CN114744155A - Quick-charging composite electrode plate, preparation method thereof and solid-state battery - Google Patents
Quick-charging composite electrode plate, preparation method thereof and solid-state battery Download PDFInfo
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- CN114744155A CN114744155A CN202210317031.4A CN202210317031A CN114744155A CN 114744155 A CN114744155 A CN 114744155A CN 202210317031 A CN202210317031 A CN 202210317031A CN 114744155 A CN114744155 A CN 114744155A
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- 239000002131 composite material Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000011888 foil Substances 0.000 claims abstract description 49
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 42
- 239000004917 carbon fiber Substances 0.000 claims abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 239000011247 coating layer Substances 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 16
- 238000005096 rolling process Methods 0.000 claims abstract description 16
- 239000011267 electrode slurry Substances 0.000 claims abstract description 12
- 239000013543 active substance Substances 0.000 claims abstract description 8
- 238000007740 vapor deposition Methods 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002955 isolation Methods 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011889 copper foil Substances 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 18
- 230000001070 adhesive effect Effects 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 239000011149 active material Substances 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229910006194 Li1+xAlxGe2-x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910006196 Li1+xAlxGe2−x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910011671 Li4-xGe1-xPxS4 Inorganic materials 0.000 claims description 3
- 229910011572 Li4−xGe1−xPxS4 Inorganic materials 0.000 claims description 3
- 229910010850 Li6PS5X Inorganic materials 0.000 claims description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 3
- 229910004600 P2S5 Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 3
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 10
- 239000012466 permeate Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- 239000012528 membrane Substances 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011268 mixed slurry Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 5
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910010848 Li6PS5Cl Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a quick-charging composite electrode plate, a preparation method thereof and a solid-state battery, wherein the preparation method comprises the following steps: placing the foil in a vapor deposition furnace, continuously introducing airflow containing a carbon source under the condition of oxygen isolation, heating the vapor deposition furnace to carbonize the carbon source to grow carbon fibers on the surface of the foil in situ, and preparing a composite current collector; mixing an active substance, a binder, an electrolyte and an organic solvent according to a predetermined ratio to obtain electrode slurry; and coating the electrode slurry on the surface of the composite current collector, and baking and rolling to form a coating layer to obtain the quick-charging composite electrode slice. In the invention, the carbon fiber grows on the foil in situ, so that the impedance can be reduced, the efficiency of current transmission from the composite current collector to the coating layer can be improved, and the quick charging effect can be realized; in addition, the carbon fibers can directly permeate into the coating layer, so that the composite electrode plate has the functions of a beam and a framework between the composite current collector and the coating layer, and the mechanical strength of the composite electrode plate is improved.
Description
Technical Field
The invention relates to the technical field of battery electrode plates, in particular to a quick-charging type composite electrode plate, a preparation method thereof and a solid-state battery.
Background
The lithium ion battery has the advantages of higher voltage platform, high energy density, environmental friendliness, long service life and the like, so that the lithium ion battery is widely applied to the fields of mobile phones, computers, automobiles, energy storage and the like.
Because the solid-state battery does not contain electrolyte, the current collector and the active material of the solid-state battery have lower current transmission efficiency, the electron and ion transmission resistance of the active material in the pole piece is higher, and the quick charging performance can be improved only by increasing the conductivity and the stability of the battery pole piece. At present, the adhesive and the electric conductivity of a positive and negative electrode material and a current collector are enhanced mainly by coating adhesive conductive layers on the surfaces of a copper foil and an aluminum foil, and meanwhile, an adhesive and conductive carbon are added in the mixing process of the positive and negative electrode materials to enhance the direct adhesive property and the electronic conduction of the positive and negative active substances. Although the introduction of the adhesive can improve the adhesion between active substances and between collectors, the impedance of the pole piece can be increased, so that an electron transmission network in the pole piece is blocked, the heat generation of the lithium ion battery is increased in the charge and discharge process, and the thermal runaway risk of the lithium ion battery is increased. In addition, adhesive and pores exist among the conductive carbons, the non-conductive carbon particles are directly communicated with the current collector, and an electron transmission channel is not smooth, so that the improvement of the conductivity of the active material and the current collector is limited.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a quick-charging composite electrode plate, a preparation method thereof and a solid-state battery, and aims to solve the problem that the efficiency of current transmission from a composite current collector to an active material in the electrode plate of the conventional battery is low.
