CN108321360B - Positive electrode slurry, positive plate and energy storage device - Google Patents
Positive electrode slurry, positive plate and energy storage device Download PDFInfo
- Publication number
- CN108321360B CN108321360B CN201710035982.1A CN201710035982A CN108321360B CN 108321360 B CN108321360 B CN 108321360B CN 201710035982 A CN201710035982 A CN 201710035982A CN 108321360 B CN108321360 B CN 108321360B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- plasticizer
- positive
- electrode slurry
- vinylidene fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 38
- 238000004146 energy storage Methods 0.000 title claims abstract description 29
- 239000004014 plasticizer Substances 0.000 claims abstract description 81
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 239000002033 PVDF binder Substances 0.000 claims abstract description 35
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 35
- 239000006258 conductive agent Substances 0.000 claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003292 glue Substances 0.000 claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims description 18
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 15
- 229920001519 homopolymer Polymers 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 claims description 2
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 11
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- 238000007731 hot pressing Methods 0.000 abstract description 10
- 238000004804 winding Methods 0.000 abstract description 10
- 238000003825 pressing Methods 0.000 description 28
- 238000000034 method Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 5
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 5
- 229940083037 simethicone Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005056 compaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- -1 citric acid triester Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- PPMCFKAXXHZLMX-UHFFFAOYSA-N 1,3-dioxocan-2-one Chemical compound O=C1OCCCCCO1 PPMCFKAXXHZLMX-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910004403 Li(Ni0.6Co0.2Mn0.2)O2 Inorganic materials 0.000 description 1
- 229910013098 LiBF2 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Images
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode slurry, a positive electrode plate and an energy storage device. The positive electrode slurry includes a positive electrode active material, a conductive agent, a binder, and N-methylpyrrolidone. The positive electrode slurry further includes a plasticizer. The plasticizer is miscible with N-methyl pyrrolidone. The plasticizer is liquid at room temperature. The boiling point of the plasticizer is not lower than 150 ℃ and the flash point of the plasticizer is not lower than 110 ℃. The molecular structure of the plasticizer contains polar functional groups, and the polar functional groups comprise one or more of-OH, -COOH and- (C ═ O) O-. The crystallinity of the glue film formed by the plasticizer and the polyvinylidene fluoride is smaller than that of the glue film formed by the polyvinylidene fluoride. The plasticizer disclosed by the invention can improve the flexibility of the positive membrane and reduce the risks of winding and hot pressing of the positive membrane and light leakage in a folding manner. The plasticizer does not deteriorate the adhesive force between the positive diaphragm and the positive current collector and the resistance of the positive diaphragm.
Description
Technical Field
The invention relates to the field of energy storage devices, in particular to anode slurry, an anode plate and an energy storage device.
Background
With the popularization of electric vehicles/buses, and the guidance of national policies and great market demands, the technical research and development and application of lithium ion secondary batteries are promoted. The cruising ability of a lithium ion secondary battery for an Electric Vehicle (EV) is a focus of much attention, and a high energy density is one of the major research directions of the lithium ion secondary battery, and is an important measure for improving the cruising ability of the lithium ion secondary battery.
At present, the improvement of the compaction density of positive and negative pole pieces is an effective method for improving the energy density of the lithium ion secondary battery, but the improvement of the energy density of the lithium ion secondary battery theoretically needs the improvement of the cold pressing pressure of the positive and negative pole pieces, so that the load on cold pressing equipment is large, the extension of positive and negative pole pieces is increased in a cold pressing process, and the risk of processing and belt breakage in the cold pressing process is greatly improved. Meanwhile, the energy density of the lithium ion secondary battery is improved, the brittleness of the positive and negative pole pieces is further deteriorated, inner ring fracture is easy to occur in the working procedure of winding and hot pressing of the positive and negative pole pieces, and the electrochemical performance and the safety performance of the lithium ion secondary battery are affected.
Disclosure of Invention
In view of the problems in the background art, an object of the present invention is to provide a positive electrode slurry, a positive electrode sheet, and an energy storage device, in which the plasticizer enables the positive electrode slurry to have good coating processability, and at the same time, the plasticizer can reduce the pressure required during cold pressing of the positive electrode sheet, reduce the extension of the positive electrode sheet, and reduce the risk of belt breakage during the cold pressing process.
The invention also aims to provide the positive electrode slurry, the positive plate and the energy storage device, wherein the plasticizer can improve the flexibility of the positive electrode membrane and reduce the risks of winding and hot pressing of the positive electrode membrane and light leakage in double folding.
