CN104037423B - Preparation method of porous nickel current collector of lithium ion battery - Google Patents
Preparation method of porous nickel current collector of lithium ion battery Download PDFInfo
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- CN104037423B CN104037423B CN201410274234.5A CN201410274234A CN104037423B CN 104037423 B CN104037423 B CN 104037423B CN 201410274234 A CN201410274234 A CN 201410274234A CN 104037423 B CN104037423 B CN 104037423B
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- lithium ion
- ion battery
- lithium
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- current collector
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011812 mixed powder Substances 0.000 claims abstract description 13
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical group CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 229940116411 terpineol Drugs 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 4
- 239000007767 bonding agent Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229960004642 ferric ammonium citrate Drugs 0.000 claims description 3
- 229960002413 ferric citrate Drugs 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000004313 iron ammonium citrate Substances 0.000 claims description 3
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001803 electron scattering Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A preparation method of a porous nickel current collector of a lithium ion battery relates to the field of lithium ion battery materials. Taking nickel oxide and graphite as starting materials, and granulating to obtain mixed powder; pressing into a green body, and calcining to obtain a green body; reducing the blank to obtain a porous nickel current collector with a lithium ion battery; and uniformly coating the mixed and ground transition metal oxide negative electrode material with the nano structure on the surface of the porous nickel current collector of the lithium ion battery, and sintering to obtain the lithium ion battery electrode. Uniformly mixing a lithium source, an iron source, a phosphate solution and an organic complexing agent, and coating the mixture on the surface of a porous nickel current collector of the lithium ion battery; aging and calcining to obtain the lithium iron phosphate membrane electrode. The porous nickel current collector of the lithium ion battery has good communication characteristic, can better transfer electrons, has a higher three-phase interface, and can better enable the electrolyte and the cathode to mutually infiltrate. The lithium iron phosphate thin film electrode has a conductive three-phase interface, so that the electrochemical dynamic characteristics of the material are improved conveniently.
Description
Technical field
The present invention relates to field of lithium ion battery material, the preparation method being specifically related to a kind of lithium ion battery nickel porous collector.
Background technology
More and more wider along with lithium ion battery applications field, lithium ion battery develops towards the direction of high-energy-density, high power density and high security.This just requires that lithium storage materials has the reversible capacity of higher running voltage or higher.Traditional lithium ion battery be adopt two kinds can embed/compound of deintercalate lithium ions is respectively as the positive and negative pole material of lithium ion battery.As: the battery of the graphite/cobalt acid lithium system of nineteen ninety SonyCorp. development, and successfully by its commercialization.Subsequently, along with the further in-depth of electric automobile concept, graphite/LiFePO4 system battery also worldwide grows up faster.
While in accordance with the kind of active material, it is more and more careful to distinguish, but the change of significance did not but occur as the both positive and negative polarity collector in lithium ion battery in the 20 of the past years.From the angle of electrochemical reaction, material is in charge and discharge process, it is necessary to material can fully ensure that the quick deintercalation of lithium ion with electrolyte；It addition, also to ensure that electronics can quickly dissipate to collector.In consideration of it, in recent years, some research groups adopt the collector with 3D structure for the application in lithium ion battery, and representative 3D structure collector is exactly nickel foam.Based on nickel foam as collector, adopt the method for electrostatic spray to prepare the transition metal oxide document as the negative material of lithium ion battery and directly as the chemical property of collector investigation LiFePO 4 material and all have been reported that.
Thin-film material can be avoided closing the operations such as slurry, coating directly as anode material for lithium-ion batteries, what is more important, material is in charge and discharge process, due to combining closely of active material and collector, make electron scattering relatively rapider, so that material has of a relatively high electrochemical kinetics characteristic.Such as: at the copper oxide negative material of the single nanostructured of copper sheet superficial growth or micro-nano multi-level structure；The method deposition lithium iron phosphate positive material of PLD and method deposition Si nano wire, all being obviously improved in the parameters such as discharge capacity, cycle performance and high rate performance of CVD is adopted at stainless steel surfaces.
But above-mentioned also exists high-temperature burning process in the process prepare electrode material, to promote the structural stability of material, so use the 3D structure collector if nickel foam is representative will certainly cause due to the problem of the not enough collector efflorescence caused of the mechanical strength of collector.In consideration of it, the present invention mainly improves the collector character of material, and the change of primary product proportioning can be passed through, the porosity of regulation and control collector, and finally realize one there is 3D structure, the preparation of three new current collector being connected.
Summary of the invention
For the technical problem existed in prior art, the preparation method that an object of the present invention is to provide a kind of lithium ion battery nickel porous collector, the preparation method that it is a further object of the present invention to provide a kind of lithium ion cell electrode, the preparation method that the three of the purpose of the present invention are to provide a kind of lithium iron phosphate membrane electrode.