The technical scheme of the invention is as follows:
a preparation method of a quick-charging composite electrode slice comprises the following steps:
placing the foil in a vapor deposition furnace, continuously introducing airflow containing a carbon source under the condition of oxygen isolation, heating the vapor deposition furnace to carbonize the carbon source to grow carbon fibers on the surface of the foil in situ, and preparing a composite current collector;
mixing an active substance, a binder, an electrolyte and an organic solvent according to a predetermined ratio to obtain electrode slurry;
and coating the electrode slurry on the surface of the composite current collector, and baking and rolling to form a coating layer to obtain the quick-charging composite electrode slice.
The preparation method of the quick-filling composite electrode plate comprises the step of preparing a composite electrode plate, wherein the foil is one of a copper foil, an aluminum foil and a lithium foil.
The preparation method of the quick-filling composite electrode plate comprises the step of preparing a carbon source, wherein the carbon source is one or more of methane, ethane, propane, ethylene and acetylene.
The preparation method of the quick-filling composite electrode plate comprises the step of preparing a composite electrode plate, wherein the length of the carbon fiber is 500-1000 nm.
The preparation method of the quick-charging type composite electrode plate comprises the following steps of preparing an active material, wherein the active material is one or more of lithium iron phosphate, lithium manganese iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, lithium nickel manganese oxide, graphite, hard carbon, mesocarbon microbeads, silica and silicon carbide; and/or the adhesive is one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber, sodium alginate, polyoxyethylene, hexafluoropropylene and polyvinyl alcohol; and/or the electrolyte is Li3+xLa3Zr2O12，Li1+xAlxGe2–x(PO4)3，Li1+xAlxTi2–x(PO4)3，Li6PS5X，P2S5,Li4-xGe1-xPxS4，Li11- xM2-xP1+xS12And Li7GeP2S12One or more of the following components, wherein X is Cl, Br or I, M is Ge, Sn or Si, and X is not less than 0 and not more than 2.
The preparation method of the quick-filling composite electrode slice comprises the following steps of (1) preparing electrode slurry, wherein the mass ratio of an adhesive to an active material is 10: 90-0.01: 99.99.
the preparation method of the quick-filling composite electrode plate comprises the following steps of: 99.99.
according to the preparation method of the quick-charging composite electrode slice, the thickness of the coating layer is 10-300 um.
The invention discloses a quick-filling composite electrode plate, which is prepared by the preparation method of the quick-filling composite electrode plate.
A solid-state battery comprises the quick-charging composite electrode plate.
Has the advantages that: the invention provides a preparation method of a quick-charging type composite electrode plate, which comprises the steps of generating carbon fibers on a foil through gas-phase in-situ deposition to obtain a composite current collector, and further coating a mixed material of a positive electrode active substance, a negative electrode active substance and an electrolyte on the composite current collector to obtain the quick-charging type composite electrode plate. According to the invention, the carbon fiber grows on the foil in situ, and no adhesive is required to be additionally added between the coating layer and the composite current collector, so that the impedance can be reduced, the efficiency of current transmission from the composite current collector to the coating layer can be improved, and a good quick-charging effect can be realized; in addition, the carbon fibers can directly permeate into the coating layer, so that the composite current collector and the coating layer can serve as a beam and a framework, the mechanical strength of the composite electrode plate is improved, and the excellent rate of the machining process and the service life of a battery are improved.
Drawings
Fig. 1 is a flow chart of a preparation method of the quick-charging composite electrode sheet.
Fig. 2 is a schematic structural view of the composite current collector of the present invention.
Fig. 3 is an electron microscope image of the quick-charging composite electrode sheet of the invention.
Detailed Description
The invention provides a quick-charging composite electrode plate, a preparation method thereof and a solid-state battery, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Referring to fig. 1, fig. 1 is a flow chart of a method for manufacturing a quick-fill composite electrode sheet according to the present invention, and as shown in the figure, the method includes the following steps:
s10, placing the foil in a vapor deposition furnace, continuously introducing airflow containing a carbon source under the condition of oxygen isolation, heating the vapor deposition furnace to carbonize the carbon source to grow carbon fibers on the surface of the foil in situ, and preparing a composite current collector;
s20, mixing the active substance, the adhesive, the electrolyte and the organic solvent according to a preset proportion to obtain electrode slurry;
and S30, coating the electrode slurry on the surface of the composite current collector, and baking and rolling to form a coating layer to obtain the quick-filling composite electrode slice.
