CN116281954A - Preparation method of conductive agent for lithium battery, conductive agent and lithium ion battery - Google Patents
Preparation method of conductive agent for lithium battery, conductive agent and lithium ion battery Download PDFInfo
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- CN116281954A CN116281954A CN202310246724.3A CN202310246724A CN116281954A CN 116281954 A CN116281954 A CN 116281954A CN 202310246724 A CN202310246724 A CN 202310246724A CN 116281954 A CN116281954 A CN 116281954A
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- conductive agent
- product
- metal
- lithium ion
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- 239000006258 conductive agent Substances 0.000 title claims abstract description 92
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000006260 foam Substances 0.000 claims abstract description 28
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 16
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 13
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005554 pickling Methods 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 239000006262 metallic foam Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000007740 vapor deposition Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 239000000047 product Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000011267 electrode slurry Substances 0.000 description 9
- 239000013543 active substance Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
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- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
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- 239000006257 cathode slurry Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Abstract
The invention belongs to the technical field of lithium battery conductive agents, and particularly relates to a preparation method of a lithium battery conductive agent, a conductive agent and a lithium ion battery. The preparation method of the conductive agent for the lithium battery comprises the steps of taking metal source to be dissolved in glycol to obtain a product 1; soaking the foam metal with the net structure in the product 1 to obtain a product 2; carrying out a first reaction on the product 2 to obtain foam metal with a network structure and metal hydroxide with a rod-shaped structure; depositing the reticular foam metal and the metal hydroxide with a rod-shaped structure on the surface through a second reaction to generate a carbon material to obtain a product 3; and (3) pickling and drying the product 3 to obtain the conductive agent. The conductive agent prepared by the method has more efficient conductive network built by the special net-shaped and rod-shaped structure, has more excellent conductive performance, and improves the multiplying power charge-discharge and cycle performance of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium battery conductive agents, and particularly relates to a preparation method of a lithium battery conductive agent, a conductive agent and a lithium ion battery.
Background
With the increasingly prominent problems of environmental pollution, energy crisis and the like, the development of sustainable development of new energy is particularly important. Lithium ion batteries have been attracting attention as a new and highly efficient green battery. The conductive agent serving as one of key non-main materials of the lithium ion battery plays a very important role on the whole lithium ion pole piece. The most basic function of the conductive agent is conduction, a certain amount of conductive substances are generally added during the manufacture of the pole piece, and micro-current collection is realized between active substances and between the active substances and the current collector, so that the contact resistance of the electrode is reduced to accelerate the movement rate of electrons, and meanwhile, the migration rate of lithium ions in the electrode material is effectively improved, so that the charge and discharge efficiency of the lithium ion battery is improved.
In the current lithium ion battery market, a relatively large number of positive and negative electrode conductive agents, such as carbon nanotubes, graphene, conductive carbon black, and carbon fibers, have been attempted to form a three-dimensional conductive network. The vapor grown carbon fiber and carbon nanotube have small particle size, but are expensive and difficult to disperse. Graphene is used as a novel conductive agent and has a unique lamellar structure, but the preparation cost is high, and the dispersion is difficult. In order to further improve the performance of the lithium ion battery conductive agent and fully exert the advantages of the conductive agent, the conductive agent with a net-shaped and rod-shaped structure is designed.
Currently, conductive materials for lithium ion batteries include conductive carbon black, conductive graphite, carbon fiber, carbon nanotubes, and graphene. The prior art for preparing the conductive agents mainly comprises a laser evaporation graphite method, a plasma jet deposition method, a condensed phase electrolysis generation method, a graphite arc method and the like. The prior art has complex process for preparing the carbon material and higher cost. The preparation process has extremely high requirements on equipment, the prepared carbon material has a single structure, and a large amount of energy is consumed in the preparation process.
The present invention has been made in view of the above problems.
Disclosure of Invention
The invention provides a preparation method of a conductive agent for a lithium battery, which is characterized in that a conductive network is easily formed in the lithium ion battery by preparing the conductive agent with a net-shaped and rod-shaped structure, so that the conductivity of an electrode material is enhanced, and the internal resistance of the lithium ion battery can be obviously reduced. In addition, as the reticular and rod-shaped structures can form good contact with the active substances, the bonding stability among the active substances is improved, a more efficient conductive network can be built, and the multiplying power charge-discharge and cycle performance of the lithium ion battery is improved.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing a conductive agent for a lithium battery, comprising:
dissolving metal in glycol to obtain a product 1;
soaking the foam metal with the net structure in the product 1 to obtain a product 2;
carrying out a first reaction on the product 2 to obtain foam metal with a network structure and metal hydroxide with a rod-shaped structure;
depositing the reticular foam metal and the metal hydroxide with a rod-shaped structure on the surface through a second reaction to generate a carbon material to obtain a product 3;
and (3) pickling and drying the product 3 to obtain the conductive agent.