It is still another object of the present invention to provide a positive electrode slurry, a positive electrode sheet, and an energy storage device, in which the addition of the plasticizer does not deteriorate the adhesive force between the positive electrode membrane and the positive electrode current collector, and does not deteriorate the resistance of the positive electrode membrane.
In order to achieve the above object, in one aspect of the present invention, there is provided a positive electrode slurry including a positive electrode active material, a conductive agent, a binder, and N-methylpyrrolidone. The positive electrode slurry further includes a plasticizer. The plasticizer is miscible with N-methyl pyrrolidone. The plasticizer is in a liquid state at room temperature, the boiling point of the plasticizer is not lower than 150 ℃, and the flash point of the plasticizer is not lower than 110 ℃. The molecular structure of the plasticizer contains polar functional groups, and the polar functional groups comprise one or more of-OH, -COOH and- (C ═ O) O-. The crystallinity of the glue film formed by the plasticizer and the polyvinylidene fluoride is smaller than that of the glue film formed by the polyvinylidene fluoride.
In another aspect of the present invention, the present invention provides a positive electrode sheet including a positive electrode current collector and a positive electrode sheet. The positive diaphragm is arranged on the surface of the positive current collector. The positive electrode membrane is formed from the positive electrode slurry according to an aspect of the present invention.
In yet another aspect of the invention, the invention provides an energy storage device comprising a positive electrode sheet according to another aspect of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the plasticizer disclosed by the invention has good coating processability, can reduce the pressure required by cold pressing of the positive diaphragm, reduces the extension of the positive diaphragm and reduces the risk of belt breakage during the cold pressing process.
The plasticizer disclosed by the invention can improve the flexibility of the positive membrane and reduce the risks of winding and hot pressing of the positive membrane and light leakage in a folding manner.
The plasticizer does not deteriorate the adhesive force between the positive diaphragm and the positive current collector and the resistance of the positive diaphragm.
Drawings
FIG. 1 is a schematic diagram of a positive diaphragm cold pressing process;
fig. 2 is a plan view of the positive electrode sheet.
Wherein the reference numerals are as follows:
1 pressure roller
2 positive electrode diaphragm
3 positive electrode current collector
Detailed Description
The positive electrode slurry, the positive electrode sheet, and the energy storage device according to the present invention are described in detail below.
First, the cathode paste according to the first aspect of the invention is explained.
The positive electrode slurry according to the first aspect of the invention includes a positive electrode active material, a conductive agent, a binder, and N-methylpyrrolidone (NMP, used as a solvent). The positive electrode slurry further includes a plasticizer. The plasticizer is miscible with N-methyl pyrrolidone. The plasticizer is in a liquid state at room temperature, the boiling point of the plasticizer is not lower than 150 ℃, and the flash point of the plasticizer is not lower than 110 ℃. The molecular structure of the plasticizer contains polar functional groups, and the polar functional groups comprise one or more of-OH, -COOH and- (C ═ O) O-. The crystallinity of the glue film formed by the plasticizer and the polyvinylidene fluoride is smaller than that of the glue film formed by the polyvinylidene fluoride.
In the positive electrode slurry according to the first aspect of the present invention, the plasticizer may perform a lubricating and friction reducing function on contact interfaces between particles of the positive electrode active material, between particles of the conductive agent, and between particles of the conductive agent and particles of the positive electrode active material, so as to reduce a pressure required for cold pressing of the positive electrode diaphragm at the same compaction density, reduce an extension degree of the positive electrode diaphragm, and further reduce a risk of band breakage during a cold pressing process. Meanwhile, the molecular structure of the plasticizer contains polar functional groups, and the plasticizer can enter molecular chains of a binder (such as common polyvinylidene fluoride) to form a junction point between the plasticizer and the polyvinylidene fluoride and replace the junction point between the polyvinylidene fluoride molecular chains, so that the acting force between the polyvinylidene fluoride molecular chains is reduced, the crystallinity and rigidity of the polyvinylidene fluoride are reduced, the flexibility of the polyvinylidene fluoride is improved, the flexibility of the positive electrode diaphragm is improved, the winding hot pressing is improved, the inner ring fracture light leakage of the positive electrode diaphragm and the risk of processing belt breakage in the cold pressing process are reduced. In addition, the plasticizer has a low melting point, is liquid at room temperature, and contains polar functional groups (-OH, -COOH, - (C ═ O) O-) in the molecular structure, so that the plasticizer can be mutually dissolved with NMP, and therefore, the positive electrode slurry can be ensured to have good stirring and coating processability. In addition, the plasticizer has high flash point and high boiling point, is not easy to volatilize or flash, and can not bring processing or safety problems in the process of coating or drying the cathode slurry. Meanwhile, the plasticizer is non-toxic and environment-friendly, does not harm the personal safety of operators, and meets the environment-friendly requirement of indoor gas emission of passenger vehicles.