Specifically, the conventional method is to directly coat conductive carbon and adhesive on the surface of the foil to improve the adhesion and conductivity of the pole piece and the foil and improve the quick charging performance of the battery. However, the excessive introduction of the adhesive can increase the impedance of the pole piece, so that an electron transmission network in the pole piece is blocked, the heat generation in the charge and discharge process of the lithium ion battery is increased, and the thermal runaway risk of the lithium ion battery is increased. In addition, excessive introduction of the binder also causes an electron transport channel to be unsmooth, so that conductivity between the active material and the current collector is limited. Based on this, in the invention, the composite current collector shown in fig. 2 is obtained by generating carbon fibers through vapor in-situ deposition on a foil, wherein 1 is the foil and 2 is the carbon fibers, a mixed material of a positive active material, a negative active material and an electrolyte is further coated on the composite current collector to obtain the quick-charging composite electrode plate, and a scanning electron microscope image of the quick-charging composite electrode plate is shown in fig. 3. According to the invention, the carbon fiber grows on the foil in situ, and no adhesive is required to be additionally added between the coating layer and the composite current collector, so that the impedance can be reduced, the efficiency of current transmission from the composite current collector to the coating layer can be improved, and a good quick-charging effect can be realized; in addition, the carbon fibers can directly permeate into the coating layer, so that the composite current collector and the coating layer can serve as a beam and a framework, the mechanical strength of the composite electrode plate is improved, and the excellent rate of the machining process and the service life of a battery are improved.
In some embodiments, the foil is one of a copper foil, an aluminum foil, and a lithium foil, but is not limited thereto; the foil may also be a composite foil comprising copper foil, aluminum foil or lithium foil.
In some embodiments, the foil has a thickness of 2-20um, but is not limited thereto.
In some embodiments, the carbon source is one or more of methane, ethane, propane, ethylene, and acetylene, but is not limited thereto.
In some embodiments, the carbon fibers are grown on one or both sides of a foil, and when the carbon fibers are grown on one side of the foil, the slurry is coated on the side of the foil on which the carbon fibers are grown; and when the carbon fibers grow on two sides of the foil, the slurry is coated on any side of the foil.
In some embodiments, the carbon fibers have a length of 500-1000nm, but are not limited thereto.
In some embodiments, the active material is one or more of lithium iron phosphate, lithium manganese iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, lithium nickel manganese oxide, graphite, hard carbon, mesocarbon microbeads, silica, silicon carbon, but is not limited thereto. In this example, the active material comprises 50 to 99% of the total weight of the slurry.
In some embodiments, the binder is one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber, sodium alginate, polyethylene oxide, hexafluoropropylene, and polyvinyl alcohol, but is not limited thereto.
In some embodiments, the electrolyte is Li3+xLa3Zr2O12，Li1+xAlxGe2–x(PO4)3，Li1+xAlxTi2–x(PO4)3，Li6PS5X，P2S5,Li4-xGe1-xPxS4，Li11-xM2-xP1+xS12And Li7GeP2S12One or more of the following components, wherein X is Cl, Br or I, M is Ge, Sn or Si, and X is not less than 0 and not more than 2.
In some embodiments, the mass ratio of the binder to the active material in the electrode slurry is 10:90 to 0.01: 99.99 of the total weight of the steel; the mass ratio of the electrolyte to the active material is 10: 90-0.01: 99.99.
in some embodiments, the coating layer has a thickness of 10-300um, but is not limited thereto.
In some embodiments, the invention also provides a quick-filling composite electrode plate, which is prepared by the preparation method of the quick-filling composite electrode plate.
In some embodiments, the invention also provides a solid-state battery, which comprises the quick-charging composite electrode plate.