One of to achieve these goals, the technical solution adopted in the present invention is:
The preparation method of a kind of lithium ion battery nickel porous collector, comprises the steps:
1., using mass ratio be 3～9:1～7 nickel oxide and graphite as parent material, add granulating solvent and carry out pelletize, it is thus achieved that mixed powder, granulating solvent is the mixture of one or more in PVA solution, PMMA solution, PVP solution；
2., by mixed powder being pressed into raw idiosome, raw idiosome calcines 3～20h at 1000～1600 DEG C, it is thus achieved that idiosome；
3., by idiosome in the carrier gas containing reducing atmosphere at 400～600 DEG C reduce 3～30h.
Preferably, described step 1. in the concentration of granulating solvent be 3～10wt%.
Preferably, described step 2. in the pressure of mixed powder compacting be 10～16Mpa, raw idiosome is disk shape, and diameter is 13mm, and thickness is 1mm.
Preferably, described step 3. in reducing atmosphere be the mixing gas of one or more in hydrogen, methane, ethane, ethanol, toluene, carrier gas is high pure nitrogen or high-purity argon gas.
In order to realize above-mentioned another object, the technical solution adopted in the present invention is:
The preparation method of a kind of lithium ion cell electrode, comprises the steps:
1), lithium ion battery nickel porous collector is obtained according to the preparation method described in claim 1；
2), after the transition metal oxide negative material of nanostructured and bonding agent, pore creating material mix grinding, it is evenly coated in lithium ion battery nickel porous collection liquid surface, under inert atmosphere protection, at 300～800 DEG C, sinters 3～20h.
Preferably, the transition metal oxide negative material of described nanostructured is the mixture of one or more in nickel oxide, manganese oxide, ferrous oxide, iron sesquioxide, cobalt oxide, Cobalto-cobaltic oxide.
Preferably, described bonding agent is terpineol, and pore creating material is ethyl cellulose and/or carboxymethyl cellulose.
Three to achieve these goals, the technical solution adopted in the present invention is:
The preparation method of a kind of lithium iron phosphate membrane electrode, comprises the steps:
1), lithium ion battery nickel porous collector is obtained according to the preparation method described in claim 1；
2), by after lithium source, source of iron, phosphate radical solution and organic complexing agent Homogeneous phase mixing, it is coated in lithium ion battery nickel porous collection liquid surface；N (Fe): n (PO4 3-): n (Li): n (organic complexing agent)=0.97～1:1:1～1.05:0.005～0.1；
3), ageing, then by material in 500～800 DEG C calcine 3～30h.
Preferably, described lithium source is the mixture of one or more in lithium acetate, Lithium hydrate, lithium oxalate, lithium carbonate, source of iron is the mixture of one or more in ferric nitrate, ferric citrate, ferric ammonium citrate, Ferrous acetate, phosphate radical solution is the mixture of one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, and organic complexing agent is the mixture of one or more in glycine, citric acid, carbamide.
Preferably, described coating is to adopt silk screen print method, azeotropic method or vacuum filtration method to realize.
The preparation method of the lithium ion battery nickel porous collector of the present invention, its beneficial effect shows:
1), improve simple using nickel foam etc. as the not enough problem of the mechanical strength existing for affluxion body in lithium ion batteries.
2), the present invention can utilize the regulation and control of different ratio in initial product, prepare different pore size distribution current collector material, in order to realize cutting out for electrode material chemical property.
3), lithium ion battery nickel porous collector not only has good UNICOM's characteristic, it is possible to transmits electronics preferably, and has higher three phase boundary, it is possible to make electrolyte and negative pole mutually infiltrate better, thus promoting the chemical property of material.
4), adopt the lithium iron phosphate membrane electrode that this collector prepares, there is the three phase boundary of conducting, it is simple to promote the electrochemical kinetics characteristic of material.
Detailed description of the invention
Below with reference to embodiment, the present invention is described in detail.
Embodiment 1
1., using mass ratio be 3:7 nickel oxide and graphite as parent material, add the PVP solution that concentration is 3wt% and carry out pelletize, it is thus achieved that mixed powder.
2., by powder compressing machine mixed powder being pressed into diameter to be 13mm, thickness be the raw idiosome of disk shape of 1mm, raw idiosome calcines 10h at 1350 DEG C, it is thus achieved that idiosome.
3., by idiosome in the high pure nitrogen containing hydrogen at 400 DEG C reduce 30h, obtain lithium ion battery nickel porous collector, it not only has good UNICOM's characteristic can transmit electronics preferably, and there is higher three phase boundary, it is possible to make electrolyte and negative pole mutually infiltrate better.
Embodiment 2
1., using mass ratio be 9:1 nickel oxide and graphite as parent material, add the PMMA solution that concentration is 10wt% and carry out pelletize, it is thus achieved that mixed powder.
2., by powder compressing machine mixed powder being pressed into diameter to be 13mm, thickness be the raw idiosome of disk shape of 1mm, raw idiosome calcines 3h at 1600 DEG C, it is thus achieved that idiosome.
3., by idiosome in the high-purity argon gas containing toluene at 600 DEG C reduce 3h, it is thus achieved that lithium ion battery nickel porous collector.
Embodiment 3
1., using mass ratio be 5:5 nickel oxide and graphite as parent material, add the PVA solution that concentration is 8wt% and carry out pelletize, it is thus achieved that mixed powder.
2., by powder compressing machine mixed powder being pressed into diameter to be 13mm, thickness be the raw idiosome of disk shape of 1mm, raw idiosome calcines 20h at 1000 DEG C, it is thus achieved that idiosome.
3., by idiosome in the high pure nitrogen containing methane and ethane at 500 DEG C reductase 12 0h, it is thus achieved that lithium ion battery nickel porous collector.
Embodiment 4
It is evenly coated in lithium ion battery nickel porous collection liquid surface prepared by embodiment 1 after Cobalto-cobaltic oxide and terpineol, carboxymethyl cellulose mix grinding; at 800 DEG C, 3h is sintered under inert atmosphere protection; obtain lithium ion cell electrode, form good degree of crystallinity thus reaching LFP and with collector, there is the purpose of good combination intensity.
Embodiment 5
After nickel oxide and terpineol, ethyl cellulose mix grinding, it is evenly coated in lithium ion battery nickel porous collection liquid surface prepared by embodiment 2, under inert atmosphere protection, at 300 DEG C, sinters 20h, it is thus achieved that lithium ion cell electrode.
Embodiment 6
After ferrous oxide and terpineol, ethyl cellulose and carboxymethyl cellulose mix grinding, it is evenly coated in lithium ion battery nickel porous collection liquid surface prepared by embodiment 3, under inert atmosphere protection, at 500 DEG C, sinters 10h, it is thus achieved that lithium ion cell electrode.
Embodiment 7
After lithium carbonate, ferric citrate, ammonium phosphate and carbamide Homogeneous phase mixing, vacuum filtration method is adopted to be coated in the lithium ion battery nickel porous collection liquid surface of embodiment 1 preparation, n (Fe): n (PO4 3-): n (Li): n (carbamide)=1:1:1.05:0.025.Ageing, then calcines 20h by material in 650 DEG C, it is thus achieved that lithium iron phosphate membrane electrode.
Embodiment 8
After lithium acetate, ferric ammonium citrate, phosphoric acid and glycine Homogeneous phase mixing, azeotropic method is adopted to be coated in the lithium ion battery nickel porous collection liquid surface of embodiment 2 preparation, n (Fe): n (PO4 3-): n (Li): n (glycine)=0.97:1:1:0.1.Ageing, then calcining 30h by material in 500 DEG C, it is thus achieved that lithium iron phosphate membrane electrode, thus reaching LFP to form good degree of crystallinity, and having the purpose of good combination intensity with collector.
Embodiment 9
After Lithium hydrate, Ferrous acetate, ammonium dihydrogen phosphate and citric acid Homogeneous phase mixing, silk screen print method is adopted to be coated in the lithium ion battery nickel porous collection liquid surface of embodiment 3 preparation, n (Fe): n (PO4 3-): n (Li): n (citric acid)=0.99:1:1.03:0.005.Ageing, then calcines 3h by material in 800 DEG C, it is thus achieved that lithium iron phosphate membrane electrode.
Above content is only citing made for the present invention and explanation; described specific embodiment is made various amendment or supplements or adopt similar mode to substitute by affiliated those skilled in the art; conceiving or surmounting the scope that present claims book is defined without departing from invention, all should belong to protection scope of the present invention.
Claims (10)
1. a preparation method for lithium ion battery nickel porous collector, is characterized in that comprising the steps:
1., using mass ratio be 3～9:1～7 nickel oxide and graphite as parent material, add granulating solvent and carry out pelletize, it is thus achieved that mixed powder, granulating solvent is the mixture of one or more in PVA solution, PMMA solution, PVP solution；
2., by mixed powder being pressed into raw idiosome, raw idiosome calcines 3～20h at 1000～1600 DEG C, it is thus achieved that idiosome；
3., by idiosome in the carrier gas containing reducing atmosphere at 400～600 DEG C reduce 3～30h.