In the positive electrode slurry according to the first aspect of the present invention, preferably, the plasticizer may include one or more of polyethylene glycol, epoxidized soybean oil, tributyl citrate, and acetyl tributyl citrate.
In the positive electrode slurry according to the first aspect of the present invention, the binder may include polyvinylidene fluoride (PVDF), and the polyvinylidene fluoride may be selected from one or more of vinylidene fluoride homopolymer and vinylidene fluoride copolymer. Preferably, the vinylidene fluoride copolymer is selected from one or more of vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer and vinylidene fluoride-chlorotrifluoroethylene copolymer.
In the positive electrode slurry according to the first aspect of the invention, the ratio of the mass of the plasticizer to the sum of the mass of the positive electrode active material, the conductive agent, the binder and the plasticizer is (0.5-5): 100, and within the range, the plasticizer can effectively improve the flexibility of the positive electrode membrane, so that the risk of electrochemical performance loss of the energy storage device is reduced, and the application requirements of the energy storage device are better met. If the content of the plasticizer is too high, the direct current/alternating current impedance of the positive electrode diaphragm is increased, so that the electrochemical performance of the energy storage device is influenced, and meanwhile, the increase of the content of the plasticizer also reduces the bonding strength between the positive electrode diaphragm and a positive electrode current collector, so that the risk of powder falling during processing and use of the energy storage device is caused, and the safety performance of the energy storage device is influenced; if the content of the plasticizer is too low or the plasticizer is not contained, the effect of improving the flexibility of the positive electrode membrane cannot be achieved, and the electrochemical performance and the safety performance of the energy storage device are not improved.
In the positive electrode slurry according to the first aspect of the present invention, the kind and content of the conductive agent are not limited, and specifically, the conductive agent may be one or more selected from conductive carbon black, superconducting carbon black, conductive graphite, acetylene black, ketjen black, graphene, and carbon nanotubes.
In the positive electrode slurry according to the first aspect of the present invention, the kind and content of the positive electrode active material are not limited, and specifically, the positive electrode active material may be selected from one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt aluminum oxide, and lithium iron phosphate.
Next, the positive electrode sheet according to the second aspect of the invention is explained.
The positive electrode sheet according to the second aspect of the invention includes a positive electrode current collector and a positive electrode sheet. The positive diaphragm is arranged on the surface of the positive current collector. The positive electrode membrane is formed by the positive electrode slurry according to the first aspect of the present invention.
In the positive plate according to the second aspect of the present invention, the positive electrode slurry is uniformly coated on a positive electrode current collector, and then the positive electrode plate is obtained by drying to remove the solvent NMP, and then cold pressing or the like.
In the positive electrode sheet according to the second aspect of the present invention, the positive electrode sheet may be provided on one or both surfaces of the positive electrode current collector.
In the positive electrode sheet according to the second aspect of the present invention, referring to fig. 1 and 2, during the cold pressing of the positive electrode sheet, the positive electrode sheet is subjected to a radial pressure N and a tangential frictional force f of the pressing roll 1, and since the thickness of the positive electrode sheet constantly changes during the cold pressing, the pressure N and the frictional force f can be respectively decomposed into a horizontal component force NxAnd fxAnd a component force N in the vertical directionyAnd fy. Wherein the component NxThe extension degree of the positive current collector 3 is less than that of the positive diaphragm 2, and the positive diaphragm is easy to process and break in the cold pressing process due to the difference of the extension degrees of the positive diaphragm 2 and the positive current collector 3. The addition of the plasticizer to the positive electrode slurry improves the lubrication between particles of the positive electrode active material, between particles of the conductive agent, and between particles of the conductive agent and particles of the positive electrode active materialTo a lesser extent, the interfacial friction, the pressure required during cold pressing and the consequent reduction of the horizontal component NxThe extension degree of the positive diaphragm 2 is reduced, the extension degree difference of the positive diaphragm 2 and the positive current collector 3 is reduced, the risk of strip breakage in the positive plate cold pressing process is reduced, and the phenomena that the grinding roller and the roller are damaged due to the fact that the compression roller 1 is in a high-pressure working condition for a long time are reduced. Meanwhile, the plasticizer can enter molecular chains of the binder (such as common VDF homopolymer or copolymer) to form a junction point of the plasticizer and polyvinylidene fluoride, the junction point between polyvinylidene fluoride molecular chains is replaced, acting force between polyvinylidene fluoride molecular chains is reduced, and crystallinity and rigidity of polyvinylidene fluoride are reduced, so that flexibility of polyvinylidene fluoride is improved, flexibility of the positive electrode diaphragm 2 is improved, pressure required during cold pressing can be reduced, winding hot pressing is reduced, risks of inner ring fracture and light leakage of the positive electrode sheet during cold pressing are reduced, and risks of processing belt breakage in the cold pressing process are reduced.