The invention is further illustrated by the following specific examples:
example 1
The micron carbon fiber positive composite current collector of the embodiment: placing an aluminum foil with the thickness of 10 microns in a chemical vapor deposition furnace, continuously introducing methane gas into the furnace, keeping the flow of the gas at 200ml/min, raising the temperature of the furnace to 800 ℃, keeping the temperature for 4 hours, and cooling to obtain a positive composite current collector with micron carbon fibers growing on the surface of the aluminum foil in situ;
the preparation method of the positive plate in the embodiment comprises the following steps: preparing nickel cobalt lithium manganate: lithium lanthanum zirconium oxide: conductive carbon black: PVDF (polyvinylidene fluoride) is mixed according to the mass ratio of 85:10:3:2, NMP (N-methyl pyrrolidone) is used as a solvent, mechanical stirring is carried out for 5 hours at 5100 r/min, then slurry is prepared, the slurry is coated on the composite current collector prepared in the previous step, the mixed slurry is made to fully permeate into the middle of conductive carbon fibers of the current collector, the coating thickness is 150 micrometers, and vacuum drying is carried out at 100 ℃ to obtain a positive pole piece; and rolling the dried pole piece to 120um in thickness, and slitting to obtain the composite positive pole piece.
Solid electrolyte membrane: mixing lithium lanthanum zirconium oxygen powder and PTFE according to the mass ratio of 95:5, and then heating and pressing at 150 ℃ to form an electrolyte membrane with the thickness of 15 um.
The application of the quick-charging composite electrode plate in the solid-state battery is as follows: and (3) stacking and assembling the obtained composite positive electrode, lithium lanthanum zirconium oxide and lithium foil to obtain a solid lithium ion battery, and performing 0.2C charge-discharge cycle test on the obtained solid lithium battery under the conditions that the charge-discharge cutoff voltage is 2.75-4.3V and the charge-discharge cutoff voltage is 0.2C and 0.5C, wherein the results are shown in Table 1.
Example 2
The micron carbon fiber positive composite current collector of the embodiment: placing an aluminum foil with the thickness of 10 microns in a chemical vapor deposition furnace, continuously introducing acetylene gas into the furnace, keeping the flow of the gas at 200ml/min, increasing the temperature of the furnace to 900 ℃, keeping the temperature for 4 hours, and cooling to obtain a positive composite current collector with micron carbon fibers growing on the surface of the aluminum foil in situ;
the preparation method of the positive plate in the embodiment comprises the following steps: preparing nickel cobalt lithium manganate: lithium lanthanum zirconium oxide: conductive carbon black: PVDF is mixed according to the mass ratio of 85:10:3:2, mechanical stirring is carried out for 5 hours at 5100 r/min by taking NMP as a solvent, slurry is prepared, the slurry is coated on the positive composite current collector prepared in the previous step, the mixed slurry is fully permeated into the middle of conductive carbon fibers of the current collector, the coating thickness is 150 micrometers, and a positive pole piece is obtained through vacuum drying at 100 ℃; and rolling the dried pole piece to 120um in thickness, and slitting to obtain the composite positive pole piece.
The micron carbon fiber composite negative current collector of the embodiment: placing a copper foil with the thickness of 10 microns in a chemical vapor deposition furnace, continuously introducing methane gas into the furnace, keeping the flow of the gas at 200ml/min, raising the temperature of the furnace to 800 ℃, keeping the temperature for 4 hours, and cooling to obtain a negative electrode composite current collector with micron carbon fibers growing on the surface of the copper foil in situ;
the preparation method of the negative plate in the embodiment comprises the following steps: mixing graphite: lithium lanthanum zirconium oxide: conductive carbon black: mixing CMC (carbon methyl cellulose) in a mass ratio of 90:5:3:2, mechanically stirring the mixture for 5 hours by taking NMP as a solvent at 5100 rpm, preparing slurry, coating the slurry on the negative electrode composite current collector prepared in the previous step to enable the mixed slurry to fully permeate into the middle of conductive carbon fibers of the current collector, wherein the coating thickness is 160 mu m, and performing vacuum drying at 100 ℃ to obtain a positive electrode piece; and rolling the dried pole piece to a rolling thickness of 130um, and slitting to obtain the composite positive pole piece.
Solid electrolyte membrane: mixing lithium lanthanum zirconium oxygen powder and PTFE according to the mass ratio of 95:5, and then heating and pressing at 150 ℃ to form an electrolyte membrane with the thickness of 15 um.
The application of the quick-charging composite electrode plate in the solid-state battery is as follows: and (3) laminating and assembling the obtained composite positive electrode, lithium lanthanum zirconium oxide and lithium foil to obtain a solid lithium ion battery, and performing 0.2C charge-discharge cycle test on the obtained solid lithium battery under the conditions that the charge-discharge cutoff voltage is 2.75-4.3V and the charge-discharge cutoff voltage is 0.2C and 0.5C for charge-discharge cycle test, wherein the results are shown in Table 1.
