CN114204125B - Preparation method of integrated solid-state lithium iron phosphate battery - Google Patents
Preparation method of integrated solid-state lithium iron phosphate battery Download PDFInfo
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- CN114204125B CN114204125B CN202111304280.1A CN202111304280A CN114204125B CN 114204125 B CN114204125 B CN 114204125B CN 202111304280 A CN202111304280 A CN 202111304280A CN 114204125 B CN114204125 B CN 114204125B
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- phosphazene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 239000005922 Phosphane Substances 0.000 claims abstract description 20
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 229910000064 phosphane Inorganic materials 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 71
- 239000010410 layer Substances 0.000 claims description 42
- 239000006258 conductive agent Substances 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 38
- 239000000945 filler Substances 0.000 claims description 32
- 239000000919 ceramic Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 24
- 239000011267 electrode slurry Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 19
- 239000005518 polymer electrolyte Substances 0.000 claims description 19
- -1 phosphazene compound Chemical class 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 15
- 239000002041 carbon nanotube Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 238000013329 compounding Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 239000006256 anode slurry Substances 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- 229920003048 styrene butadiene rubber Polymers 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 229920000867 polyelectrolyte Polymers 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 6
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910012672 LiTiO Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 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
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/61—Types of temperature control
- H01M10/613—Cooling or keeping cold
-
- 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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of an integrated solid-state lithium iron phosphate battery, which relates to the technical field of lithium battery preparation and comprises a preparation step of a negative electrode plate containing a phosphane affinity layer, a preparation step of a positive electrode plate containing an electrolyte film and a preparation step of the integrated solid-state lithium iron phosphate battery, wherein the phosphane affinity layer is added on the negative electrode plate, so that the interface impedance between the negative electrode plate of the solid-state battery and a solid electrolyte is improved, and the migration capacity of lithium ions in the electrolyte is increased, thereby obtaining the negative electrode plate with improved cycle performance; in addition, the polymer solid electrolyte is directly formed into a film on the positive electrode plate, so that after the positive electrode plate and the solid electrolyte are integrated, the interface impedance between the solid electrolyte and the positive electrode plate is reduced, the path of lithium ion transmission is shortened, the circulation capacity of the battery is further improved, and the method has great production practice significance.
Description
Technical Field
The invention relates to the technical field of lithium battery preparation, in particular to a preparation method of an integrated solid-state lithium iron phosphate battery.
Background
Lithium batteries are a type of battery using a nonaqueous electrolyte solution with lithium metal or a lithium alloy as a positive/negative electrode material. The chemical characteristics of lithium metal are very active, so that the processing, storage and use of lithium metal have very high requirements on environment. With the development of science and technology, lithium batteries have become the mainstream. Lithium batteries can be broadly divided into two categories: lithium metal batteries and lithium ion batteries. Lithium ion batteries do not contain lithium in the metallic state and can be charged.
At present, the energy density, the cycle life and the safety of the lithium ion battery for the energy storage system are more and more important, but the cycle life of the traditional lithium ion battery is limited, the common service life of the lithium iron phosphate single battery at present is only 2000-4000 circles, and the lithium iron phosphate single battery is a certain distance from the targets of the 10 years at home and abroad and is far from the targets of the 15 years of service cycle of the photovoltaic field station. In addition, because the liquid electrolyte is used, the battery is easy to burn at high temperature, overcharge and overdischarge, and has great potential safety hazard.
In order to further meet the requirements of power grid energy storage and electric automobiles on lithium ion batteries, battery systems with longer cycle life, higher safety and higher energy density become research hotspots. In view of the foregoing, it is desirable to provide a method for preparing an integrated solid-state lithium iron phosphate battery to obtain a long cycle life, high safety lithium iron phosphate battery.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of an integrated solid-state lithium iron phosphate battery, which improves interface impedance between a negative electrode plate of the solid-state battery and a solid electrolyte by adding a phosphane affinity layer on the negative electrode plate, and increases migration capacity of lithium ions in the electrolyte so as to obtain the negative electrode plate and the battery with improved cycle performance, wherein the prepared battery has longer cycle life and excellent electrochemical performance.
In order to achieve the above purpose, the present invention adopts the technical scheme that:
the preparation method of the integrated solid-state lithium iron phosphate battery comprises the steps of preparing a negative pole piece containing a phosphane affinity layer, preparing a positive pole piece containing an electrolyte film and preparing the integrated solid-state lithium iron phosphate battery;
the preparation of the negative electrode plate containing the phosphazene affinity layer comprises the following steps:
s1, sequentially adding 95-98% of graphite anode material, 0-2% of phosphazene composite conductive agent and 2-3% of binder SBR into pyrrolidone solvent according to a preset weight ratio to obtain anode slurry.