Further, in a preferred embodiment of the present invention, the first reaction includes a microwave-assisted heating method, a solvothermal method, a coprecipitation method, or a homogeneous precipitation method.
Further, in a preferred embodiment of the present invention, the second reaction includes a vapor deposition method, an arc method, a laser evaporation method, or a solid phase pyrolysis method.
Further, in a preferred embodiment of the present invention, the metal source includes at least one of nickel chloride hexahydrate, nickel nitrate, nickel sulfate, nickel bromide, nickel fluoride, iron chloride, copper chloride, cobalt chloride, zinc chloride, copper nitrate, and cobalt nitrate.
Further, in a preferred embodiment of the present invention, the metal foam mesh comprises one of nickel, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, and alloys thereof.
Further, in a preferred embodiment of the present invention, the first reaction is a microwave-assisted heating method, and the heating temperature is 100 ℃ to 170 ℃.
Further, in a preferred embodiment of the present invention, the gas added in the second reaction is H 2 And a carbon source gas;
the carbon source gas includes methane, ethane, propane, ethylene or acetylene.
Further, in a preferred embodiment of the present invention, the metal foam mesh structure is washed and dried before use.
Further, in a preferred embodiment of the present invention, the washing includes low concentration acid washing, water washing and alcohol washing.
Further, in a preferred embodiment of the present invention, the acid required for pickling the product 3 is nitric acid.
In a second aspect, the present invention provides a conductive agent for lithium ion batteries, wherein the microstructure of the conductive agent is a network-rod structure-, and the surface of the network structure is attached with a rod structure.
In a third aspect, the present invention provides a lithium ion battery comprising the above-described conductive agent.
Compared with the prior art, the invention has at least the following technical effects:
according to the preparation method of the conductive agent for the lithium ion battery, disclosed by the invention, the conductive carbon material can be deposited on a large scale by adopting the foam metal with the net-shaped structure, so that the preparation method is simple, and the cost is reduced. The first reaction mainly comprises modes of microwave auxiliary heating and the like, and is more beneficial to crystallization of products and more controllable in morphology in a wider temperature range. Through the second reaction, the carbon material is effectively and uniformly deposited on the net structure and the rod-shaped structure, the conductive agent with larger surface area is obtained, a continuous conductive network can be formed between the anode material and the cathode material and the particles, and the electronic conductivity of the material is improved. The method can build a more efficient conductive network, thereby reducing the consumption of conductive agents, improving the capacity of the lithium ion battery and reducing the polarization of the battery.
According to the conductive agent for the lithium ion battery, the structural characteristics of the foam metal with the reticular structure and the metal hydroxide with the rod-shaped structure are used as the substrates, carbon materials are deposited on the surfaces, metals are removed after pickling, and the prepared conductive agent with the reticular and rod-shaped carbon nano structure has more excellent conductive performance; and because of the conductive agent with a net-shaped and rod-shaped structure, a conductive network is easy to form in the lithium ion battery, the conductivity of the electrode material is enhanced, and the internal resistance of the lithium ion battery can be obviously reduced. In addition, as the net-rod structure can form good contact with active substances, the bonding stability between the active substances is improved, a more efficient conductive network can be built, and the multiplying power charge-discharge and cycle performance of the lithium ion battery is improved.
Drawings
FIG. 1 is a schematic diagram showing the result of a scanning electron microscope of a conductive agent having a net-rod structure in example 2.
Fig. 2 is an internal resistance diagram of the lithium ion battery corresponding to examples 1-3.
Fig. 3 is a graph showing the ratio-discharge capacity retention ratio of the lithium ion battery corresponding to examples 1-3.
Fig. 4 is a graph showing the results of the cycle performance test of the lithium ion batteries prepared in example 2 and comparative example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the following examples, which are to be construed as merely illustrative and not limitative of the scope of the invention, but are not intended to limit the scope of the invention to the specific conditions set forth in the examples, either as conventional or manufacturer-suggested, nor are reagents or apparatus employed to identify manufacturers as conventional products available for commercial purchase.