In the positive electrode sheet according to the second aspect of the present invention, the positive electrode current collector may be selected from an aluminum foil, a nickel foil, or a stainless steel foil.
An energy storage device according to a third aspect of the invention is explained again.
The energy storage device according to the third aspect of the invention includes the positive electrode sheet according to the second aspect of the invention.
In the energy storage device according to the third aspect of the invention, the energy storage device further includes a negative electrode sheet, a separator, a packaging case, an electrolyte, and the like.
In the energy storage device according to the third aspect of the present invention, it should be noted that the energy storage device may be a super capacitor, a lithium ion secondary battery, or a sodium ion secondary battery. In the embodiments of the present invention, only the embodiment in which the energy storage device is a lithium ion secondary battery is shown, but the present invention is not limited thereto.
In the lithium ion secondary battery, the negative electrode sheet includes a negative electrode current collector and a negative electrode membrane on the negative electrode current collector. The negative current collector may be a copper foil.
In the lithium ion secondary battery, the negative active material may be selected from artificial graphite or natural graphite. The negative electrode conductive agent can be one or more selected from acetylene black, conductive carbon black (Super P, Super S, 350G), carbon fiber (VGCF), Carbon Nanotube (CNT) and Ketjen black.
In the lithium ion secondary battery, the specific type of the separator is not particularly limited, and may be selected according to actual needs.
In the lithium ion secondary battery, the electrolyte may be a liquid electrolyte or a polymer electrolyte. The liquid electrolyte may include a lithium salt and an organic solvent.
In the lithium ion secondary battery, the specific kind of the lithium salt is not limited. Specifically, the lithium salt may be selected from LiPF6、LiBF4、LiN(SO2F)2(abbreviated LiFSI), LiN (CF)3SO2)2(abbreviated as LiTFSI) and LiClO4、LiAsF6、LiB(C2O4)2(abbreviated as LiBOB) and LiBF2C2O4(abbreviated as LiDFOB).
In the lithium ion secondary battery, the specific type of the organic solvent is not particularly limited, and may be selected according to actual needs. Preferably, a non-aqueous organic solvent is used. The non-aqueous organic solvent may include any kind of carbonate, carboxylate. The carbonate may include a cyclic carbonate or a chain carbonate. The non-aqueous organic solvent may further include a halogenated compound of a carbonate. Specifically, the organic solvent is selected from one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), butylene carbonate, pentylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, methylethyl carbonate, gamma-butyrolactone, methyl formate, ethyl propionate, propyl propionate and tetrahydrofuran.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. In the embodiment, only the case where the energy storage device is a lithium ion secondary battery is shown, but the present invention is not limited thereto.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
Example 1
97% by mass of a positive electrode active material Li (Ni)0.6Co0.2Mn0.2)O2The positive electrode plate is prepared by dry-mixing and stirring 1% of binder vinylidene fluoride homopolymer, 1.5% of conductive agent conductive carbon black and 0.5% of plasticizer polyethylene glycol (400), adding solvent NMP, uniformly stirring to obtain positive electrode slurry, uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil, drying at 85 ℃, and then cold-pressing to obtain the positive electrode plate with the compacted density of 3.5 g/cc.
Example 2
The positive electrode sheet was prepared as in example 1, except that,
96.5% by mass of Li (Ni) as a positive electrode active material was added0.6Co0.2Mn0.2)O2The conductive carbon black comprises 1% of a vinylidene fluoride homopolymer serving as a binder, 1.5% of conductive carbon black serving as a conductive agent and 1% of polyethylene glycol (400) serving as a plasticizer.
Example 3
The positive electrode sheet was prepared as in example 1, except that,
94.5% by mass of Li (Ni) as a positive electrode active material was added0.6Co0.2Mn0.2)O2The conductive carbon black comprises 1% of a vinylidene fluoride homopolymer serving as a binder, 1.5% of conductive carbon black serving as a conductive agent and 3% of polyethylene glycol (400) serving as a plasticizer.
Example 4
The positive electrode sheet was prepared as in example 1, except that,
92.5% by mass of a positive electrode active material Li (Ni) was added0.6Co0.2Mn0.2)O2The conductive carbon black comprises 1% of a vinylidene fluoride homopolymer serving as a binder, 1.5% of conductive carbon black serving as a conductive agent and 5% of polyethylene glycol (400) serving as a plasticizer.
