CN113991057A - Lithium battery negative electrode material and preparation method of lithium battery negative electrode material applied to lithium battery - Google Patents
Lithium battery negative electrode material and preparation method of lithium battery negative electrode material applied to lithium battery Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000011888 foil Substances 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 239000011267 electrode slurry Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000013110 organic ligand Substances 0.000 claims description 9
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 9
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000006256 anode slurry Substances 0.000 claims description 4
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- 238000007765 extrusion coating Methods 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 238000007580 dry-mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011883 electrode binding agent Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000007581 slurry coating method Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
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- 239000012621 metal-organic framework Substances 0.000 description 13
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- 238000001556 precipitation Methods 0.000 description 3
- 101000761811 Chlamydia pneumoniae 4-hydroxybenzoate decarboxylase subunit C Proteins 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910007566 Zn-MOF Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000011889 copper foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002808 molecular sieve Substances 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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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- Composite Materials (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium battery negative electrode material and a preparation method thereof applied to a lithium battery. The MOF @ C composite material prepared by the method disclosed by the invention maintains the advantages of the MOF, improves the conductivity and increases active sites in the charging and discharging processes; the influence of the adhesive on the surface migration in the drying process is compensated by adopting a multilayer coating mode, the peel strength of the negative electrode material on the foil is effectively improved, and the preparation of a thick electrode is facilitated so as to improve the capacity of the negative electrode.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a lithium battery negative electrode material and a preparation method thereof applied to a lithium battery.
Background
Lithium ion batteries are becoming a focus of further research as a very promising electrochemical storage means today.
The lithium ion battery gradually permeates the living aspects, and the lithium ion battery is small enough to be electronic products and large enough to be seen by heavy machinery such as ships, cranes and the like. The gradual temperature rise of application scenes such as electric vehicles, energy storage batteries and the like puts forward higher requirements on the batteries, wherein the continuous optimization of the performances such as consistency, safety, rate capability, long service life and the like is particularly important. The key for improving the performances is to develop enough anode and cathode materials of the lithium ion battery to be reversibly and rapidly embedded and de-embedded under unit mass or volume, wherein the cathode material is a main component of the lithium ion battery, and the performance of the lithium ion battery is directly influenced by the performance of the cathode material.
Graphite, which is a conventional carbon material, is widely commercially used as a lithium ion battery cathode material at present, and is considered to be an ideal lithium battery cathode material at present due to the advantages of high stability, good conductivity, wide sources and the like. However, the theoretical capacity is low, and lithium precipitation is easily caused when large-current charging is carried out. At present, most of the negative pole pieces of lithium ion batteries are made of carbon materials with graphite structures, generally, the carbon materials, a conductive agent, a binder and the like are mixed according to a certain proportion and directly coated on a copper foil at one time, and then the copper foil is dried and rolled. When a high energy density battery is designed, the thickness of an electrode is generally larger, and if a traditional coating method is used, the stable peeling strength of a negative electrode is difficult to ensure, so that the capacity and the safety performance of the battery are influenced.
Metal organic framework Materials (MOFs), a coordination polymer material that has developed rapidly in the last decade. The material is obtained by self-assembly of metal ions and organic ligands, has a high specific surface area, a rich and adjustable pore structure and a modifiable surface, is beneficial to material transmission, has good capacity of accommodating active materials and reaction products, and relieves volume change in the charging and discharging process. On the basis, the composite material obtained by compounding the MOF and the conductive material retains the advantages of the MOF, improves the conductivity, has advantages in aspects of material transfer, material loading and the like, and further shows better battery performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a lithium battery negative electrode material and a preparation method thereof applied to a lithium battery, overcoming the defect that the lithium precipitation is easy to occur when the graphite-based negative electrode material of the lithium battery is charged and discharged at a large current, and simultaneously solving the problem of unstable peeling strength caused by the migration of an adhesive to the surface in the drying process when the negative electrode material with thicker coating is coated.