In the step S1, the phosphazene compound conductive agent includes one or more conductive agents formed by compounding phosphazene with carbon black, compounding phosphazene with graphitized conductive agent, compounding phosphazene with carbon nano tube and compounding phosphazene with carbon fiber. For example, conductive carbon blacks KS-6, KS-15 are compounded with phosphane, SPUPER Li is compounded with phosphane, meteorological growth type carbon fiber VGCF is compounded with phosphane, carbon nanotube CNT is compounded with phosphane and the like, and phosphane has high carrier ion mobility close to graphene and good electric conduction and thermal conductivity.
Preferably, the phosphazene composite conductive agent is a black phosphazene-graphene composite conductive agent, wherein the mixing ratio of the phosphazene to the graphene is 1:1-1:5. The black phosphazene-graphene composite conductive agent has high conductivity.
Preferably, the phosphazene is spherical or blocky particles with the average particle diameter of 50nm-10um, and the particle diameter of the carbon black or graphitized conductive agent is 5nm-10um.
S2, performing viscosity adjustment on the negative electrode slurry obtained in the step S1, uniformly coating the negative electrode slurry on a copper foil current collector after adjustment, and drying to obtain a negative electrode plate.
In the step S2, the viscosity of the slurry is 4000-7000cP.
S3, mixing the black phosphazene into the acrylonitrile polymer solution, heating and stirring for 6-8 hours to obtain the acrylonitrile polymer solution containing the phosphazene.
And S4, coating the phosphazene-containing acrylonitrile polymerization solution obtained in the step S3 on the surface of the negative electrode plate obtained in the step S2 while the solution is hot, so as to obtain the negative electrode plate containing the phosphazene affinity layer.
In the step S4, the coating thickness of the phosphazene affinity conductive layer is 2-6 um.
The preparation of the positive electrode plate containing the electrolyte film comprises the following steps:
s1, mixing and coating the positive electrode active material, the lithium ion conductive agent, the binder and the pyrrolidone solvent according to the preparation proportion of the positive electrode plate of the ion battery to prepare the positive electrode plate, and drying for later use.
In the step s1, the positive electrode active material includes one of lithium iron phosphate, nickel cobalt manganese (ternary positive electrode), lithium cobaltate and lithium manganate; the lithium ion conductive agent comprises one of carbon black KS-6, KS-15, carbon Nanotube (CNT) and carbon fiber (VGCF); the binder includes one of an oily binder PVDF and PAALi.
And s2, adding the lithium salt, the ceramic filler and the high molecular monomer into a solvent DMF, and heating to obtain the polymer electrolyte emulsion containing the ceramic filler.
In the step s2, the lithium salt comprises one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium trifluoromethane sulfonate and lithium bistrifluoromethyl sulfonimide, and the dosage of the lithium salt is 5-60% of the mass of the polymer electrolyte.
In the step s2, the ceramic filler includes barium titanate (BaTiO 3 ) Lithium titanate (LiTiO) 3 ) One or more of nano aluminum oxide, nano silicon dioxide and nano titanium dioxide for enhancing ionic conductivity and electrolyte mechanical strength; the particle size of the ceramic filler is 20nm-1um, and the dosage of the ceramic filler is 2% -40% of the mass of the polymer electrolyte.
In the step s2, the high molecular monomer comprises one of ethylene oxide and methyl formate, and the polymer comprises one of polyethylene oxide (PEO), polymethyl formate (PMMA), polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF) which is a high molecular polymer of easily soluble lithium salt.
And S3, coating the polymer electrolyte emulsion containing the ceramic filler obtained in the step S2 on the surface layer of the positive electrode plate dried in the step S1 to obtain the net-shaped cross-linked positive electrode plate containing the electrolyte film.
The integrated solid-state lithium iron phosphate battery is prepared by hot-pressing and compounding the negative electrode plate containing the phosphane affinity layer obtained in the negative electrode plate preparation step and the positive electrode plate containing the electrolyte film obtained in the positive electrode plate preparation step.