Example 5
The positive electrode sheet was prepared as in example 1, except that,
96.5% by mass of a positive electrode active material Li (Ni0.6Co0.2Mn0.2)O2The conductive adhesive comprises 1% of a vinylidene fluoride homopolymer serving as a binder, 1.5% of conductive carbon black serving as a conductive agent and 1% of epoxidized soybean oil serving as a plasticizer.
Example 6
The positive electrode sheet was prepared as in example 1, except that,
96.5% by mass of Li (Ni) as a positive electrode active material was added0.6Co0.2Mn0.2)O2The conductive carbon black comprises 1% of a vinylidene fluoride homopolymer serving as a binder, 1.5% of conductive carbon black serving as a conductive agent and 1% of citric acid triester serving as a plasticizer.
Example 7
The positive electrode sheet was prepared as in example 1, except that,
96.5% by mass of Li (Ni) as a positive electrode active material was added0.6Co0.2Mn0.2)O2The conductive adhesive comprises 1% of a vinylidene fluoride homopolymer serving as a binder, 1.5% of conductive carbon black serving as a conductive agent and 1% of acetyl citric acid triester serving as a plasticizer.
Example 8
The positive electrode sheet was prepared as in example 1, except that,
the binder is selected from vinylidene fluoride-hexafluoropropylene copolymer (VDF-HFP).
Comparative example 1
The positive electrode sheet was prepared as in example 1, except that,
97.5% by mass of Li (Ni) as a positive electrode active material was added0.6Co0.2Mn0.2)O 21 percent of binder vinylidene fluoride homopolymer, 1.5 percent of conductive agent conductive carbon black and no plasticizer.
Comparative example 2
The positive electrode sheet was prepared as in example 1, except that,
91.5% by mass of Li (Ni) as a positive electrode active material was added0.6Co0.2Mn0.2)O2The conductive carbon black comprises 1% of a vinylidene fluoride homopolymer serving as a binder, 1.5% of conductive carbon black serving as a conductive agent and 6% of polyethylene glycol (400) serving as a plasticizer.
Comparative example 3
The positive electrode sheet was prepared as in example 1, except that,
96.5% by mass of Li (Ni) as a positive electrode active material was added0.6Co0.2Mn0.2)O2The conductive adhesive comprises 1% of a vinylidene fluoride homopolymer, 1.5% of conductive agent conductive carbon black and 1% of plasticizer dimethyl silicone oil.
Comparative example 4
The positive electrode sheet was prepared as in example 1, except that,
96.5% by mass of Li (Ni) as a positive electrode active material was added0.6Co0.2Mn0.2)O2The conductive carbon black comprises 1% of a binder vinylidene fluoride homopolymer, 1.5% of a conductive agent conductive carbon black and 1% of a plasticizer sulfolane.
The test procedure of the positive electrode sheet is explained next.
(1) Crystallinity test of PVDF adhesive film
PVDF (vinylidene fluoride homopolymer or vinylidene fluoride copolymer) and a plasticizer are added into a stirring tank (wherein the plasticizer is not added into the comparative example 1) according to the content ratio of the PVDF and the plasticizer in the examples 1 to 8 and the comparative examples 1 to 4, the stirring speed is set to be 25r/min, the dispersion speed is set to be 1500r/min, and the stirring time is set to be 6 hours, so that glue solution preparation is completed. And drying the glue solution at 80 ℃ for 6h, and carrying out DSC test on the obtained PVDF glue film to obtain the crystallinity of the PVDF glue film. Each group was tested 5 times and the average was taken.
(2) Testing of elongation of positive membrane
Removing aluminum foils on the two side edges of the positive plate, then scribing 3 sections of flat straight lines (incapable of piercing the positive membrane) on the positive plate, wherein the straight lines are parallel to the length direction of the positive membrane, and measuring the lengths of the 3 sections of straight lines, which are respectively marked as L1, L2 and L3; and (3) placing the positive plate on a cold press for cold pressing, adjusting cold pressing parameters to ensure that the actual compaction density of the positive plate is 3.5g/cc, and measuring the lengths of the 3 sections of straight lines after cold pressing, wherein the lengths are respectively marked as L1 ', L2 ' and L3 '. The elongation of the positive electrode membrane sheet is calculated according to the formula of (L' -L)/L, and the results are respectively expressed as E1, E2, and E3, and the average value of the three data is expressed as the actual elongation of the positive electrode membrane sheet.