The specific technical scheme provided by the embodiment of the invention has the following ideas:
in a first aspect, the present invention provides a method for preparing a conductive agent for a lithium battery, comprising:
dissolving metal source in glycol, and stirring uniformly to obtain a product 1;
washing the foam metal with a reticular structure by using a low-concentration hydrochloric acid solution, and then soaking the foam metal in the product 1 to obtain a product 2;
carrying out a first reaction on the product 2 to obtain foam metal with a network structure and metal hydroxide with a rod-shaped structure;
depositing the reticular foam metal and the metal hydroxide with a rod-shaped structure on the surface through a second reaction to generate a carbon material to obtain a product 3;
and (3) pickling and drying the product 3 to obtain the conductive agent.
According to the preparation method of the conductive agent for the lithium ion battery, disclosed by the invention, the conductive carbon material can be deposited on a large scale by adopting the foam metal with the net-shaped structure, so that the preparation method is simple, and the cost is reduced. The first reaction mainly comprises modes of microwave auxiliary heating and the like, and is more beneficial to crystallization of products and more controllable in morphology in a wider temperature range. Through the second reaction, the carbon material is effectively and uniformly deposited on the net structure and the rod-shaped structure, the conductive agent with larger surface area is obtained, a continuous conductive network can be formed between the anode material and the cathode material and the particles, and the electronic conductivity of the material is improved. The method can build a more efficient conductive network, thereby reducing the consumption of conductive agents, improving the capacity of the lithium ion battery and reducing the polarization of the battery.
As an implementation of the examples herein, the metal source includes at least one of nickel chloride hexahydrate, nickel nitrate, nickel sulfate, nickel bromide, nickel fluoride, iron chloride, copper chloride, cobalt chloride, zinc chloride, copper nitrate, and cobalt nitrate.
As an implementation of the examples herein, the metal includes nickel chloride hexahydrate, nickel nitrate, nickel sulfate, nickel bromide, nickel fluoride.
Further preferably, the metal source is most preferably nickel chloride hexahydrate; mainly because the solubility is good, the cost is low, and the hydroxide structure synthesized by taking the nickel chloride hexahydrate as a metal source has good morphology.
As an implementation of the examples of the present application, the above-mentioned mesh-structure foam metal includes nickel, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, and one of the above-mentioned metal alloys.
The reticular foam metal can deposit conductive carbon materials on a large scale due to the self structure, the preparation method is simple, and the enterprise cost is reduced.
Further preferably, the mesh-structured foam metal is nickel; the reasons are as follows: 1. compared with the metal, the reticular metal foam nickel has low price and low cost for preparing the conductive agent, and can realize larger-scale production. 2. The reticular metal foam nickel has stable structure in microwave auxiliary heating, and is favorable for the generation of metal hydroxide with a rod-shaped structure on the surface of the reticular metal foam nickel. 3. The netlike structure metal foam nickel has good ductility, and can enable the conductive agent carbon material to be deposited on the surface of the metal foam nickel better in vapor deposition.
As an implementation of the examples herein, the first reaction described above includes a microwave-assisted heating process, a solvothermal process, a co-precipitation process, or a homogeneous precipitation.
The microwave-assisted heating method can achieve the aim of rapidly preparing the nano material, has a wider temperature range, is more beneficial to crystallization of the product, and has more controllable morphology.
The reaction of solvothermal method in organic solvent can effectively inhibit the oxidation process of the product. However, the process of removing the residual solvent is complicated because the reaction temperature of the synthesized product is low.
The coprecipitation method or the uniform precipitation method has the advantages that the corresponding products can be quickly synthesized by the coprecipitation method or the uniform precipitation method, but the final products of the coprecipitation method and the uniform precipitation method are low in separation degree and selectivity, and morphology particles of the synthesized products are difficult to control.
Further preferably, the first reaction is a microwave-assisted heating method. The heating temperature is 100-170 ℃.
When the temperature is higher than 170 ℃, the speed of the generated product is too high, and the morphology of the product is irregular; when the temperature is lower than 100 ℃, the reaction is incomplete because the heating temperature is too low and the amount of metal hydroxide produced is small.
As an implementation of the examples of the present application, the second reaction includes a vapor deposition method, an arc method, a laser evaporation method, or a solid-phase pyrolysis method.
Further preferably, the second reaction is a vapor phase precipitation process, the temperature being 700-900 ℃, and the precipitation time being 2-3 hours.
