CN111430692B - Lithium ion battery cathode material and preparation method thereof - Google Patents
Lithium ion battery cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN111430692B CN111430692B CN202010244312.2A CN202010244312A CN111430692B CN 111430692 B CN111430692 B CN 111430692B CN 202010244312 A CN202010244312 A CN 202010244312A CN 111430692 B CN111430692 B CN 111430692B
- Authority
- CN
- China
- Prior art keywords
- sio
- lithium ion
- ion battery
- preparation
- carbon source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010406 cathode material Substances 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 239000011247 coating layer Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 12
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000007773 negative electrode material Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 17
- 229920001568 phenolic resin Polymers 0.000 claims description 17
- 238000005507 spraying Methods 0.000 claims description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 9
- 229930006000 Sucrose Natural products 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000005720 sucrose Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000713 high-energy ball milling Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 83
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910004750 SiO0.8 Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910004674 SiO0.5 Inorganic materials 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910020381 SiO1.5 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012073 inactive phase Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery cathode material and a preparation method thereof, belonging to the technical field of lithium ion batteries. The lithium ion battery cathode material is internally provided with a three-dimensional carbon material conductive network, is externally provided with a uniform carbon material coating layer and is SiOxThe nano particles are uniformly dispersed in the three-dimensional carbon material conductive network. By mixing SiOxThe material, the solvent, the metal compound and the carbon source are uniformly mixed and mechanically crushed to obtain slurry, the slurry is subjected to spray drying and then to a fluidized bed coating process to obtain powder containing a coating layer, and finally the powder is sintered at high temperature in an inert atmosphere to obtain the material. The lithium ion battery cathode material has the advantages of high conductivity, long cycle life and high first efficiency, and the preparation method has the advantages of simplicity and convenience in operation, high repeatability, easiness in industrialization and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery cathode material and a preparation method thereof.
Background
The theoretical capacity of the graphite cathode material is 372mAh/g, and the requirement of a novel lithium ion battery on high energy density cannot be met. Although silicon has the highest theoretical specific capacity of 4200mAh/g, the problem of excessive volume expansion (more than or equal to 300%) in the lithium intercalation process of the silicon material causes the cycle decay of the silicon material to be serious. Silicon oxides also have higher theoretical specific capacity, but compared with pure silicon, the silicon oxide has Si-O bonds with higher bond energy in a silicon oxide structure and Li is generated in the lithium intercalation process2O and Li4SiO4The inactive phase can well play a role in inhibiting and buffering the volume expansion of the material, so that the cycle performance is more advantageous. However, the formation of the inactive phase consumes a part of lithium, resulting in a problem that the silica material has a low first efficiency.
CN108493438A discloses SiO for lithium ion batteryxThe material is disproportionated to generate silicate, so that Li due to silicon oxide in the process of lithium intercalation for the first time is avoided+The irreversible consumption of the energy-saving power source improves the first coulomb efficiency. But the high-temperature sintering is carried out twice in the preparation process, so that the energy consumption is high and the cost is high; meanwhile, the outer carbon coating mode of the sol-gel method is not beneficial to generating uniform coating layers, and the improvement effect on the cycle performance is not obvious.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a lithium ion battery cathode material and a preparation method thereof.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiOxUniformly mixing a material, a solvent, a metal compound and a carbon source, and mechanically crushing until the median particle size of SiOx is 0.1-3 um to obtain slurry;
s2, spray drying the slurry to obtain powder with a median particle size of 5-20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized gas to keep the powder in a suspended state;
s3, spraying the solution containing the organic carbon source into the cavity of the fluidized bed reactor, and cooling after the solution containing the organic carbon source completely reacts to obtain powder containing a coating layer;
and S4, heating the powder obtained in the step S3 to 700-1000 ℃ at a heating rate of 1-10 ℃/min in an inert atmosphere, and carrying out constant-temperature heat treatment for 1-6h to obtain the cathode material.
In a preferred embodiment of the present invention, the SiO in step S1xThe material is SiOxParticles, or a mixture of Si and SiO, wherein 0.5. ltoreq. x.ltoreq.1.5.
In a preferred embodiment of the present invention, the solvent and SiO in step S1xThe mass ratio of the materials is 1-5: 1; the solvent is at least one of deionized water, ethanol, methanol and isopropanolAnd (4) seed preparation.