(3) Winding hot-pressing test of positive membrane
Winding a positive plate, an isolating membrane and a negative plate (prepared from graphite, acetylene black, SBR and CMC in a mass ratio of 96:1:1: 1) into a square battery cell, then carrying out hot pressing at 60 ℃ under the pressure of 0.4MPa, then disassembling the battery cell, and observing whether light leaks from the crease, wherein in the wound battery cell, the total number of 45 creases is calculated. Each group was tested 5 times and the average was taken.
(4) Positive diaphragm folding test
And folding the positive electrode film in half, rolling the positive electrode film for 3 times back and forth by using a press roller with the weight of 2Kg, then paving the positive electrode film, repeating the operation until the folded part leaks light, and recording the folding times. Each group was tested 5 times and the average was taken.
(5) Test of 180-degree shear strength of positive membrane
Cutting a positive plate into a rectangle with the length of 100mm and the width of 20mm, taking a stainless steel plate with the width of 30mm, pasting double-faced adhesive tapes (with the length of 9mm and the width of 9mm), pasting the cut positive plate on the double-faced adhesive tapes on the stainless steel plate, rolling the surface of the positive plate back and forth for 3 times (300mm/min) by using a 2Kg compression roller, fixing the sample on a testing machine, keeping the axial direction of the pole piece consistent with the force application direction, loading the testing machine at the stripping speed of 10mm/min until the positive plate is broken, stopping testing, recording the maximum shearing force as F (unit N), wherein the bonding area S is 9mm, × 9mm, 81mm, and the bonding area S is 9mm, 899 mm2The shear strength P (unit MPa) was calculated from P ═ F/S.
(6) Resistance testing of positive diaphragm
And testing the resistance of the positive membrane by using a CRM-01 pole piece resistance tester. Each group was tested 5 times and the average was taken.
TABLE 1 results of Performance test of examples 1 to 8 and comparative examples 1 to 4
In the test of the positive electrode sheet, the elongation of the positive electrode sheet is used to characterize the elongation of the positive electrode sheet, wherein the larger the elongation of the positive electrode sheet, the larger the elongation. And (3) representing the flexibility of the positive membrane by using the crystallinity of the PVDF glue film, the folding light leakage times of the positive membrane and the light leakage number of the winding hot pressing crease. The lower the crystallinity of the PVDF adhesive film is, the greater the flexibility of the positive electrode film is; the more the light leakage times of the anode membrane during folding, the greater the flexibility of the anode membrane; in the winding and hot pressing of the anode membrane, the smaller the number of creases leaking light, the larger the flexibility of the anode membrane. The adhesive force between the positive membrane and the positive current collector is represented by the 180-degree peel strength of the positive membrane, and the higher the peel strength is, the better the adhesive force between the positive membrane and the positive current collector is. And characterizing the electronic conductivity of the positive electrode diaphragm by using the resistance of the positive electrode diaphragm, wherein the smaller the resistance of the positive electrode diaphragm is, the better the electronic conductivity of the positive electrode diaphragm is.
From the test results in table 1, it can be seen that, at the same compaction density, compared with comparative example 1 containing no plasticizer, the pressure required by the positive electrode films of examples 1 to 8 in cold pressing is obviously reduced, the elongation of the positive electrode film is obviously reduced, and the risk of strip breakage in the cold pressing process is greatly reduced; the number of light leakage times of the anode diaphragm after being wound and hot-pressed is obviously reduced, the light leakage times of the anode diaphragm during folding are obviously increased, the crystallinity of the PVDF adhesive film is greatly reduced, and the flexibility of the anode diaphragm is obviously improved; the adhesive force between the positive membrane and the positive current collector and the resistance of the positive membrane are not obviously deteriorated, and the normal use requirement can be still met; meanwhile, the positive electrode slurry has good coating processability.
In examples 1 to 4, with the increase of the content of the plasticizer polyethylene glycol (400), the elongation of the positive electrode membrane is reduced, the flexibility of the positive electrode membrane is obviously improved, but the adhesive force between the positive electrode membrane and the positive electrode current collector is gradually reduced, and the resistance of the positive electrode membrane is gradually increased, but the use requirement of the positive electrode sheet can still be met, and meanwhile, the increase of the content has no influence on the processing performance of the positive electrode slurry, compared with the optimal overall performance of the positive electrode membrane containing 1% of the plasticizer polyethylene glycol (400). In comparative example 2, the plasticizer content is too high, which may cause the resistance of the positive diaphragm to become large, resulting in serious decrease of the electrochemical performance of the energy storage device, and meanwhile, the shear strength of the positive diaphragm is reduced, i.e., the adhesive strength between the positive diaphragm and the positive current collector is reduced, so that the risk of powder falling during processing and using of the positive diaphragm is increased, and the safety performance of the energy storage device is affected.