Example 3
The micron carbon fiber positive composite current collector of the embodiment: placing a copper foil with the thickness of 10 microns in a chemical vapor deposition furnace, continuously introducing ethylene gas into the furnace, keeping the flow of the gas at 200ml/min, raising the temperature of the furnace to 800 ℃, keeping the temperature for 4 hours, and cooling to obtain a positive composite current collector with micron carbon fibers growing on the surface of the copper foil in situ;
the preparation method of the positive plate in the embodiment comprises the following steps: preparing nickel cobalt lithium manganate: li6PS5Cl: conductive carbon black: PVDF is mixed according to the mass ratio of 85:10:3:2, NMP is used as a solvent, mechanical stirring is carried out for 5 hours at 5100 r/min, then slurry is prepared, the slurry is coated on the composite current collector prepared in the previous step, the mixed slurry is made to fully permeate into the conductive carbon fibers of the current collector, the coating thickness is 150 microns, and vacuum drying is carried out at 100 ℃ to obtain a positive pole piece; and rolling the dried pole piece to 120um in thickness, and slitting to obtain the composite positive pole piece.
The micron carbon fiber composite negative current collector of the embodiment: placing a copper foil with the thickness of 10 microns in a chemical vapor deposition furnace, continuously introducing acetylene gas into the furnace, keeping the flow of the gas at 200ml/min, raising the temperature of the furnace to 800 ℃, keeping the temperature for 4 hours, and cooling to obtain a negative electrode composite current collector with micron carbon fibers growing on the surface of the copper foil in situ;
the preparation method of the negative plate in the embodiment comprises the following steps: mixing silicon and carbon: li6PS5Cl: conductive carbon black: mixing CMC 85:10:3:2 in a mass ratio, mechanically stirring the mixture for 5 hours at 5100 r/min by taking NMP as a solventPreparing slurry, coating the slurry on the negative composite current collector prepared in the previous step to enable the mixed slurry to fully permeate into the conductive carbon fibers of the current collector, wherein the coating thickness is 150 microns, and performing vacuum drying at 100 ℃ to obtain a positive pole piece; and rolling the dried pole piece to 120um in thickness, and slitting to obtain the composite positive pole piece.
Solid electrolyte membrane: mixing Li6PS5Cl powder and PTFE were mixed in a mass ratio of 95:5, and then heated at 150 ℃ to roll-press into an electrolyte membrane 15um thick.
The application of the quick-charging composite electrode plate in the solid-state battery is as follows: the obtained composite positive electrode, an electrolyte membrane and a lithium foil are laminated and assembled to obtain a solid lithium ion battery, the obtained solid lithium battery is charged and discharged by 0.2C and 0.5C, and the charge and discharge cycle test of 0.2C is carried out under the condition that the charge and discharge cut-off voltage is 2.75-4.3V, and the results are shown in Table 1.
Example 4
The micron carbon fiber composite current collector of the embodiment: placing a copper foil with the thickness of 10 microns in a chemical vapor deposition furnace, continuously introducing propane gas into the furnace, wherein the flow rate of the gas is 200ml/min, raising the temperature of the furnace to 800 ℃, keeping the temperature for 4 hours, and cooling to obtain a composite current collector with micron carbon fibers growing on the surface of the foil in situ;
the preparation method of the positive plate in the embodiment comprises the following steps: and (3) preparing nickel cobalt lithium manganate: li7GeP2S12: conductive carbon black: mixing the adhesives according to the mass ratio of 85:10:3:2, mechanically stirring the mixture for 5 hours at 5100 r/min by taking NMP as a solvent, preparing slurry, coating the slurry on the composite current collector prepared in the previous step to enable the mixed slurry to fully permeate into the conductive carbon fibers of the current collector, wherein the coating thickness is 150 microns, and performing vacuum drying at 100 ℃ to obtain a positive pole piece; and rolling the dried pole piece to 120um in thickness, and slitting to obtain the composite positive pole piece.