According to the invention, the phosphane affinity layer is added on the negative electrode plate, so that the interface impedance between the negative electrode plate of the solid battery and the solid electrolyte is improved, and the migration capability of lithium ions in the electrolyte is increased, thereby obtaining the negative electrode plate with improved cycle performance; in addition, the polymer solid electrolyte is directly formed into a film on the positive electrode plate, so that after the positive electrode plate and the solid electrolyte are integrated, the interface impedance between the solid electrolyte and the positive electrode plate is reduced, the path of lithium ion transmission is shortened, the circulation capacity of the battery is further improved, and the method has great production practice significance.
The invention also provides an integrated solid-state lithium iron phosphate battery which is prepared by adopting the preparation method and comprises a negative electrode plate containing a phosphane affinity layer, a cross-linked reticular flexible solid polymer electrolyte containing a ceramic coating and an integrated lithium iron phosphate positive electrode plate loaded with the solid electrolyte.
The invention has the beneficial effects that:
1. the cathode material adopts the novel high-conductivity black phosphazene-graphene composite conductive agent, the excellent heat conductivity of the phosphazene material can timely conduct away high heat accumulated by the battery due to charge and discharge besides the conductivity of the pole piece, and the graphene can increase the flexibility of the pole piece, after the graphene and the pole piece are compounded, the temperature rise of the battery in the later charge and discharge process can be restrained, and the cycle life of the battery can be prolonged.
2. The integrated battery formed by adding the phosphoene-containing polymer affinity layer on the surface layer of the anode material and hot-pressing the phosphoene-containing polymer affinity layer with the electrolyte overcomes the defect of poor ionic conductivity of the traditional polymer electrolyte, so that the ionic conductivity of the polymer electrolyte is close to that of the inorganic solid electrolyte, and the integrated battery has good flexibility of the organic polymer electrolyte and excellent conductivity of the inorganic electrolyte.
3. The polymer electrolyte is compounded with oxide filler with higher conductivity and dielectric constant, so that the mechanical strength of the electrolyte membrane is enhanced, the possibility that dendrites pierce the diaphragm in the process of fully electrifying lithium ions is reduced, and the safety of the battery is improved.
4. The polymeric solid electrolyte is directly formed on the positive electrode plate, so that the interface impedance between the solid electrolyte and the positive electrode plate is reduced, and the transmission path of lithium ions in the electrolyte is shortened.
Drawings
FIG. 1 is a process flow diagram of a preparation method of the present invention;
fig. 2 is a graph showing a comparison of the full cell cycle performance test obtained in examples 1, 2 and 5 of the present invention and comparative 1.
Detailed Description
The conception, specific structure, and technical effects produced by the present invention will be clearly and completely described below with reference to the embodiments and the drawings to fully understand the objects, features, and effects of the present invention.
Example 1
The preparation method of the integrated solid-state lithium iron phosphate battery is shown in fig. 1, and comprises the steps of preparation of a negative electrode plate containing a phosphane affinity layer, preparation of a positive electrode plate containing an electrolyte film and preparation of the integrated solid-state lithium iron phosphate battery, and specifically comprises the following steps:
1. preparation of negative electrode plate containing phosphazene affinity layer
S1, sequentially adding 95-98% of graphite anode material, 0-2% of black phosphazene-graphene composite conductive agent and 2-3% of binder styrene butadiene rubber SBR into pyrrolidone NMP solvent according to a preset weight ratio to obtain anode slurry.
Wherein the phosphazene is spherical or blocky particles with the average particle diameter of 50nm-10um, and the mixing ratio of the phosphazene and the graphene is 1:1-1:5.
S2, adjusting the viscosity of the negative electrode slurry obtained in the step S1, adjusting the viscosity to 4000-7000cP, uniformly coating the negative electrode slurry on a copper foil current collector, and drying the negative electrode slurry for later use to obtain the negative electrode plate.
S3, mixing the black phosphazene into the acrylonitrile polymer solution, heating and stirring for 6-8 hours, and preparing the acrylonitrile polymer solution containing the phosphazene.
And S4, coating the phosphazene-containing acrylonitrile polymerization solution obtained in the step S3 on the surface of the negative electrode plate obtained in the step S2 while the solution is hot, so as to obtain the negative electrode plate containing the phosphazene affinity layer. The coating thickness of the phosphazene affinity conductive layer is 2-6 um.
2. Preparation of positive electrode plate containing electrolyte film
S1, mixing and coating the positive active material lithium iron phosphate, a lithium ion conductive agent, an oily adhesive PVDF and a solvent pyrrolidone (NMP) according to the preparation proportion of the positive electrode plate of the conventional ion battery to prepare the positive electrode plate, and drying for later use.