In comparative example 3, the polarity of the plasticizer simethicone is low, and the plasticizer simethicone is incompatible with the solvent NMP, so that the phenomenon of the demixing of the simethicone and the NMP is easy to occur in the process of coating the anode slurry, and the anode slurry has poor coating processability and can not be coated, and in addition, the simethicone is incompatible with the solvent NMP, so that the plasticizer simethicone can not be made into a PVDF adhesive film, and the data of the crystallinity of the PVDF adhesive film is avoided.
In comparative example 4, the plasticizer sulfolane is solid at room temperature, which results in poor coating processability of the positive electrode slurry and coating failure, the crystallinity of the PVDF glue film by sulfolane is not obviously reduced, the light leakage frequency of the positive electrode film in folding is still low (only 1.8), and the flexibility of the positive electrode film is still poor.
Claims (9)
1. A positive electrode slurry comprising:
a positive electrode active material;
a conductive agent;
a binder; and
n-methyl pyrrolidone;
it is characterized in that the preparation method is characterized in that,
the positive electrode slurry further includes: a plasticizer;
the plasticizer and the N-methyl pyrrolidone are mutually soluble;
the plasticizer is in a liquid state at room temperature, the boiling point of the plasticizer is not lower than 150 ℃, and the flash point of the plasticizer is not lower than 110 ℃;
the molecular structure of the plasticizer contains polar functional groups, and the polar functional groups comprise one or more of-OH, -COOH and- (C ═ O) O-;
the crystallinity of the glue film formed by the plasticizer and the polyvinylidene fluoride is less than that of the glue film formed by the polyvinylidene fluoride;
the ratio of the mass of the plasticizer to the sum of the mass of the positive electrode active material, the conductive agent, the binder and the plasticizer is (0.5-5): 100.
2. The positive electrode slurry according to claim 1, wherein the plasticizer comprises one or more of polyethylene glycol, epoxidized soybean oil, tributyl citrate and acetyl tributyl citrate.
3. The positive electrode slurry according to claim 1, wherein the binder comprises polyvinylidene fluoride, and the polyvinylidene fluoride is selected from one or more of vinylidene fluoride homopolymer and vinylidene fluoride copolymer.
4. The positive electrode slurry according to claim 3, wherein the vinylidene fluoride copolymer is one or more selected from vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer and vinylidene fluoride-chlorotrifluoroethylene copolymer.
5. The positive electrode slurry according to claim 1, wherein the conductive agent is one or more selected from conductive carbon black, superconducting carbon black, conductive graphite, acetylene black, ketjen black, graphene, and carbon nanotubes.
6. The positive electrode slurry according to claim 1, wherein the positive electrode active material is one or more selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt aluminum oxide, and lithium iron phosphate.
7. A positive electrode sheet, comprising:
a positive current collector; and
the positive diaphragm is arranged on the surface of the positive current collector;
it is characterized in that the preparation method is characterized in that,
the positive electrode membrane is formed from the positive electrode slurry according to any one of claims 1 to 6.
8. An energy storage device, characterized by comprising the positive electrode sheet according to claim 7.
9. The energy storage device of claim 8, wherein the energy storage device is selected from the group consisting of a supercapacitor, a lithium ion secondary battery, and a sodium ion secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710035982.1A CN108321360B (en) | 2017-01-17 | 2017-01-17 | Positive electrode slurry, positive plate and energy storage device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710035982.1A CN108321360B (en) | 2017-01-17 | 2017-01-17 | Positive electrode slurry, positive plate and energy storage device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108321360A CN108321360A (en) | 2018-07-24 |
| CN108321360B true CN108321360B (en) | 2020-07-03 |
Family
ID=62891299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710035982.1A Active CN108321360B (en) | 2017-01-17 | 2017-01-17 | Positive electrode slurry, positive plate and energy storage device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108321360B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110896140B (en) | 2018-09-13 | 2021-01-15 | 宁德时代新能源科技股份有限公司 | Lithium-rich negative plate, battery cell and lithium ion battery |
| CN110148705B (en) * | 2019-05-29 | 2021-04-23 | 珠海冠宇电池股份有限公司 | Method and device for improving drying crack of pole piece |
| CN110459773B (en) * | 2019-09-09 | 2022-05-27 | 江苏正力新能电池技术有限公司 | Lithium ion battery pole piece slurry, pole piece, preparation method and application thereof |