As a preferred embodiment of the present invention, in the metal compound in step S1, the metal element M is one of aluminum, magnesium, lithium and calcium; the compound is at least one of nitrate, sulfate, carbonate, chloride, hydroxide and oxide of the metal element M; wherein, the metal elements M and SiOxThe mass ratio of the materials is 1: 1 to 12.
As a preferred embodiment of the present invention, the carbon source and SiO in step S1xThe mass ratio of the materials is 0.05-0.5: 1; the carbon source is at least one of carbon nano tube, graphene, glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone, phenolic resin and sodium carboxymethylcellulose.
In a preferred embodiment of the present invention, the fluidizing gas in step S2 is one of air and nitrogen.
As a preferred embodiment of the present invention, the organic carbon source and SiO of step S3xThe mass ratio of the materials is 0.05-0.2: 1; wherein the organic carbon source is at least one of glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone and phenolic resin.
In a preferred embodiment of the present invention, the mass ratio of the organic carbon source to the solvent in the organic carbon source-containing solution in step S3 is 0.1 to 0.5: 1; wherein the solvent is at least one of deionized water, ethanol and methanol.
In a preferred embodiment of the present invention, the reaction time of the organic carbon source-containing solution in step S3 is 1 to 4 hours.
As a preferred embodiment of the present invention, the mechanical crushing in the step S1 is planetary ball milling or high energy ball milling or sand milling.
As a preferred embodiment of the present invention, the inert atmosphere in step S4 is nitrogen or argon.
The invention also provides the lithium ion battery cathode material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the invention isThe provided lithium ion battery cathode material has a three-dimensional carbon material conductive network inside, a uniform carbon material coating layer outside and SiOxThe nano particles are uniformly dispersed in the three-dimensional carbon material conductive network. The invention improves the electronic conductivity of the cathode material by constructing an internal three-dimensional carbon material conductive network, and combines the characteristic of high stability of the structure with the nano SiOxThe function of inhibiting volume expansion is achieved; by adding metal salts or oxides to SiOxHigh temperature disproportionation of the product to avoid or mitigate irreversible Li+Consumption, and the first coulombic efficiency of the negative electrode material is improved; the dynamic and continuous coating of the fluidized bed is utilized to enable the coating to continuously exist on the surface of the material, and a compact and uniform coating layer is obtained through heat treatment, so that the electrochemical performance of the cathode material is obviously improved; and the traditional multiple sintering process is reduced to single sintering, so that the process is simplified and the cost is reduced. In conclusion, the lithium ion battery cathode material has the advantages of high conductivity, long cycle life and high first-effect, and the preparation method has the advantages of simplicity and convenience in operation, high repeatability, easiness in industrialization and the like.
Drawings
FIG. 1 is a schematic structural diagram of a three-dimensional carbon material conductive network provided by the present invention;
FIG. 2 is a schematic structural diagram of a negative electrode material for a lithium ion battery provided by the present invention;
fig. 3 is a scanning electron microscope image of the negative electrode material of the lithium ion battery with the three-dimensional carbon material conductive network in example 5 of the present invention.
FIG. 4 is a transmission electron microscope image of the lithium ion battery cathode material of example 5 after SiO is etched away.
The reference numbers illustrate: 1. a three-dimensional carbon material conductive network; 2. a carbon material coating layer; 3. SiOx nanoparticles.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
A preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiOxThe material,Uniformly mixing a solvent, a metal compound and a carbon source, and mechanically crushing the mixture in a planetary ball milling or high-energy ball milling or sanding mode until the median particle size of SiOx is 0.1-3 um to obtain slurry; wherein, SiOxThe material is SiOxParticles or a mixture of Si and SiO, and x is 0.5-1.5;
s2, spray drying the slurry to obtain powder with a median particle size of 5-20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized gas air or nitrogen to keep the powder in a suspension state;
s3, spraying the solution containing the organic carbon source into the cavity of the fluidized bed reactor, and cooling after the solution containing the organic carbon source completely reacts to obtain powder containing a coating layer;
and S4, heating the powder obtained in the step S3 to 700-1000 ℃ at a heating rate of 1-10 ℃/min in an inert atmosphere of nitrogen or argon, and carrying out constant-temperature heat treatment for 1-6h to obtain the cathode material.
In step S1, the solvent and SiOxThe mass ratio of the materials is 1-5: 1; the solvent is at least one of deionized water, ethanol, methanol and isopropanol. The metal element M in the metal compound is one of aluminum, magnesium, lithium and calcium; the compound is at least one of nitrate, sulfate, carbonate, chloride, hydroxide and oxide of the metal element M; wherein, the metal elements M and SiOxThe mass ratio of the materials is 1: 1 to 12. Carbon source and SiOxThe mass ratio of the materials is 0.05-0.5: 1; the carbon source is at least one of carbon nano tube, graphene, glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone, phenolic resin and sodium carboxymethylcellulose.
In step S3, the organic carbon source is mixed with SiOxThe mass ratio of the materials is 0.05-0.2: 1; wherein the organic carbon source is at least one of glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone and phenolic resin. The mass ratio of the organic carbon source to the solvent in the solution containing the organic carbon source is 0.1-0.5: 1; wherein the solvent is at least one of deionized water, ethanol and methanol. The reaction time of the solution containing the organic carbon source is 1-4 h.
Referring to fig. 1 and 2, the lithium ion battery negative electrode material of the present invention has a three-dimensional carbon material conductive network 1 inside, a uniform carbon material coating layer 2 outside, and SiOx nanoparticles 3 uniformly dispersed in the three-dimensional carbon material conductive network. The invention improves the electronic conductivity of the cathode material by constructing an internal three-dimensional carbon material conductive network, and combines the characteristic of high stability of the structure with the nano SiOxPlays a role in inhibiting volume expansion.
Example 1:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing SiO particles, deionized water, magnesium oxide, carbon nanotubes and polyvinylpyrrolidone, and carrying out planetary ball milling and crushing to obtain SiO slurry with a median particle size of 0.1-3 um; wherein the mass ratio of the deionized water to the SiO is 1: 1, the mass ratio of magnesium oxide to SiO is 1: 2, the mass ratio of the carbon nano tube to the SiO is 0.1: 1, the mass ratio of polyvinylpyrrolidone to SiO is 0.4: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 5 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying the ethanol solution of the phenolic resin into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 1 hour, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the mass ratio of the phenolic resin to the SiO is 0.2: 1, the mass ratio of the phenolic resin to the ethanol is 0.5: 1;
and S4, heating the powder obtained in the step S3 to 700 ℃ at a heating rate of 1 ℃/min in a nitrogen atmosphere, and carrying out constant-temperature heat treatment for 6h to obtain the cathode material.
Example 2:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing Si particles, SiO particles, isopropanol, aluminum chloride, graphene and sodium carboxymethyl cellulose, and grinding and crushing the mixture to obtain slurry with a median particle size of 0.1 um; wherein the mass ratio of Si to SiO is 1: 1, the mass ratio of the isopropanol to the Si-containing material is 5: 1, the mass ratio of aluminum element in the alumina to Si-containing material is 1: 12, the mass ratio of the graphene to the Si-containing material is 0.01: 1, the mass ratio of the sodium carboxymethyl cellulose to the Si-containing material is 0.04: 1;
s2, spray drying the slurry to obtain powder with the median particle size of 20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized air to keep the powder in a suspended state;
s3, spraying the deionized water solution of glucose into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 4 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the mass ratio of the glucose to the Si-containing material is 0.05: 1, the mass ratio of glucose to deionized water is 0.1: 1;
and S4, heating the powder obtained in the step S3 to 1000 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 1h to obtain the cathode material.
Example 3:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiO0.5Uniformly mixing particles, isopropanol, aluminum chloride, graphene and sodium carboxymethylcellulose, and grinding by using a high-energy ball mill to obtain slurry with the median particle size of 0.1 um; wherein, isopropanol and SiO0.5The mass ratio of (A) to (B) is 5: 1, aluminum element and SiO in alumina0.5The mass ratio of (1): 12, graphene and SiO0.5Is 0.01: 1, sodium carboxymethylcellulose and SiO0.5Is 0.04: 1;
s2, spray drying the slurry to obtain powder with the median particle size of 20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying the deionized water solution of glucose into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 4 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the glucose and SiO0.5Mass ratio ofIs 0.05: 1, the mass ratio of glucose to deionized water is 0.1: 1;
and S4, heating the powder obtained in the step S3 to 1000 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 1h to obtain the cathode material.
Example 4:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiO1.5Uniformly mixing the particles, ethanol, lithium hydroxide and polyethylene glycol, and carrying out planetary ball milling and crushing to obtain slurry with a median particle size of 3 um; wherein, ethanol and SiO1.5The mass ratio of (A) to (B) is 3: 1, lithium element and SiO in lithium carbonate1.5The mass ratio of (1): 1, polyethylene glycol and SiO1.5Is 0.1: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 15 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying the deionized water solution of the sucrose into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be sprayed within 2 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the sucrose is in contact with SiO1.5Is 0.1: 1, the mass ratio of the sucrose to the deionized water is 0.2: 1;
and S4, heating the powder obtained in the step S3 to 800 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 3h to obtain the cathode material.