2. the preparation method of lithium ion battery nickel porous collector according to claim 1, it is characterised in that: described step 1. in the concentration of granulating solvent be 3～10wt%.
3. the preparation method of lithium ion battery nickel porous collector according to claim 1, it is characterised in that: described step 2. in the pressure of mixed powder compacting be 10～16Mpa, raw idiosome is disk shape, and diameter is 13mm, and thickness is 1mm.
4. the preparation method of lithium ion battery nickel porous collector according to claim 1, it is characterized in that: described step 3. in reducing atmosphere be the mixing gas of one or more in hydrogen, methane, ethane, ethanol, toluene, carrier gas is high pure nitrogen or high-purity argon gas.
5. a preparation method for lithium ion cell electrode, is characterized in that comprising the steps:
1), lithium ion battery nickel porous collector is obtained according to the preparation method described in claim 1；
2), after the transition metal oxide negative material of nanostructured and bonding agent, pore creating material mix grinding, it is evenly coated in lithium ion battery nickel porous collection liquid surface, under inert atmosphere protection, at 300～800 DEG C, sinters 3～20h.
6. the preparation method of lithium ion cell electrode according to claim 5, it is characterised in that: the transition metal oxide negative material of described nanostructured is the mixture of one or more in nickel oxide, manganese oxide, ferrous oxide, iron sesquioxide, cobalt oxide, Cobalto-cobaltic oxide.
7. the preparation method of lithium ion cell electrode according to claim 5, it is characterised in that: described bonding agent is terpineol, and pore creating material is ethyl cellulose and/or carboxymethyl cellulose.
8. a preparation method for lithium iron phosphate membrane electrode, is characterized in that comprising the steps:
1), lithium ion battery nickel porous collector is obtained according to the preparation method described in claim 1；
2), by after lithium source, source of iron, phosphate radical solution and organic complexing agent Homogeneous phase mixing, it is coated in lithium ion battery nickel porous collection liquid surface；N (Fe): n (PO4 3-): n (Li): n (organic complexing agent)=0.97～1:1:1～1.05:0.005～0.1；
3), ageing, then by material in 500～800 DEG C calcine 3～30h.
9. the preparation method of lithium iron phosphate membrane electrode according to claim 8, it is characterized in that: described lithium source is the mixture of one or more in lithium acetate, Lithium hydrate, lithium oxalate, lithium carbonate, source of iron is the mixture of one or more in ferric nitrate, ferric citrate, ferric ammonium citrate, Ferrous acetate, phosphate radical solution is the mixture of one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, and organic complexing agent is the mixture of one or more in glycine, citric acid, carbamide.
10. the preparation method of lithium iron phosphate membrane electrode according to claim 8, it is characterised in that: described coating is to adopt silk screen print method or vacuum filtration method to realize.
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| CN106601986A (en) * | 2016-12-29 | 2017-04-26 | 中国电子科技集团公司第十八研究所 | Preparation method of AGO electrode |
| CN108075119B (en) * | 2017-12-11 | 2020-04-24 | 合肥国轩电池材料有限公司 | Si/Li lithium ion battery4Ti5O12Preparation method of/C composite material membrane electrode |
| CN109647418A (en) * | 2018-12-19 | 2019-04-19 | 陕西科技大学 | A kind of preparation method of foamed nickel supported samarium doping titania photocatalyst |
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| US5197993A (en) * | 1991-07-11 | 1993-03-30 | The United States Of America As Represented By The Secretary Of The Navy | Lightweight battery electrode and method of making it |
| CN103370757A (en) * | 2011-02-18 | 2013-10-23 | 住友电气工业株式会社 | Three-dimensional porous aluminum mesh for use in collector, and collector, electrode, nonaqueous-electrolyte battery, capacitor, and lithium-ion capacitor using said porous aluminum |
| CN103839694A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/metal current collector preparing method |
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| JPS5626367A (en) * | 1979-08-09 | 1981-03-13 | Yuasa Battery Co Ltd | Current collector for alkaline cell |
| JP2001110425A (en) * | 1999-10-06 | 2001-04-20 | Toyo Kohan Co Ltd | Current collector body for secondary battery, secondary battery using current collector body, and manufacturing method for the current collector body and the secondary battery |
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| US5197993A (en) * | 1991-07-11 | 1993-03-30 | The United States Of America As Represented By The Secretary Of The Navy | Lightweight battery electrode and method of making it |
| CN103370757A (en) * | 2011-02-18 | 2013-10-23 | 住友电气工业株式会社 | Three-dimensional porous aluminum mesh for use in collector, and collector, electrode, nonaqueous-electrolyte battery, capacitor, and lithium-ion capacitor using said porous aluminum |
| CN103839694A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/metal current collector preparing method |
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