| CN111029581B (en) * | 2019-11-14 | 2023-03-10 | 孚能科技(赣州)股份有限公司 | Positive electrode slurry and preparation method thereof, positive plate and preparation method thereof, lithium ion battery and application thereof |
| CN111224063A (en) * | 2020-01-14 | 2020-06-02 | 广州鹏辉能源科技股份有限公司 | Positive plate, aqueous electrode slurry and preparation method thereof |
| CN113178577A (en) * | 2021-05-20 | 2021-07-27 | 昆山宝创新能源科技有限公司 | Positive electrode slurry, positive plate and lithium ion battery |
| CN114784272B (en) * | 2022-06-07 | 2024-04-12 | 江西安驰新能源科技有限公司 | Environment-friendly lithium iron phosphate battery and preparation method thereof |
| CN116632249B (en) * | 2023-07-26 | 2023-09-29 | 中创新航科技集团股份有限公司 | Lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102368557A (en) * | 2011-11-01 | 2012-03-07 | 东莞新能源科技有限公司 | Lithium ion battery and anode sheet thereof |
| CN103840135A (en) * | 2014-03-27 | 2014-06-04 | 合肥国轩高科动力能源股份公司 | Preparation method for lithium titanate material membrane electrode |
| CN104854741A (en) * | 2012-12-28 | 2015-08-19 | 日东电工株式会社 | Positive electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery using positive electrode, and method for producing positive electrode |
| CN105304945A (en) * | 2015-09-16 | 2016-02-03 | 顾程松 | Alkaline polymer electrolyte film for zinc-nickel battery and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030039886A1 (en) * | 2001-08-22 | 2003-02-27 | Guiping Zhang | Modified lithium ion polymer battery |
-
2017
- 2017-01-17 CN CN201710035982.1A patent/CN108321360B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102368557A (en) * | 2011-11-01 | 2012-03-07 | 东莞新能源科技有限公司 | Lithium ion battery and anode sheet thereof |
| CN104854741A (en) * | 2012-12-28 | 2015-08-19 | 日东电工株式会社 | Positive electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery using positive electrode, and method for producing positive electrode |
| CN103840135A (en) * | 2014-03-27 | 2014-06-04 | 合肥国轩高科动力能源股份公司 | Preparation method for lithium titanate material membrane electrode |
| CN105304945A (en) * | 2015-09-16 | 2016-02-03 | 顾程松 | Alkaline polymer electrolyte film for zinc-nickel battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108321360A (en) | 2018-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108321360B (en) | Positive electrode slurry, positive plate and energy storage device | |
| US10923707B2 (en) | Dry process method for producing electrodes for electrochemical devices and electrodes for electrochemical devices | |
| JP5163439B2 (en) | FIBER-CONTAINING POLYMER FILM AND METHOD FOR PRODUCING SAME, ELECTROCHEMICAL DEVICE AND METHOD FOR PRODUCING SAME | |
| JP2011065984A (en) | Separator for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery | |
| JP7106762B2 (en) | Positive electrode sheet, manufacturing method thereof, and lithium ion secondary battery | |
| JP5359444B2 (en) | Lithium ion secondary battery | |
| EP4012816A1 (en) | Method for manufacturing lithium ion cell | |
| CN111199833A (en) | Electrochemical device | |
| WO2023142670A1 (en) | Positive electrode active material composition, aqueous positive electrode slurry, positive electrode sheet, secondary battery, and electric device | |
| US20230361305A1 (en) | Aqueous positive electrode sheet, and secondary battery including the electrode sheet, and power consumption apparatus | |
| CN116581249B (en) | Dry-method positive plate, lithium ion battery and preparation method of dry-method positive plate | |
| CN109461935B (en) | Electrode slice and electrochemical energy storage device | |
| CN112864360A (en) | High-voltage positive pole piece and lithium ion secondary battery containing same | |
| CN116114114A (en) | Separator, electrochemical device and electronic device comprising same | |
| CN118336294A (en) | Separator, and electrochemical device and electronic device including same | |
| CN108511680B (en) | Positive plate, preparation method thereof and energy storage device | |
| WO2023130791A1 (en) | Electrode pole piece and preparation method therefor, secondary battery, battery module, and battery pack | |
| CN114039027B (en) | Electrode plate and lithium ion battery comprising same | |
| JP7138228B1 (en) | Positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery, battery module, and battery system using the same | |
| CN114531925B (en) | Carbon current collector, electrochemical device and electronic device including the same | |
| EP3358652B1 (en) | Positive electrode for lithium-ion secondary cell, and lithium-ion secondary cell | |
| JP2018133297A (en) | Nonaqueous electrolyte secondary battery | |
| JP2011238476A (en) | Laminate, nonaqueous electrolyte secondary battery and laminate manufacturing method | |
| CN115036464B (en) | Electrochemical device and power utilization device | |
| JP7280913B2 (en) | Non-aqueous electrolyte secondary battery and battery module |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |