber 95.0%: 3.3%: 1.7 percent. Preparing polyvinylidene fluoride and a positive electrode slurry solvent N-methyl pyrrolidone according to a metering ratio, adding the N-methyl pyrrolidone firstly, and then adding the polyvinylidene fluoride to make the concentration of the polyvinylidene fluoride be 4.0 wt%; stirring at revolution speed of 35rpm and rotation speed of 200rpm for 10min, scraping, and performing normal stirring, and performing vacuum stirring at revolution speed of 35rpm and rotation speed of 2200rpm for 4 h; adding oily carbon nanofibers according to the weight ratio, stirring at 55rpm for revolution and 600rpm for 20min, scraping, then revolving at 65rpm and 2600rpm for rotation, and stirring for 2h in vacuum; adding a ternary material LiNi according to a metering ratio0.5Co0.2Mn0.3O2Stirring at 45rpm and 2300rpm for 15min, scraping, and stirring at 65rpm and 2700rpm for 150 min. After the slurry is stirred, adjusting the viscosity, and adjusting the viscosity in sequence from high to low according to the solid content, wherein the adjusting time is 30min each time, the revolution is 25rpm, and the rotation is 1600 rpm; the viscosity is required to be 7000-9000 cp; and the reference solid content is 45-53 wt%. And transferring the qualified slurry to a feeding system, and preparing the positive pole piece meeting the technical requirements through the procedures of coating, drying, rolling, slitting, brushing and the like.
And (3) negative electrode slurry:
lithium titanate: sodium carboxymethylcellulose: styrene-butadiene rubber emulsion: SP type conductive carbon black: c45Type conductive carbon black: KS-6 type conductive graphite 92.8%: 1.2%: 3.5%: 0.8%: 0.5%: 1.2 percent. Preparing sodium carboxymethylcellulose and deionized water according to a metering ratio, adding deionized water and then adding sodium carboxymethylcellulose to make the concentration of sodium carboxymethylcellulose be 5 wt%; stirring at revolution speed of 35rpm and rotation speed of 400rpm for 10min, scraping, and then performing normal stirring at revolution speed of 35rpm and rotation speed of 2600rpm for 120 min; adding styrene-butadiene rubber emulsion, and stirring for 90 minutes at revolution speed of 45rpm and rotation speed of 500 rpm; adding SP type conductive carbon black and C according to the metering ratio45Conducting carbon black, KS-6 conducting graphite and lithium titanate, stirring at 65rpm for revolution and 700rpm for rotation for 30min, scraping, and then normally stirring at 60rpm for revolution and 2600rpm for 180 min. After the slurry is stirred, adjusting the viscosity, and adjusting the viscosity in sequence from high to low according to the solid content, wherein the adjusting time is 30min each time, the revolution is 20rpm, and the rotation is 1200 rpm; the viscosity is required to be 3000-4500 cp; and the reference solid content is 40-45 wt%. And transferring the qualified slurry to a feeding system, and preparing the negative pole piece meeting the technical requirements through the procedures of coating, drying, rolling, slitting, brushing and the like.
The diaphragm of the battery is coated with a coating material which is palygorskite.
The electrolyte of the battery is a quinary system functional material added with ionic liquid, the concentration of the ionic liquid is 0.8mol/L, the lithium salt in the electrolyte is lithium hexafluorophosphate, the concentration in the electrolyte is 1.1mol/L, and the volume ratio of a solvent in the electrolyte is ethylene carbonate: ethyl methyl carbonate: vinylene carbonate: ethylene sulfite: heptamethyldisiminoalkane ═ 1.8: 4.2: 1.0: 2.0: 0.8. wherein the chemical structures of the anions and the cations are shown as a formula (three) and a formula (four):
and (3) preparing the qualified positive pole piece, the qualified negative pole piece and the palygorskite-coated diaphragm into a battery cell with the rated capacity of 10.0AH by using a laminating machine, and performing procedures of assembling, injecting, laying aside, forming, grading and the like. And detecting various indexes of the battery cell, and warehousing after the indexes are qualified. The battery performance was measured, and the measurement results are shown in the following table. The battery related performance test method is required to be executed according to GB/T31484-2015, GB/T31485 and 2015 and GB/T31486 and 2016 standards.
| Voltage of | Internal resistance of | Capacity of | Puncture, squeeze, etc. test | 2000 cycle rear volume (1C) |
| 3.79V | 0.85mΩ | 10.35AH | Smoke and non-combustion | 8.38AH |
At present, in the prior art, the ternary material battery has different degrees of violent combustion in the safety test processes of puncture, extrusion and the like, and the battery capacity is attenuated to be less than 80.0 percent of the rated capacity after 800 times of circulation under a 1C charging and discharging system.
The above-mentioned embodiments are merely descriptions of the preferred embodiments of the present invention, and do not limit the concept and the protection scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention.
Claims (5)
1. A ternary material battery is characterized in that the battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and positive and negative electrode conductive agents;
the solvent used in the slurry of the anode of the battery is N-methyl pyrrolidone, and the mass percentage of each solid matter is as follows: ternary materials: 92.0% -95.5%; polyvinylidene fluoride: 3.0% -7.0%; oily carbon nanofiber: 1.5% -2.5%; the sum of the mass percentages of all the substances is 100.0 percent;
the solvent used in the slurry of the negative electrode of the battery is deionized water, and the mass percent of each solid matter is as follows: lithium titanate: 90.0% -93.5%; sodium carboxymethylcellulose: 1.0% -2.4%; adhesive: 3.5% -7.0%; SP type conductive carbon black: 0.3% -1.0%; c45Type conductive carbon black: 0.5 to 1.8 percent; KS-6 type conductive graphite: 1.2% -2.4%; the sum of the mass percentages of all the substances is 100.0 percent;
the ternary material is LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.15Al0.05O2One or more of the above;
the electrolyte of the battery is a five-element system functional material added with ionic liquid, and the concentration of the ionic liquid is 0.5-1.0 mol/L; the lithium salt in the electrolyte is lithium hexafluorophosphate, and the concentration of the lithium salt in the electrolyte is 0.8-1.3 mol/L; the volume ratio of the solvent in the electrolyte is ethylene carbonate: ethyl methyl carbonate: vinylene carbonate: ethylene sulfite: heptamethyldisiminoalkane = 1.5-2.5: 3.5-4.5: 0.5-1.5: 1.5-2.5: 0.5 to 1.5;
the diaphragm of the battery is coated with a coating material, and the coating material is one or more of aluminum oxide, alumina monohydrate, barium sulfate and palygorskite.
2. The ternary material battery according to claim 1, wherein the binder is one or more of styrene-butadiene rubber emulsion, LA132 type aqueous adhesive and LA133 type aqueous adhesive.
3. The ternary material battery according to claim 1, wherein the chemical structure of the anion of the ionic liquid is represented by formula (one):
the formula (I).
4. The ternary material battery according to claim 1, wherein the cation of the ionic liquid comprises one or more of quaternary ammonium ion, piperidine ion, pyrrole ion, quaternary phosphonium ion, pyrazole ion and imidazole ion.
5. The ternary material battery according to claim 4, wherein the chemical structure of the quaternary ammonium ion, the piperidine ion, the pyrrole ion, the quaternary phosphonium ion, the pyrazole ion, and the imidazole ion is represented by formula (II):
a formula (II);
wherein R is1-R4And R18-R21Independently selecting alkyl or substituted alkyl with 1-8 carbon atoms; r5、R6、R12、R13、R26、R31Independently selecting alkyl with 1-6 carbon atoms; r7-R11、R14-R17、R22-R25、R27-R30Each independently selected from a hydrogen atom, a halogen atom, or an alkyl group or substituted alkyl group having 1 to 6 carbon atoms.
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