Wherein the lithium ion battery conductive agent is carbon black KS-6, KS-15, carbon Nano Tube (CNT), carbon fiber (VGCF) and the like, and the adhesive is PAALi and the like.
s2, lithium hexafluorophosphate and ceramic filler BaTiO 3 Adding 20% and 10% of polymer electrolyte into DMF solvent containing ethylene oxide monomer, heating to prepare ceramic filler-containing polyelectrolyte emulsion.
And S3, coating the polymer emulsion prepared in the step S2 on the surface layer of the positive electrode plate prepared in the step S1 to obtain the net-shaped cross-linked positive electrode plate containing the electrolyte film.
3. Preparation of integrated solid-state lithium iron phosphate battery
And (3) carrying out hot-pressing compounding on the negative pole piece containing the phosphane affinity layer prepared in the step (S4) and the positive pole piece containing the electrolyte film prepared in the step (S3) to obtain the integrated solid-state lithium iron phosphate battery.
Example 2
The preparation method of the integrated solid-state lithium iron phosphate battery comprises the following steps of;
1. preparation of negative electrode plate containing phosphazene affinity layer
S1, sequentially adding 95-98% of graphite anode material, 0-2% of black phosphazene-carbon nano tube composite conductive agent and 2-3% of binder styrene butadiene rubber SBR into pyrrolidone NMP solvent according to a preset weight ratio to obtain anode slurry.
S2, adjusting the viscosity of the negative electrode slurry obtained in the step S1, adjusting the viscosity to 4000-7000cP, uniformly coating the negative electrode slurry on a copper foil current collector, and drying the negative electrode slurry for later use to obtain the negative electrode plate.
S3, mixing the black phosphazene into the acrylonitrile polymer solution, heating and stirring for 6-8 hours, and preparing the acrylonitrile polymer solution containing the phosphazene.
And S4, coating the phosphazene-containing acrylonitrile polymerization solution obtained in the step S3 on the surface of the negative electrode plate obtained in the step S2 while the solution is hot, so as to obtain the negative electrode plate containing the phosphazene affinity layer. The coating thickness of the phosphazene affinity conductive layer is 2-6 um.
2. Preparation of positive electrode plate containing electrolyte film
S1, mixing and coating the positive active material lithium iron phosphate, a lithium ion conductive agent, an oily adhesive PVDF and a solvent pyrrolidone (NMP) according to the preparation proportion of the positive electrode plate of the conventional ion battery to prepare the positive electrode plate, and drying for later use.
s2, lithium hexafluorophosphate and ceramic filler BaTiO 3 Adding 20% and 10% of polymer electrolyte into DMF solvent containing ethylene oxide monomer, heating to prepare ceramic filler-containing polyelectrolyte emulsion.
And S3, coating the polymer emulsion prepared in the step S2 on the surface layer of the positive electrode plate prepared in the step S1 to obtain the net-shaped cross-linked positive electrode plate containing the electrolyte film.
3. Preparing an integrated solid-state lithium iron phosphate battery:
and (3) carrying out hot-pressing compounding on the negative pole piece containing the phosphane affinity layer prepared in the step (S4) and the positive pole piece containing the electrolyte film prepared in the step (S3) to obtain the integrated solid-state lithium iron phosphate battery.
Example 2 is different from example 1 in that the phosphazene composite conductive agent added in the step S1 is a black phosphazene-carbon nanotube, the complexing agent of the black phosphazene-carbon nanotube is added in an acrylonitrile solution to form an affinity layer, and the rest of the process is exactly the same as example 1. The purpose of example 2 was to compare the effect of different phosphazene compound conductive agents on the performance index of the battery.
Example 3
The preparation method of the integrated solid-state lithium iron phosphate battery comprises the following steps of;
1. preparation of negative electrode plate containing phosphazene affinity layer
S1, sequentially adding 95-98% of graphite anode material, 0-2% of black phosphazene/conductive carbon black KS-6 composite conductive agent and 2-3% of binder styrene butadiene rubber SBR into pyrrolidone NMP solvent according to a preset weight ratio to obtain anode slurry.
S2, adjusting the viscosity of the negative electrode slurry obtained in the step S1, adjusting the viscosity to 4000-7000cP, uniformly coating the negative electrode slurry on a copper foil current collector, and drying the negative electrode slurry for later use to obtain the negative electrode plate.