The micron carbon fiber composite negative current collector of the embodiment: placing a copper foil with the thickness of 10 microns in a chemical vapor deposition furnace, continuously introducing ethane gas into the furnace, keeping the flow of the gas at 200ml/min, raising the temperature of the furnace to 800 ℃, keeping the temperature for 4 hours, and cooling to obtain a negative electrode composite current collector with micron carbon fibers growing on the surface of the copper foil in situ;
the preparation method of the negative plate in the embodiment comprises the following steps: mixing silicon oxide: li7GeP2S12: conductive carbon black: mixing CMC (85: 10:3: 2) in a mass ratio, mechanically stirring the mixture for 5 hours at 5100 r/min by taking NMP as a solvent, preparing slurry, coating the slurry on the negative composite current collector prepared in the previous step to enable the mixed slurry to fully permeate into the conductive carbon fibers on the copper foil, wherein the coating thickness is 150 mu m, and performing vacuum drying at 100 ℃ to obtain a negative pole piece; and rolling the dried pole piece to 120um in thickness, and slitting to obtain the composite negative pole piece.
Solid electrolyte membrane: mixing Li7GeP2S12The powder was mixed with PTFE at a mass ratio of 95:5 and then hot-rolled at 150 ℃ into a 15um thick electrolyte membrane.
The application of the quick-charging composite electrode plate in the solid-state battery is as follows: and (3) stacking and assembling the obtained composite anode, the electrolyte membrane and the composite cathode sheet to obtain the solid lithium ion battery, and performing 0.2C charge-discharge cycle test on the obtained solid lithium battery under the conditions that the charge-discharge cutoff voltage is 2.75-4.3V and the charge-discharge cutoff voltage is 0.2C and 0.5C for charge-discharge cycle test, wherein the results are shown in Table 1.
Comparative example 1
Carbon coating of the anode aluminum foil: mixing and dissolving conductive carbon black and PVDF in an NMP solvent according to a mass ratio of 95:5 to prepare slurry, coating the slurry on an aluminum foil, and drying at 100 ℃ to obtain a carbon-coated aluminum foil;
the preparation method of the positive plate of the comparative example comprises the following steps: preparing nickel cobalt lithium manganate: lithium aluminum titanium phosphate: conductive carbon black: mixing the adhesives in a mass ratio of 85:10:3:2, mechanically stirring the mixture for 5 hours at 5100 r/min by taking NMP as a solvent, preparing slurry, coating the slurry on an aluminum foil to a thickness of 150 microns, and performing vacuum drying at 100 ℃; and (4) rolling the dried pole piece to a rolling thickness of 120um, and cutting the piece to obtain the positive pole piece.
Carbon coating of negative copper foil: mixing and dissolving conductive carbon black and PVDF (polyvinylidene fluoride) in an NMP (N-methyl pyrrolidone) solvent according to a mass ratio of 95:5 to prepare slurry, and coating the slurry on a copper foil and drying at 100 ℃ to obtain a carbon-coated aluminum foil;
the preparation method of the comparative example negative plate comprises the following steps: mixing silicon oxide: lithium aluminum titanium phosphate: conductive carbon black: mixing CMC (85: 10:3: 2) in a mass ratio, mechanically stirring the mixture for 5 hours at 5100 r/min by taking NMP as a solvent, preparing slurry, coating the slurry on a copper foil to form a coating thickness of 150 microns, performing vacuum drying at 100 ℃, rolling the dried pole piece to form a rolling thickness of 120 microns, and slitting to obtain the positive pole piece.
Solid electrolyte membrane: mixing the lithium aluminum titanium phosphate powder and PTFE according to the mass ratio of 95:5, and then heating and pressing the mixture into an electrolyte membrane with the thickness of 15um at 150 ℃.
The application of the quick-charging composite electrode plate in the solid-state battery is as follows: and (3) stacking and assembling the obtained positive plate, the electrolyte membrane and the negative plate to obtain the solid lithium ion battery, and performing 0.2C charge-discharge cycle test on the obtained solid lithium battery under the conditions of 0.2C and 0.5C charge-discharge and charge-discharge cut-off voltage of 2.75-4.3V, wherein the results are shown in Table 1.