The technical scheme of the invention is as follows:
a preparation method of a lithium battery negative electrode material comprises the following steps:
(1) and pretreating the carbon-based material: soaking the carbon-based material in acetone and washing the carbon-based material with deionized water, drying the carbon-based material in inert gas at 40-60 ℃, and then putting the carbon-based material into an oxidant for refluxing, wherein the refluxing temperature is controlled to be 60-80 ℃; taking out the carbon-based material after 1-3 hours, washing the carbon-based material to be neutral, and finally fully drying the carbon-based material in a vacuum drying oven at the temperature of 60-80 ℃ to obtain an activated carbon-based material;
(2) adding the activated carbon-based material prepared in the step (1), a transition metal ion salt and a polydentate organic ligand into N, N-dimethylformamide to be uniformly mixed, slowly introducing inert gas to fully discharge oxygen in the mixture, and continuously reacting for 5-10 h in a constant-temperature oil bath at the temperature of 120-150 DEG C(ii) a Wherein the chemical formula of the transition metal ion salt is Mx(NO3)y·zH2O, wherein M is a transition metal element, the chemical formula of the polydentate organic ligand is R-BDC, wherein R is alkyl or H, BDC is benzoylate, and M isx(NO3)y·zH2The molar ratio of O to R-BDC is 1: 2-5, and the mass of the activated carbon-based material accounts for the mass of the activated carbon-based material and Mx(NO3)y·zH280-98% of the total mass of the O and the R-BDC;
(3) and after the reaction is finished, slowly cooling the reactant to room temperature, filtering out precipitated crystals, washing with N, N-dimethylformamide for multiple times to remove unreacted transition metal ion salts and polydentate organic ligands, soaking in an organic solvent for 3-5 times, filtering out, and drying and activating in inert gas at 120-150 ℃ for 6-12 hours to obtain the MOF @ C composite material serving as the lithium battery cathode material.
In the step (1), the carbon-based material is soaked in acetone for 1-5 hours at room temperature, and is washed by deionized water for 3-5 times after being filtered.
In the step (1), the carbon-based material comprises one or a mixture of more of natural graphite, artificial graphite, mesophase carbon microspheres, soft carbon and hard carbon, and one or a mixture of more of conductive carbon black, graphene and carbon nanotubes, and the mixing mass ratio of the two carbon-based materials is 8-9: 1; the oxidant comprises one or more of nitric acid, sulfuric acid, acidic permanganate, acidic dichromate, hypochlorite, hydrogen peroxide and persulfate, and is a stable mixed solution formed by mixing.
In the step (1), the carbon-based material is washed to be neutral by using inorganic base or organic base, the inorganic base is selected from sodium hydroxide, sodium bicarbonate or sodium carbonate, and the organic base is selected from triethylamine, ethylenediamine or tetrabutylammonium hydroxide.
The inert gas is argon; in the step (2), the flow rate of slowly introducing argon is 0.1-1L/min, and the purity of argon is 99.999%.
In the step (3), the reactant is slowly cooled at a speed of 1-5 ℃/min, and the organic solvent is methanol or ethanol.
A method for preparing a lithium battery by using a lithium battery negative electrode material specifically comprises the following steps:
(a) preparing anode slurry: the method comprises the following steps of (1) carrying out dry mixing on a lithium battery negative electrode material and binder powder according to different proportions to obtain a plurality of mixtures, and adding the mixtures into a proper amount of solvent respectively to obtain negative electrode slurry with various proportions;
(b) and preparing a negative pole piece: sequentially coating negative electrode slurry with various proportions on a foil in a slit type extrusion coating mode, sequentially decreasing the content of a binding agent in the negative electrode slurry from the inner layer to the outer layer in a multi-layer negative electrode slurry coating, and then drying, rolling, slitting, cutting a tab by laser and die cutting the multi-layer coated negative electrode plate to obtain the negative electrode plate;
(c) and preparing the lithium ion battery: and (c) assembling the negative pole piece prepared in the step (b), the positive pole piece, the diaphragm and the electrolyte to finish the assembly of the lithium ion battery.
The mass of the binder powder accounts for 1-5 wt% of the total mass of the dry-mixed mixture, the proportioning types of the negative electrode slurry are 2-5, namely 2-5 layers of negative electrode slurry with different proportioning are sequentially coated on the foil; the binder powder is selected from an oil binder or a water binder, the oil binder is polyvinylidene fluoride or polytetrafluoroethylene, and the water binder is carboxymethyl cellulose plus styrene-butadiene rubber, polyvinyl alcohol or acrylic resin; when the binder powder is an oil-based binder, the solvent is N-methylpyrrolidone; when the binder powder is a water-based binder, the solvent is deionized water.
In the step (b), the compacted density of the rolling is 1.65-1.75 g-cm-3。
In the step (c), the positive pole piece is selected to have a compacted density of 3.45-3.75 g-cm-3The positive electrode plate of (2).
The invention has the advantages that:
(1) the MOF @ C composite material which is loaded on the carbon-based material and contains the metal ions with the redox property and the ligand structure, prepared by the preparation method disclosed by the invention, has the advantages of the MOF, the conductivity is improved, the increase of active sites in the charging and discharging process is facilitated, the capacity and the rate capability are further improved, the problem of lithium precipitation on the surface of a negative electrode caused by large-current charging and discharging can be effectively avoided, and the better battery performance is represented.
(2) The invention adopts a multilayer coating mode in the coating process of the negative pole piece, namely, the coating is carried out from inside to outside according to the concentration gradient of the adhesive in a gradually decreasing mode, so as to make up the influence caused by the migration of the adhesive to the outer surface in the drying process, effectively improve the peeling strength of the negative pole material on the foil, and simultaneously be beneficial to the preparation of a thick electrode and further improve the capacity of the negative pole.
(3) The MOF has the greatest advantages of high controllability and regular pore channel structure, and the components and the structure of the MOF preparation material can be designed and optimized according to the requirements of different battery systems, so that the method is suitable for the preparation of lithium batteries in different application scenes.
Drawings
FIG. 1 is a schematic flow diagram of the present invention for making MOF @ C composites.
FIG. 2 is a schematic view of an apparatus for performing multilayer coating of a negative electrode tab according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, a method for preparing a negative electrode material for a lithium battery includes the following steps:
(1) and pretreating the carbon-based material: soaking the carbon-based material in acetone for 3h at room temperature, filtering, washing with deionized water for 5 times, drying at 60 ℃ in inert gas, and refluxing in an oxidant at the reflux temperature of 60 ℃; taking out the carbon-based material after 3 hours, washing the carbon-based material to be neutral by using 0.1mol/L hydrochloric acid, and finally fully drying the carbon-based material in a vacuum drying oven at the temperature of 80 ℃ to obtain an activated carbon-based material;
(2) the activated carbon-based material prepared in the step (1) is combined with a transition metal ion salt Zn (NO)3)2·6H2Adding O and a polydentate organic ligand HBDC into N, N-dimethylformamide DMF (dimethyl formamide) dehydrated by a molecular sieve, uniformly mixing, then introducing 99.999% high-purity argon for 3 hours at the speed of 0.5L/min, fully discharging oxygen in the mixture, and continuously reacting for 8 hours under a constant-temperature oil bath at the temperature of 120 ℃; wherein Zn (NO)3)2·6H2The molar ratio of O to HBDC is 1:3, and the mass of the activated carbon-based material accounts for the mass of the activated carbon-based material and Mx(NO3)y·zH290% of the total mass of O and R-BDC;
(3) and after the reaction is finished, slowly cooling the reactant to room temperature at the cooling speed of 2 ℃/min, filtering out precipitated crystals, washing the crystals for 5 times by using DMF (dimethyl formamide) to remove unreacted transition metal ion salts and polydentate organic ligands, soaking the crystals in methanol for 5 times, filtering out the crystals, and drying and activating the crystals at 120 ℃ for 10 hours in an argon atmosphere to obtain the Zn-MOF @ C composite material which is used as a lithium battery negative electrode material.
A method for preparing a lithium battery by using a lithium battery negative electrode material specifically comprises the following steps:
(a) preparing anode slurry: the method comprises the following steps of (1) carrying out dry mixing on a Zn-MOF @ C composite material and binder powder (carboxymethyl cellulose SBR + styrene butadiene rubber CMC) according to different proportions to obtain three mixtures, wherein the mass of the binder powder accounts for 3 wt%, 4 wt% and 5 wt% of the total mass of the dry-mixed mixtures respectively, and then adding the three mixtures into deionized water according to the proportion of 55% of solid content to obtain negative electrode slurry with three proportions; wherein the mass ratio of SBR to CMC is 3: 2;
(b) and preparing a negative pole piece: referring to fig. 2, the cathode slurry with three proportions is respectively injected into three slurry homogenizing devices 11, 12 and 13, and then passes through corresponding delivery pumps 2 and pipes3, feeding the negative electrode slurry with three proportions into three slits 41, 42 and 43 of a coating die head 4, and carrying out three-layer coating on the foil 6 by adopting a slit extrusion coating method along with the driving of a back roll 5 according to the sequence that the concentration of the binder is gradually reduced from the inner layer to the outer layer, wherein the coating surface density is 50 g.m-2Then drying the negative pole piece after the three-layer coating according to the proportion of 1.65g cm-3Rolling, slitting, cutting tabs by laser and die cutting are carried out on the compacted density to obtain a negative pole piece;
(c) and preparing the lithium ion battery: the negative pole piece prepared in the step (b) and the surface density of the negative pole piece are 30 g.m-2The compacted density was 3.5 g/cm-3The NCM811 ternary material anode plate, the PP dry-method diaphragm and the electrolyte complete the assembly of the soft package lithium ion battery.
Example 2
A method for preparing a negative electrode material for a lithium battery is the same as in example 1 except that a transition metal ion salt Zn (NO) in step (2)3)2·6H2Conversion of O to Cu (NO)3)2·6H2And O, finally preparing the Cu-MOF @ C composite material.
The method for preparing the lithium battery by using the lithium battery negative electrode material is completely consistent with the method in the example 1.
Example 3
A preparation method of a lithium battery negative electrode material and a preparation method of a lithium battery are completely the same as the embodiment 1, except that in the step (c), the negative electrode plate and the surface density are 30 g.m-2The compacted density was 3.5 g/cm-3The positive pole piece of the NCM811 ternary material, the PP dry-method diaphragm and the electrolyte complete the assembly of the square-shell lithium ion battery.
Comparative example 1
A method of manufacturing a lithium battery using the negative electrode material for a lithium battery is the same as that of example 1 except that in step (a), the negative electrode material for a lithium battery dry-mixed with the binder powder is a carbon-based material.
Comparative example 2
A method of preparing a lithium battery using the negative electrode material for a lithium battery is the same as that of example 3 except that in step (a), the negative electrode material for a lithium battery dry-mixed with the binder powder is a carbon-based material.
Comparative example 3
A method for preparing a lithium battery by using a lithium battery negative electrode material specifically comprises the following steps:
(a) preparing anode slurry: mixing the carbon-based material and binder powder (SBR + CMC, the mass ratio of SBR to CMC is 3:2) in proportion, and then obtaining a mixture, wherein the mass of the binder powder in the mixture accounts for 4 wt% of the total mass of the dry-mixed mixture, and then adding the mixture into deionized water according to the proportion of 55% of solid content to mix to obtain negative electrode slurry;
(b) and preparing a negative pole piece: coating the negative electrode slurry on a foil according to a conventional slit extrusion coating method, wherein the coating surface density is 50 g.m-2Then drying the coated negative pole piece according to the proportion of 1.65 g-cm-3Rolling, slitting, cutting tabs by laser and die cutting are carried out on the compacted density to obtain a negative pole piece;
(c) and preparing the lithium ion battery: the negative pole piece prepared in the step (b) and the surface density of the negative pole piece are 30 g.m-2The compacted density was 3.5 g/cm-3The NCM811 ternary material anode plate, the PP dry-method diaphragm and the electrolyte complete the assembly of the soft package lithium ion battery.
The negative electrode materials obtained in examples 1 and 2 were subjected to a charging test together with the carbon-based material, and the test results are shown in table 1.
TABLE 1
The negative electrode sheets prepared in example 1, example 2, comparative example 1 and comparative example 3 were subjected to peel strength and resistivity tests, and the test results are shown in table 2.
TABLE 2
| Examples of the experiments | Example 1 | Example 2 | Comparative example 1 | Comparative example 3 |
| Peel strength/N.m-1 | 156 | 147 | 144 | 107 |
| Resistivity/Ω · cm | 5.03 | 5.21 | 4.97 | 4.73 |
The lithium ion batteries prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to electrical property tests (both test data at normal temperature, and the charging and discharging interval was 3.0 to 4.2V), and the test results are shown in table 3.
TABLE 3
It can be seen from table 1 that the MOF @ C materials prepared in examples 1 and 2 are slightly lower than the conventional carbon-based materials in the first efficiency, mainly because the MOF structures in the MOF @ C materials provide more reaction sites, more side reactions occur at the electrode-electrolyte interface, and the coulombic efficiency in the next second and third rounds is equivalent to that of the carbon-based materials, namelyObviously, a stable SEI film is basically formed in the first week of circulation. Both MOF @ C materials have significant advantages over carbon-based materials in terms of gram capacity performance, mainly due to the abundant redox sites provided by the MOF structure, more Li+Can be stored and released therein. EIS tests show that the two MOF @ C materials have smaller interface resistance and charge transfer resistance than carbon-based materials, the formed SEI film is more regular and the ionic conductivity is higher, and Li is also caused by rich redox sites provided by the MOF structure and the porous structure of the MOF structure+In which more shuttle paths are possible.
It can be seen from table 2 that the negative electrode sheets prepared by multilayer coating in examples 1 and 2 and the negative electrode sheet prepared by multilayer coating in comparative example 1 from the carbon-based material both showed higher peel strength, while the negative electrode sheet prepared by single layer coating in comparative example 3 showed significantly lower peel strength, indicating that the multilayer coating method can effectively improve the problem of low peel strength caused by binder migration in the negative electrode. Meanwhile, the resistivity difference between the MOF @ C material and the carbon-based material is not large, which shows that the conductivity of the carbon-based material is not obviously influenced in the compounding process.
It can be seen from a comparison of examples 1 and 2 in table 3 that the performance of the cell can be improved by a reasonable selection of the MOF structure, and better electrical performance can be obtained when Cu salt is used as the metal center of the MOF structure in example 2. Comparing example 1 with comparative example 1, and comparing example 3 with comparative example 2, it can be seen that the use of the MOF @ C material provided by the present invention in soft pack, square shell lithium ion battery application systems can effectively improve long cycle and rate performance. Comparative example 1 and comparative example 3 demonstrate that the use of multi-layer coating can effectively improve the cycle and rate performance of the battery in addition to improving the peel strength of the negative electrode, probably due to the formation of a more uniform active material-conductor-binder network in the negative electrode coating under the multi-layer coating.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a lithium battery negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) and pretreating the carbon-based material: soaking the carbon-based material in acetone and washing the carbon-based material with deionized water, drying the carbon-based material in inert gas at 40-60 ℃, and then putting the carbon-based material into an oxidant for refluxing, wherein the refluxing temperature is controlled to be 60-80 ℃; taking out the carbon-based material after 1-3 hours, washing the carbon-based material to be neutral, and finally fully drying the carbon-based material in a vacuum drying oven at the temperature of 60-80 ℃ to obtain an activated carbon-based material;
(2) adding the activated carbon-based material prepared in the step (1), a transition metal ion salt and a polydentate organic ligand into N, N-dimethylformamide to be uniformly mixed, slowly introducing inert gas to fully discharge oxygen in the mixture, and continuously reacting for 5-10 hours in a constant-temperature oil bath at the temperature of 120-150 ℃; wherein the chemical formula of the transition metal ion salt is Mx(NO3)y·zH2O, wherein M is a transition metal element, the chemical formula of the multidentate organic ligand is R-BDC, wherein R is alkyl or H, BDC is benzenedicarboxylates, and Mx(NO3)y·zH2The molar ratio of O to R-BDC is 1: 2-5, and the mass of the activated carbon-based material accounts for the mass of the activated carbon-based material and Mx(NO3)y·zH280-98% of the total mass of the O and the R-BDC;
(3) and after the reaction is finished, slowly cooling the reactant to room temperature, filtering out precipitated crystals, washing with N, N-dimethylformamide for multiple times to remove unreacted transition metal ion salts and polydentate organic ligands, soaking in an organic solvent for 3-5 times, filtering out, and drying and activating in an inert gas at 120-150 ℃ for 6-12 hours to obtain the MOF @ C composite material serving as the lithium battery cathode material.
2. The method for preparing a negative electrode material for a lithium battery according to claim 1, wherein: in the step (1), the carbon-based material is soaked in acetone for 1-5 hours at room temperature, and is washed by deionized water for 3-5 times after being filtered.
3. The method for preparing a negative electrode material for a lithium battery according to claim 1, wherein: in the step (1), the carbon-based material comprises one or a mixture of more of natural graphite, artificial graphite, mesocarbon microbeads, soft carbon and hard carbon, and one or a mixture of more of conductive carbon black, graphene and carbon nanotubes, and the mixing mass ratio of the two carbon-based materials is 8-9: 1; the oxidant comprises a stable mixed solution formed by mixing one or more of nitric acid, sulfuric acid, acidic permanganate, acidic dichromate, hypochlorite, hydrogen peroxide and persulfate.
4. The method for preparing a negative electrode material for a lithium battery according to claim 1, wherein: in the step (1), the carbon-based material is washed to be neutral by using inorganic base or organic base, the inorganic base is selected from sodium hydroxide, sodium bicarbonate or sodium carbonate, and the organic base is selected from triethylamine, ethylenediamine or tetrabutylammonium hydroxide.
5. The method for preparing a negative electrode material for a lithium battery according to claim 1, wherein: the inert gas is argon; in the step (2), the flow rate of slowly introducing argon is 0.1-1L/min, and the purity of argon is 99.999%.
6. The method for preparing a negative electrode material for a lithium battery according to claim 1, wherein: in the step (3), the reactant is slowly cooled at a speed of 1-5 ℃/min, and the organic solvent is methanol or ethanol.
7. The method for preparing a lithium battery from the negative electrode material of the lithium battery as claimed in claim 1, wherein: the method specifically comprises the following steps:
(a) preparing anode slurry: the method comprises the following steps of (1) carrying out dry mixing on a lithium battery negative electrode material and binder powder according to different proportions to obtain a plurality of mixtures, and adding the mixtures into a proper amount of solvent respectively to obtain negative electrode slurry with various proportions;
(b) and preparing a negative pole piece: sequentially coating negative electrode slurry with various proportions on a foil in a slit type extrusion coating mode, sequentially decreasing the content of a binder in the negative electrode slurry from the inner layer to the outer layer in a multi-layer negative electrode slurry coating, and then drying, rolling, slitting, cutting tabs by laser and die cutting the multi-layer coated negative electrode plate to obtain the negative electrode plate;
(c) and preparing the lithium ion battery: and (c) assembling the negative pole piece prepared in the step (b), the positive pole piece, the diaphragm and the electrolyte to finish the assembly of the lithium ion battery.
8. A method of manufacturing a lithium battery according to claim 7, characterized in that: the mass of the binder powder accounts for 1-5 wt% of the total mass of the dry-mixed mixture, the proportioning types of the negative electrode slurry are 2-5, namely 2-5 layers of negative electrode slurry with different proportioning are sequentially coated on the foil; the binder powder is an oil-based binder or a water-based binder, the oil-based binder is polyvinylidene fluoride or polytetrafluoroethylene, and the water-based binder is carboxymethyl cellulose plus styrene-butadiene rubber, polyvinyl alcohol or acrylic resin; when the binder powder is an oil-based binder, the solvent is N-methylpyrrolidone; when the binder powder is a water-based binder, the solvent is deionized water.
9. A method of manufacturing a lithium battery according to claim 7, characterized in that: in the step (b), the compacted density of the rolling is 1.65-1.75 g-cm-3。
10. A method of manufacturing a lithium battery according to claim 9, characterized in that: in the step (c), the positive pole piece is selected to have a compacted density of 3.45-3.75 g-cm-3The positive electrode plate of (2).
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