The vapor deposition method can effectively ensure that the carbon material is uniformly deposited on the net-shaped structure and the rod-shaped structure, so as to obtain the conductive agent with larger surface area; the vapor deposition method is more favorable for uniform deposition of carbon materials, and the conductive agent with excellent performance is prepared.
As an implementation mode of the embodiment of the application, the gas added in the second reaction is H 2 And a carbon source gas;
further preferably, H is added in the second reaction 2 And the volume ratio of the carbon source gas is 1: (0.7-1.3);
most preferably H 2 And the volume ratio of the carbon source gas is 1:1, a step of; at this volume ratio, the carbon material can be uniformly deposited on the network structure and the rod-like structure.
The carbon source gas includes methane, ethane, propane, ethylene, or acetylene.
As an implementation mode of the embodiment of the application, the foam metal with the mesh structure needs to be washed and dried before being used.
The purpose of the washing and drying is to remove impurities from the metal surface, on the one hand, the washing removes impurities and oxides remaining on the metal surface, and the drying is to evaporate residual moisture from the foam metal surface. For the next microwave-assisted heating, the formation of metal hydroxide on the foam metal surface is ready.
As an embodiment of the examples herein, the washing includes low concentration acid washing, water washing and alcohol washing.
As an embodiment of the examples of the present application, the acid required in the acid washing of the above product 3 is dilute nitric acid, dilute sulfuric acid or dilute hydrochloric acid; the concentration of acid is controlled to be 3-5mol/l;
in a second aspect, the present invention provides a conductive agent for a lithium battery, which has a microstructure of a network-rod structure, wherein the surface of the network structure is attached with a rod structure. The conductive agent prepared by the prior art is of a single structure, such as a common conductive agent material, the conductive carbon black is of a single spherical structure, and the carbon fiber is of a single linear structure; in this patent, because of the specific conductive agent with the net-rod structure, a conductive three-dimensional structure can be quickly established, and the conductive agent can form net-type and chain-type conductive structures with active materials in the lithium ion battery, thereby being beneficial to improving the electronic conductivity of the materials and improving the performance of the lithium ion battery.
In a third aspect, the present invention provides a lithium ion battery comprising the above-described conductive agent.
As an implementation of the examples of the present application, the lithium ion battery includes a positive electrode, a negative electrode, an electrolyte, a separator, and a case. The positive electrode is prepared by coating positive electrode slurry on a positive electrode aluminum foil current collector;
the positive electrode slurry includes a solid component and a solvent; the solid component includes a positive electrode active material, a binder, and a conductive agent.
Wherein, in the positive electrode slurry, the mass percentages of the solid components are respectively 90-98% of positive electrode active material, 1-3% of adhesive and 1-5% of conductive agent;
the positive electrode active material is nickel cobalt lithium manganate (NCM) ternary positive electrode material, the adhesive is polyvinylidene fluoride (PVDF), and the conductive agent is a conductive agent material with a net-shaped and rod-shaped structure.
As an implementation mode of the embodiment of the application, the negative electrode is prepared by coating a negative electrode slurry on a negative electrode copper foil current collector;
as an embodiment of the examples of the present application, the negative electrode slurry includes a solid component and a solvent.
As an embodiment of the present application, the solid component includes a negative electrode active material, a binder, a thickener, and a conductive agent.
Wherein, in the anode slurry, the mass percentage of the solid components is 90-96% of anode active material, 1-2% of adhesive, 1-2% of thickener and 1-3% of conductive agent.
The negative electrode active material is graphite, the adhesive is Styrene Butadiene Rubber (SBR), the thickener is sodium carboxymethylcellulose (CMC), and the conductive agent is a conductive agent material with a net-shaped and rod-shaped structure.
In summary, the present invention has at least the following technical effects:
1) The method for preparing the conductive agent is unique, simple in process and low in cost. On the foam metal, a metal hydroxide having a rod-like structure is synthesized by a first reaction, particularly microwave-assisted heating, and then a conductive agent material is prepared by a second reaction including vapor deposition.
2) The prepared conductive agent has a net-shaped and rod-shaped structure, and is beneficial to enhancing the conductivity of the electrode material. The conductive agents are in the form of net-net contact and net-line contact, and can form a conductive network structure with a certain scale. Such a structure is advantageous in that the conductive agent plays a role of collecting micro-current between active materials and between the active materials and a current collector to be further enhanced.
3) The prepared conductive agent has a net-shaped and rod-shaped structure, so that the conductive agent is easy to disperse, and the bonding and stability between active materials are improved. And the net-shaped and rod-shaped structure of the conductive agent can form a continuous conductive network in the electrode active material, and the anode and the cathode electrode plates have higher toughness after being added, so that the peeling caused by the volume change of the material in the charge and discharge process can be improved, and the cycle life of the lithium ion battery can be prolonged.
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Example 1
The embodiment provides a preparation method of a conductive agent for a lithium battery, which comprises the following steps:
step 1: weigh 2mmol NiCl 2 ·6H 2 O is dissolved in 15mL of deionized water, the solution is stirred to obtain a uniform dispersion solution, the obtained solution is poured into 45mL of glycol solution, and the solution is stirred for 0.5h to obtain a product 1.
Step 2: pouring the obtained product 1 into a reaction container, adding the netlike structure foam nickel to obtain a product 2, putting the product 2 into a microwave auxiliary heating instrument, setting the reaction time to be 1h, setting the reaction temperature of the microwave auxiliary heating instrument to be 120 ℃, cooling to room temperature after the reaction is completed, taking out the foam nickel in the reaction container, washing with deionized water, and washing away impurities and ions remained on the surface to obtain nickel hydroxide with the netlike structure foam nickel and a bar-shaped structure as reaction products, wherein the nickel hydroxide with the bar-shaped structure is adhered on the netlike structure foam nickel.
Step 3: in a tube furnace H 2 And the product of nickel hydroxide with a reticular structure foam nickel and a rod-shaped structure, which is prepared in the step 2, is grown for 2 hours at 800 ℃ under the atmosphere condition that the volume ratio of propane is 1:1, so as to obtain a product 3;
the product 3 was washed with nitric acid to obtain a net-like and rod-like conductive agent.
The present embodiment provides a lithium ion battery:
step 1: preparation of lithium ion battery positive electrode slurry: polyvinylidene fluoride (PVDF) is dissolved in 100g of N-methyl pyrrolidone (NMP) solvent, and then nickel cobalt lithium manganate (NCM) ternary positive electrode material and conductive agent are continuously added and uniformly mixed. Wherein, the positive electrode slurry of the lithium ion battery is added with the NCM, PVDF and conductive agent in the NMP in the amounts of 4815 g,5g and 10g respectively.
Preparing lithium ion battery negative electrode slurry: sodium carboxymethylcellulose (CMC) is dissolved in 100g of deionized water, and then graphite, a conductive agent and Styrene Butadiene Rubber (SBR) are added and mixed uniformly. Wherein, the mass added in graphite, conductive agent, CMC and SBR in the lithium ion battery cathode slurry is 96g,2g,1g and 1g respectively.
Step 2: coating the obtained lithium ion battery anode slurry on an aluminum foil current collector, and rolling, slitting, die cutting and baking to obtain a lithium ion battery anode;
the negative electrode slurry is coated on a copper foil current collector and is subjected to rolling, slitting, die cutting and baking to obtain the negative electrode of the lithium ion battery.
Step 3: and (3) assembling the positive electrode and the negative electrode in the step (2) with the diaphragm, the electrolyte and the shell to form the lithium ion battery.
Example 2
The embodiment provides a preparation method of a conductive agent for a lithium battery, which comprises the following steps: steps 1 and 3 were the same as in example 1, and in step 2, the reaction temperature of the microwave-assisted heating apparatus was changed to 140℃only, and the reaction time was set to 1.2 hours. The scanning electron microscope result of the conductive agent obtained in this example is shown in fig. 1;
the present embodiment provides a lithium ion battery: the preparation method is the same as in example 1.
Example 3
The embodiment provides a preparation method of a conductive agent for a lithium battery, which comprises the following steps: step 1 is the same as example 1, and in step 2, the reaction temperature of the microwave auxiliary heating apparatus is changed to 160 ℃ and the reaction time is set to 1.1h; in the step 3, the temperature of the tube furnace is changed to 850 ℃, and the precipitation time is 2.5h.
The present embodiment provides a lithium ion battery: the preparation method is the same as in example 1.
Comparative example 1
This comparative example provides a lithium ion battery:
the specific preparation procedure was the same as in example 1, except that the conductive agent material in step (2) was carbon black having a surface area of 150m 2 /g。
In order to illustrate that the conductive agent with the net-shaped and rod-shaped structures provided by the application can improve the performance of the lithium ion battery, the following experiment is specially carried out:
experimental example 1
The surface areas of the conductive agents of examples 1 to 3 and comparative examples were measured, and the test results are shown in Table 1;
test instrument: kang Da specific surface area Analyzer (model: evoTM-4);
the internal resistance and the high-temperature rate discharge capacity retention rate of the lithium ion batteries of examples 1 to 3 and comparative example 1 were measured, and the test results are shown in table 1;
test instrument: cleaning and grinding a precise battery tester (model: NBT5V100AC 24-T);
the testing method comprises the following steps: and calculating the internal resistance of the lithium ion battery by using the current difference and the voltage difference of different loading currents. And discharging the lithium ion battery with the 1C current of 61A to obtain the rate discharge capacity retention rate.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Surface area m 2 /g | 260 | 350 | 200 | 150 |
| Internal resistance (mΩ) | 1.8 | 1.0 | 2.2 | 3 |
| High-temperature rate discharge capacity retention (%) | 90 | 98 | 87 | 76 |
From the above, the surface area of example 2 was found to be 350m at the maximum 2 And/g, wherein the internal resistance of the corresponding lithium ion battery is 1.8mΩ at minimum, and the high-temperature rate discharge retention rate is 98% at maximum.
The lithium ion batteries assembled in comparative example 1 and example 2 were subjected to performance tests. The resistance of the lithium ion battery of the comparative example was 3mΩ, which is greater than the internal resistance of the lithium ion battery of example 2 by 1.8mΩ. The high-temperature rate discharge retention rates of comparative example 1 and example 2 were 76% and 98%, respectively. After the net-shaped and rod-shaped conductive agent materials are added, the internal resistance of the lithium ion battery is reduced, and the rate discharge retention rate is obviously improved.
Experimental example 2
Reversible capacity retention rates of lithium ion batteries of example 2 and comparative example 1 were measured: the test results are shown in FIG. 4.
Test instrument: precision battery tester (type: NBT5V100AC 16-T)
The testing method comprises the following steps: performing 1000 times of cycle test under the charge-discharge multiplying power performance of 1C at high temperature (45 ℃), and comparing the capacity after 1000 times of cycle with the initial capacity to obtain the capacity retention rate;
as can be seen from fig. 4, the reversible capacity retention rates of comparative example 1 and example 2 were 87% and 92.8%, respectively, by 1000 cycle test at high temperature (45 ℃) and charge-discharge rate performance of 1C. After the net-shaped and rod-shaped conductive agent materials are added into the battery, the cycle performance of the lithium ion battery is obviously improved.
Finally, it should be noted that: the foregoing description is only of the preferred embodiments of the invention and is not intended to limit the scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a conductive agent for a lithium battery, comprising the steps of:
dissolving metal in glycol to obtain a product 1;
soaking the foam metal with the net structure in the product 1 to obtain a product 2;
carrying out a first reaction on the product 2 to obtain foam metal with a network structure and metal hydroxide with a rod-shaped structure;
depositing the reticular foam metal and the metal hydroxide with a rod-shaped structure on the surface through a second reaction to generate a carbon material to obtain a product 3;
and (3) pickling and drying the product 3 to obtain the conductive agent.
2. The method for producing a conductive agent according to claim 1, wherein the first reaction comprises a microwave-assisted heating method, a solvothermal method, a coprecipitation method, or a homogeneous precipitation.
3. The method for producing a conductive agent according to claim 1, wherein the second reaction comprises a vapor deposition method, an arc method, a laser evaporation method, or a solid-phase pyrolysis method.
4. The method for producing a conductive agent according to claim 1, wherein the metal source comprises at least one of nickel chloride hexahydrate, nickel nitrate, nickel sulfate, nickel bromide, nickel fluoride, ferric chloride, cupric chloride, cobalt chloride, zinc chloride, cupric nitrate, and cobalt nitrate.
5. The method of producing a conductive agent according to claim 1, wherein the metal foam of a mesh structure comprises nickel, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, or one of the foregoing metal alloys.
6. The method for producing a conductive agent according to claim 3, wherein the gas added in the second reaction is H 2 And a carbon source gas;
the carbon source gas includes methane, ethane, propane, ethylene or acetylene.
7. The method of producing a conductive agent according to claim 1, wherein the metal foam of a network structure is washed and dried before use.
8. The method for producing a conductive agent according to claim 1, wherein the washing includes low-concentration acid washing, water washing and alcohol washing.
9. A conductive agent for lithium ion battery prepared by the preparation method of any one of claims 1 to 8, characterized in that the microstructure of the conductive agent is a net-rod structure, wherein the surface of the net structure is attached with a rod structure.
10. A lithium ion battery comprising the conductive agent of claim 9.
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