TABLE 1 Battery Charge-discharge cycling test results
As can be seen from the data in table 1, the 0.5C capacity retention rates of examples 1 to 4 are significantly improved compared to comparative example 1, which indicates that the current transmission efficiency inside the battery cell is relatively high, and thus the large-rate capacity retention rate is high; in addition, the capacity retention rate of the embodiments 1 to 4 after 300 cycles is between 90 and 93 percent and is much higher than 61 percent of the comparative example 1, which shows that the stability of the structures and the performances of the pole piece and the battery cell is obviously improved in the cycle process, and the micron carbon fiber framework plays a good role in supporting and consolidating the pole piece.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a quick-filling composite electrode plate is characterized by comprising the following steps:
placing the foil in a vapor deposition furnace, continuously introducing airflow containing a carbon source under the condition of oxygen isolation, heating the vapor deposition furnace to carbonize the carbon source to grow carbon fibers on the surface of the foil in situ, and preparing a composite current collector;
mixing an active substance, a binder, an electrolyte and an organic solvent according to a predetermined ratio to obtain electrode slurry;
and coating the electrode slurry on the surface of the composite current collector, and baking and rolling to form a coating layer to obtain the quick-charging composite electrode slice.
2. The method for preparing the quick-filling composite electrode sheet according to claim 1, wherein the foil is one of copper foil, aluminum foil and lithium foil.
3. The preparation method of the quick-charging composite electrode sheet according to claim 1, wherein the carbon source is one or more of methane, ethane, propane, ethylene and acetylene.
4. The method for preparing the quick-filling composite electrode sheet as claimed in claim 1, wherein the length of the carbon fiber is 500-1000 nm.
5. The method for preparing the fast-charging composite electrode sheet according to claim 1, wherein the active material is one or more of lithium iron phosphate, lithium manganese iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, lithium nickel manganese oxide, graphite, hard carbon, mesocarbon microbeads, silica, and silicon carbon; and/or the adhesive is one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber, sodium alginate, polyoxyethylene, hexafluoropropylene and polyvinyl alcohol; and/or the electrolyte is Li3+xLa3Zr2O12，Li1+xAlxGe2–x(PO4)3，Li1+xAlxTi2–x(PO4)3，Li6PS5X，P2S5,Li4-xGe1-xPxS4，Li11-xM2-xP1+xS12And Li7GeP2S12One or more of the following components, wherein X is Cl, Br or I, M is Ge, Sn or Si, and X is not less than 0 and not more than 2.
6. The preparation method of the quick-filling composite electrode sheet according to claim 1, wherein the mass ratio of the binder to the active material in the electrode slurry is 10: 90-0.01: 99.99.
7. the preparation method of the quick-filling composite electrode sheet according to claim 1, wherein the mass ratio of the electrolyte to the active material in the electrode slurry is 10: 90-0.01: 99.99.
8. the method for preparing the quick-filling composite electrode sheet according to claim 1, wherein the thickness of the coating layer is 10-300 um.
9. A quick-filling composite electrode sheet, characterized by being prepared by the method for preparing the quick-filling composite electrode sheet according to any one of claims 1 to 8.
10. A solid-state battery comprising the quick-charge type composite electrode tab according to claim 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115810760A (en) * | 2022-11-30 | 2023-03-17 | 宁德时代新能源科技股份有限公司 | Current collector and preparation method thereof, electrode plate, secondary battery and power utilization device |
| CN116417567A (en) * | 2023-06-09 | 2023-07-11 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, energy storage device and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102832392A (en) * | 2012-06-27 | 2012-12-19 | 长沙业翔能源科技有限公司 | Current collector carbon coated aluminum foil and its preparation method |
| CN109004225A (en) * | 2018-08-01 | 2018-12-14 | 太仓斯迪克新材料科技有限公司 | A kind of anode slice of lithium ion battery and its preparation |
| CN112751030A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Negative pole piece and lithium ion battery thereof |
| CN112751075A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Lithium ion battery and preparation method thereof |
-
2022
- 2022-03-29 CN CN202210317031.4A patent/CN114744155A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102832392A (en) * | 2012-06-27 | 2012-12-19 | 长沙业翔能源科技有限公司 | Current collector carbon coated aluminum foil and its preparation method |
| CN109004225A (en) * | 2018-08-01 | 2018-12-14 | 太仓斯迪克新材料科技有限公司 | A kind of anode slice of lithium ion battery and its preparation |
| CN112751030A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Negative pole piece and lithium ion battery thereof |
| CN112751075A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Lithium ion battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115810760A (en) * | 2022-11-30 | 2023-03-17 | 宁德时代新能源科技股份有限公司 | Current collector and preparation method thereof, electrode plate, secondary battery and power utilization device |
| CN116417567A (en) * | 2023-06-09 | 2023-07-11 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, energy storage device and preparation method |
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