S3, mixing the black phosphazene into the acrylonitrile polymer solution, heating and stirring for 6-8 hours, and preparing the acrylonitrile polymer solution containing the phosphazene.
And S4, coating the phosphazene-containing acrylonitrile polymerization solution obtained in the step S3 on the surface of the negative electrode plate obtained in the step S2 while the solution is hot, so as to obtain the negative electrode plate containing the phosphazene affinity layer. The coating thickness of the phosphazene affinity conductive layer is 2-6 um.
2. Preparation of positive electrode plate containing electrolyte film
S1, mixing and coating the positive active material lithium iron phosphate, a lithium ion conductive agent, an oily adhesive PVDF and a solvent pyrrolidone (NMP) according to the preparation proportion of the positive electrode plate of the conventional ion battery to prepare the positive electrode plate, and drying for later use.
s2, lithium hexafluorophosphate and ceramic filler BaTiO 3 Adding 20% and 10% of polymer electrolyte into DMF solvent containing ethylene oxide monomer, heating to prepare ceramic filler-containing polyelectrolyte emulsion.
And S3, coating the polymer emulsion prepared in the step S2 on the surface layer of the positive electrode plate prepared in the step S1 to obtain the net-shaped cross-linked positive electrode plate containing the electrolyte film.
3. Preparing an integrated solid-state lithium iron phosphate battery:
and (3) carrying out hot-pressing compounding on the negative pole piece containing the phosphane affinity layer prepared in the step (S4) and the positive pole piece containing the electrolyte film prepared in the step (S3) to obtain the integrated solid-state lithium iron phosphate battery.
Example 3 is different from example 1 in that the phosphazene compound conductive agent added in the S1 st step is black phosphazene/conductive carbon black KS-6, and the complexing agent of black phosphazene-carbon nanotubes is added in the acrylonitrile solution to form an affinity layer, and the rest of the process is exactly the same as example 1. The purpose of example 3 was to compare the effect of different phosphazene compound conductive agents on the performance index of the battery.
Example 4
The preparation method of the integrated solid-state lithium iron phosphate battery comprises the following steps of;
1. preparation of negative electrode plate containing phosphazene affinity layer
S1, sequentially adding 95-98% of graphite anode material, 0-2% of black phosphazene-graphene composite conductive agent and 2-3% of binder styrene butadiene rubber SBR into pyrrolidone NMP solvent according to a preset weight ratio to obtain anode slurry.
S2, adjusting the viscosity of the negative electrode slurry obtained in the step S1, adjusting the viscosity to 4000-7000cP, uniformly coating the negative electrode slurry on a copper foil current collector, and drying the negative electrode slurry for later use to obtain the negative electrode plate.
S3, mixing the black phosphazene into the acrylonitrile polymer solution, heating and stirring for 6-8 hours, and preparing the acrylonitrile polymer solution containing the phosphazene.
And S4, coating the phosphazene-containing acrylonitrile polymerization solution obtained in the step S3 on the surface of the negative electrode plate obtained in the step S2 while the solution is hot, so as to obtain the negative electrode plate containing the phosphazene affinity layer. The coating thickness of the phosphazene affinity conductive layer is 2-6 um.
2. Preparation of positive electrode plate containing electrolyte film
S1, mixing and coating the positive active material lithium iron phosphate, a lithium ion conductive agent, an oily adhesive PVDF and a solvent pyrrolidone (NMP) according to the preparation proportion of the positive electrode plate of the conventional ion battery to prepare the positive electrode plate, and drying for later use.
And s2, adding 20% of lithium tetrafluoroborate and 10% of ceramic filler nano titanium dioxide into DMF (dimethyl formamide) which is a solvent in which ethylene oxide monomers are dissolved according to the content of polymer electrolyte, and heating to prepare the ceramic filler-containing polyelectrolyte emulsion.
And S3, coating the polymer emulsion prepared in the step S2 on the surface layer of the positive electrode plate prepared in the step S1 to obtain the net-shaped cross-linked positive electrode plate containing the electrolyte film.
3. Preparing an integrated solid-state lithium iron phosphate battery:
and (3) carrying out hot-pressing compounding on the negative pole piece containing the phosphane affinity layer prepared in the step (S4) and the positive pole piece containing the electrolyte film prepared in the step (S3) to obtain the integrated solid-state lithium iron phosphate battery.
Example 4 differs from example 1 in that the ceramic filler added to prepare the polymer network electrolyte in step s2 is nano titanium dioxide, the lithium salt is lithium tetrafluoroborate, and the rest of the process is exactly the same as example 1. The purpose of example 4 was to compare the effect of different ceramic fillers and lithium salts on the cell performance index.
Example 5
The preparation method of the integrated solid-state lithium iron phosphate battery comprises the following steps of;
1. preparation of negative electrode plate containing phosphazene affinity layer
S1, sequentially adding 95-98% of graphite anode material, 0-2% of black phosphazene-graphene composite conductive agent and 2-3% of binder styrene butadiene rubber SBR into pyrrolidone NMP solvent according to a preset weight ratio to obtain anode slurry.
S2, adjusting the viscosity of the negative electrode slurry obtained in the step S1, adjusting the viscosity to 4000-7000cP, uniformly coating the negative electrode slurry on a copper foil current collector, and drying the negative electrode slurry for later use to obtain the negative electrode plate.
S3, mixing the black phosphazene into the acrylonitrile polymer solution, heating and stirring for 6-8 hours, and preparing the acrylonitrile polymer solution containing the phosphazene.
And S4, coating the phosphazene-containing acrylonitrile polymerization solution obtained in the step S3 on the surface of the negative electrode plate obtained in the step S2 while the solution is hot, so as to obtain the negative electrode plate containing the phosphazene affinity layer. The coating thickness of the phosphazene affinity conductive layer is 2-6 um.
2. Preparation of positive electrode plate containing electrolyte film
S1, mixing and coating the positive active material lithium iron phosphate, a lithium ion conductive agent, an oily adhesive PVDF and a solvent pyrrolidone (NMP) according to the preparation proportion of the positive electrode plate of the conventional ion battery to prepare the positive electrode plate, and drying for later use.
And s2, adding the lithium bistrifluorosulfonate and the ceramic filler nano titanium dioxide into DMF (dimethyl formamide) which is a solvent in which ethylene oxide monomers are dissolved according to the content of 20% and 10% of polymer electrolyte, and heating to prepare the polyelectrolyte emulsion containing the ceramic filler.
And S3, coating the polymer emulsion prepared in the step S2 on the surface layer of the positive electrode plate prepared in the step S1 to obtain the net-shaped cross-linked positive electrode plate containing the electrolyte film.
3. Preparing an integrated solid-state lithium iron phosphate battery:
and (3) carrying out hot-pressing compounding on the negative pole piece containing the phosphane affinity layer prepared in the step (S4) and the positive pole piece containing the electrolyte film prepared in the step (S3) to obtain the integrated solid-state lithium iron phosphate battery.
Example 5 differs from example 1 in that the ceramic filler added to prepare the polymer network electrolyte in step s2 is nano titanium dioxide, the lithium salt is lithium bistrifluorosulfonate, and the rest of the process is exactly the same as example 1. The purpose of example 5 was to compare the effect of different ceramic fillers and lithium salts on the cell performance index.
Comparative example
The first step: preparation of negative pole piece
(a) According to the preset weight proportion, 95-98% of graphite anode material, 0-2% of black phosphorus alkene-graphene composite conductive agent and 2-3% of binder styrene butadiene rubber SBR are sequentially added into a solvent pyrrolidone NMP to prepare anode slurry.
(b) And d, uniformly coating the negative electrode slurry obtained in the step a on a copper foil current collector after adjusting the viscosity, and drying for later use to obtain a negative electrode plate.
The average particle diameter of the composite conductive agent is spherical or blocky particles within the range of 50nm-10um, and the mixing ratio of the phosphazene and the graphene is 1:1-1:5.
Wherein in step b, the slurry viscosity is preferably in the range of 4000-7000cP.
And a second step of: preparation of lithium iron phosphate positive electrode plate
And mixing and coating the positive active material lithium iron phosphate, a lithium ion conductive agent, an oily adhesive PVDF and a solvent pyrrolidone (NMP) according to the preparation proportion of the conventional positive electrode plate of the ion battery to prepare the positive electrode plate, and drying for later use.
The lithium ion battery conductive agent is carbon black KS-6, KS-15, carbon Nano Tube (CNT), carbon fiber (VGCF) and the like, and the adhesive is PAALi and the like.
And a third step of: lithium hexafluorophosphate and ceramic filler BaTiO 3 Adding 20% and 10% of polymer electrolyte into DMF solvent containing ethylene oxide monomer, heating to prepare ceramic filler-containing polyelectrolyte emulsion,
fourth step: and coating the polymer emulsion obtained in the third step on the surface layer of the positive electrode plate prepared in the second step to obtain the positive electrode integrated plate containing the electrolyte film.
Fifth step: and (3) carrying out hot-pressing compounding on the first-step negative electrode plate and the fourth-step positive electrode plate containing the polymer solid electrolyte to prepare the integrated solid lithium iron phosphate battery.
The comparative example is different from example 1 in that the comparative example does not have the step of preparing an acrylonitrile polymer solution containing S3 phosphazene and the step of preparing a negative electrode sheet containing S4 phosphazene affinity layer in preparing a negative electrode sheet. The purpose of the comparative example was to compare the effect of the negative electrode tab without the phosphazene-containing affinity layer on the cell performance index.
The electrochemical performance of the integrated solid-state batteries prepared in examples 1 to 5 and comparative examples was tested, and the test items and results thereof are shown in the following table:
in the above table, cycle life refers to the number of cycles the battery runs when the battery capacity retention rate is 80%.
From the above table, the difference between example 1 and examples 2 and 3 is that the type of the phosphazene compound conductive agent added in the step S1 is different, and the performance indexes of the result are that the ionic conductivity, the direct current internal resistance, the cycle life and other performance results of example 1 are obviously better than those of examples 2 and 3, which shows that the effect of adding the black phosphazene-graphene compound conductive agent in the preparation of the negative electrode slurry is the best. Example 1 is different from examples 4 and 5 in that the types of ceramic filler and lithium salt added in step s2 are different, and as a result, the performance indexes of the ceramic filler and lithium salt are obviously superior to those of examples 4 and 5 in terms of ionic conductivity, DC internal resistance, cycle life and the like of example 1, and the addition of lithium hexafluorophosphate and BaTiO in the preparation of polyelectrolyte emulsion 3 The ceramic filler works best.
Examples 1 to 5 are different from comparative examples in that in examples 1 to 5, in the preparation step of the negative electrode sheet, the preparation step of the phosphazene-containing acrylonitrile polymer solution and the preparation step of the negative electrode sheet containing the phosphazene affinity layer were added, and in the result performance index, the results of the performances such as the ionic conductivity, the direct current internal resistance, the cycle life and the like of examples 1 to 5 were significantly superior to those of comparative examples, which showed that by adding the phosphazene affinity layer on the negative electrode sheet, the interface resistance between the negative electrode sheet and the solid electrolyte of the solid battery was improved, the migration ability of lithium ions in the electrolyte was increased, and thus the negative electrode sheet and the battery with improved cycle performance and the cycle life of the battery were obtained, as shown in fig. 2.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the embodiments described above, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present invention, and these are intended to be included in the scope of the present invention as defined in the appended claims.
Claims (9)
1. The preparation method of the integrated solid-state lithium iron phosphate battery is characterized by comprising the following steps of: the preparation method comprises the steps of preparing a negative pole piece containing a phosphane affinity layer, preparing a positive pole piece containing an electrolyte film and preparing an integrated solid-state lithium iron phosphate battery;
the preparation of the negative electrode plate containing the phosphazene affinity layer comprises the following steps:
s1, sequentially adding 95-98% of graphite anode material, less than or equal to 2% of phosphazene composite conductive agent and 2-3% of binder SBR into pyrrolidone solvent according to a preset weight ratio to obtain anode slurry; wherein the phosphazene compound conductive agent comprises one or more of phosphazene and carbon black, phosphazene and graphitized conductive agent, phosphazene and carbon nano tube and phosphazene and carbon fiber;
s2, performing viscosity adjustment on the negative electrode slurry obtained in the step S1, uniformly coating the negative electrode slurry on a copper foil current collector after adjustment, and drying to obtain a negative electrode plate;
s3, mixing the black phosphazene into the acrylonitrile polymer solution, heating and stirring for 6-8 hours to obtain a phosphazene-containing acrylonitrile polymer solution;
s4, coating the acrylonitrile polymerization solution containing the phosphazene obtained in the step S3 on the surface of the negative electrode plate obtained in the step S2 while the acrylonitrile polymerization solution is hot to obtain a negative electrode plate containing a phosphazene affinity layer;
the preparation of the positive electrode plate containing the electrolyte film comprises the following steps:
s1, mixing and coating an anode active material, a lithium ion conductive agent, a binder and a pyrrolidone solvent according to the preparation proportion of an anode plate of an ion battery to prepare the anode plate, and drying for later use;
s2, adding the lithium salt, the ceramic filler and the high molecular monomer into a solvent DMF, and heating to obtain a polymer electrolyte emulsion containing the ceramic filler;
s3, coating the polymer electrolyte emulsion containing the ceramic filler obtained in the step S2 on the surface layer of the positive electrode plate dried in the step S1 to obtain a net-shaped cross-linked positive electrode plate containing the electrolyte film;
the integrated solid-state lithium iron phosphate battery is prepared by hot-pressing and compounding the negative electrode plate containing the phosphane affinity layer obtained in the negative electrode plate preparation step and the positive electrode plate containing the electrolyte film obtained in the positive electrode plate preparation step.
2. The method of manufacturing according to claim 1, wherein: in the step S1, the phosphazene composite conductive agent is a black phosphazene-graphene composite conductive agent, wherein the mixing ratio of phosphazene and graphene is 1:1-1:5.
3. The method of manufacturing according to claim 1, wherein: in the step S1, the phosphazene is spherical or blocky particles with the average particle diameter of 50nm-10um, and the particle diameter of the carbon black or graphitized conductive agent is 5nm-10um.
4. The method of manufacturing according to claim 1, wherein: in the step S2, the viscosity of the slurry is 4000-7000cP.
5. The method of manufacturing according to claim 1, wherein: in the step S4, the coating thickness of the phosphazene affinity conductive layer is 2-6 um.
6. The method of manufacturing according to claim 1, wherein: in the step s1, the positive electrode active material comprises one of lithium iron phosphate, nickel cobalt manganese, lithium cobaltate and lithium manganate; the lithium ion conductive agent comprises one of carbon black KS-6, KS-15, carbon nano tubes and carbon fibers; the binder includes one of an oily binder PVDF and PAALi.
7. The method of manufacturing according to claim 1, wherein: in the step s2, the lithium salt comprises one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium trifluoromethane sulfonate and lithium bistrifluoromethyl sulfonimide, and the dosage of the lithium salt is 5-60% of the mass of the polymer electrolyte.
8. The method of manufacturing according to claim 1, wherein: in the step s2, the ceramic filler comprises one or more of barium titanate, lithium titanate, nano aluminum oxide, nano silicon dioxide and nano titanium dioxide; the particle size of the ceramic filler is 20nm-1um, and the dosage of the ceramic filler is 2% -40% of the mass of the polymer electrolyte.
9. The method of manufacturing according to claim 1, wherein: in the step s2, the high molecular monomer comprises one of ethylene oxide and methyl formate, and the polymer comprises one of polyethylene oxide, polymethyl formate, polyacrylonitrile and polyvinylidene fluoride.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017200338A1 (en) * | 2016-05-19 | 2017-11-23 | 주식회사 엘지화학 | Composite anode material for secondary battery, anode comprising same, and lithium secondary battery |
| CN107434838A (en) * | 2016-05-27 | 2017-12-05 | 台光电子材料股份有限公司 | Phosphorus-containing olefin polymer, preparation method thereof, composition thereof and finished product |
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN110233284A (en) * | 2019-07-17 | 2019-09-13 | 江西省汇亿新能源有限公司 | A kind of low form high-energy density long circulating ferric phosphate lithium cell |
| CN111430778A (en) * | 2019-01-09 | 2020-07-17 | 通用汽车环球科技运作有限责任公司 | Rechargeable lithium ion battery chemistry with fast charging capability and high energy density |
-
2021
- 2021-11-05 CN CN202111304280.1A patent/CN114204125B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017200338A1 (en) * | 2016-05-19 | 2017-11-23 | 주식회사 엘지화학 | Composite anode material for secondary battery, anode comprising same, and lithium secondary battery |
| CN107434838A (en) * | 2016-05-27 | 2017-12-05 | 台光电子材料股份有限公司 | Phosphorus-containing olefin polymer, preparation method thereof, composition thereof and finished product |
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN111430778A (en) * | 2019-01-09 | 2020-07-17 | 通用汽车环球科技运作有限责任公司 | Rechargeable lithium ion battery chemistry with fast charging capability and high energy density |
| CN110233284A (en) * | 2019-07-17 | 2019-09-13 | 江西省汇亿新能源有限公司 | A kind of low form high-energy density long circulating ferric phosphate lithium cell |
Non-Patent Citations (1)
| Title |
|---|
| 黑磷烯稳定性增强研究进展;刘艳奇;何路东;廉培超;陈鑫智;梅毅;;化工学报(第03期);全文 * |
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