Example 5:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing SiO particles, methanol, calcium carbonate and phenolic resin, and carrying out planetary ball milling and crushing to obtain slurry with the median particle size of 1 um; wherein the mass ratio of methanol to SiO is 2: 1, the mass ratio of aluminum nitrate to SiO is 1: 3, the mass ratio of the phenolic resin to the SiO is 0.2: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 10 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized air to keep the powder in a suspended state;
s3, spraying a methanol solution of polyethylene glycol and polyvinylpyrrolidone into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 2 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the mass ratio of polyethylene glycol to SiO is 0.1: 1, the mass ratio of polyvinylpyrrolidone to SiO is 0.1: 1, the mass ratio of the organic carbon source to the methanol is 0.4: 1;
and S4, heating the powder obtained in the step S3 to 900 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 4h to obtain the cathode material.
Fig. 3 is a scanning electron microscope image of the lithium ion battery anode material of the present embodiment; fig. 4 is a transmission electron microscope photograph of the residual three-dimensional carbon material conductive network after the SiO is etched away from the lithium ion battery negative electrode material of this embodiment. As can be seen from fig. 3 and 4, in the lithium ion battery negative electrode material prepared in the embodiment, the SiO nanoparticles are uniformly dispersed in the three-dimensional carbon material conductive network, the three-dimensional carbon material conductive network has a highly stable structure and higher electronic conductivity, and can inhibit volume expansion of the material in the charging and discharging processes, thereby significantly improving the electrochemical performance of the negative electrode material.
Example 6:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiO0.8Uniformly mixing particles, deionized water, magnesium nitrate, polyvinylpyrrolidone and glucose, and carrying out planetary ball milling and crushing to obtain slurry with the median particle size of 2 um; wherein, the deionized water and SiO0.8The mass ratio of (A) to (B) is 4: 1, magnesium nitrate and SiO0.8The mass ratio of (1): 2, polyvinylpyrrolidone and SiO0.8Is 0.1: 1, glucose and SiO0.8Is 0.1: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 12 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying a methanol solution of polyethylene glycol into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 3 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the polyethylene glycol and SiO0.8Is 0.1: 1, the mass ratio of polyethylene glycol to methanol is 0.2: 1;
and S4, heating the powder obtained in the step S3 to 700 ℃ at a heating rate of 3 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 4h to obtain the cathode material.
Comparative example 1:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing SiO particles, deionized water, carbon nanotubes and polyvinylpyrrolidone, and carrying out planetary ball milling and crushing to obtain SiO slurry with the median particle size of 1 um; wherein the mass ratio of the deionized water to the SiO is 1: 1, the mass ratio of the carbon nano tube to the SiO is 0.1: 1, the mass ratio of polyvinylpyrrolidone to SiO is 0.4: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 5 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying the ethanol solution of the phenolic resin into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 1 hour, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the mass ratio of the phenolic resin to the SiO is 0.2: 1, the mass ratio of the phenolic resin to the ethanol is 0.5: 1;
and S4, heating the powder obtained in the step S3 to 700 ℃ at a heating rate of 1 ℃/min in a nitrogen atmosphere, and carrying out constant-temperature heat treatment for 6h to obtain the cathode material.
Comparative example 2:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing SiO particles, deionized water, magnesium oxide, carbon nanotubes and polyvinylpyrrolidone, and carrying out planetary ball milling and crushing to obtain SiO slurry with the median particle size of 1 um; wherein the mass ratio of the deionized water to the SiO is 1: 1, the mass ratio of magnesium oxide to SiO is 1: 2, the mass ratio of the carbon nano tube to the SiO is 0.1: 1, the mass ratio of polyvinylpyrrolidone to SiO is 0.4: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 5 um;
s3, heating the powder obtained in the step S2 to 700 ℃ at a heating rate of 1 ℃/min in a nitrogen atmosphere, and carrying out constant-temperature heat treatment for 2h to obtain black powder;
s4, adding the black powder obtained in the step S3 into an ethanol solution of phenolic resin, stirring and evaporating to dryness to obtain powder containing a coating layer; wherein the mass ratio of the phenolic resin to the SiO is 0.2: 1, the mass ratio of the phenolic resin to the ethanol is 0.5: 1;
and S5, heating the powder containing the coating layer obtained in the step S4 to 700 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, and carrying out constant-temperature heat treatment for 6h to obtain the cathode material.
Performance comparison experiment:
the materials prepared in the above examples and comparative examples are respectively made into pole pieces as working electrodes and LiPF6The button cell is assembled by using/DMC + EC + DEC (1: 1: 1) as the electrolyte, the charging and discharging cut-off voltage is 0.005-1.5V, and the charging and discharging are carried out at a constant current of 150mA/g, and the result is shown in table 1.
TABLE 1 comparison of initial specific charge capacity, initial coulombic efficiency, 50 cycle retention
| Specific capacity for first charge (mAh/g) | First coulombic efficiency (%) | 50-week cycle maintenance (%) | |
| Example 1 | 1265 | 76 | 89 |
| Example 2 | 1647 | 83 | 75 |
| Example 3 | 1592 | 81 | 72 |
| Example 4 | 581 | 68 | 94 |
| Example 5 | 1318 | 74 | 86 |
| Example 6 | 1506 | 80 | 78 |
| Comparative example 1 | 1053 | 59 | 79 |
| Comparative example 2 | 1229 | 75 | 65 |
As can be seen from Table 1, example 1 is comparable to comparative example 1 in that it is compatible with SiO by additionxHigh temperature disproportionation product SiO2The reacted metal oxide or metal salt can reduce the irreversible reaction of Li in the first discharge process and improve the first coulombic efficiency of the silicon-based composite cathode. Compared with the traditional drying coating method of the comparative example 2, the fluidized bed coating process of the embodiment 1 has the effects of reducing high-temperature sintering steps, simplifying operation flow and improving the cycle performance of the silicon-based composite cathode, because the fluidized bed coating process can realize uniform coating of the particle surface, avoid the contact of a silicon-based material and an electrolyte, and reduce the occurrence of side reactions and structural degradation.
In conclusion, the lithium ion battery cathode material has the advantages of high conductivity, long cycle life and high first-effect, and the preparation method has the advantages of simplicity and convenience in operation, high repeatability, easiness in industrialization and the like.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (8)
1. A preparation method of a lithium ion battery cathode material is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing SiOxUniformly mixing the material, the solvent, the metal compound and the carbon source, mechanically crushing the mixture until the mixture is SiOxThe median particle size of the slurry is 0.1-3 um to obtain slurry; wherein, the metal element M in the metal compound is one of aluminum, magnesium, lithium and calcium;
s2, spray drying the slurry to obtain powder with a median particle size of 5-20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized gas to keep the powder in a suspended state;
s3, spraying the solution containing the organic carbon source into the cavity of the fluidized bed reactor, and cooling after the solution containing the organic carbon source completely reacts to obtain powder containing a coating layer;
s4, raising the temperature of the powder obtained in the step S3 to 700-1000 ℃ at the heating rate of 1-10 ℃/min under the inert atmosphere, and carrying out constant-temperature heat treatment for 1-6h to obtain the cathode material;
the metal compound in the step S1 is at least one of nitrate, sulfate, carbonate, chloride, hydroxide and oxide of the metal element M; wherein, the mass ratio of the metal element M to the SiOx material is 1: 1 to 12;
SiO of the step S1xThe material is SiOxParticles, or a mixture of Si and SiO, wherein 0.5. ltoreq. x.ltoreq.1.5.
2. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the solvent and SiO in the step S1xThe mass ratio of the materials is 1-5: 1; the solvent is at least one of deionized water, ethanol, methanol and isopropanol.
3. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the carbon source and SiO in the step S1xThe mass ratio of the materials is 0.05-0.5: 1; the carbon source is at least one of carbon nano tube, graphene, glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone, phenolic resin and sodium carboxymethylcellulose.
4. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the organic carbon source and SiO of step S3xThe mass ratio of the materials is 0.05-0.2: 1; wherein the organic carbon source is at least one of glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone and phenolic resin.
5. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the mass ratio of the organic carbon source to the solvent in the organic carbon source-containing solution in the step S3 is 0.1-0.5: 1; wherein the solvent is at least one of deionized water, ethanol and methanol.
6. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the reaction time of the solution containing the organic carbon source in the step S3 is 1-4 h.
7. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the mechanical crushing in the step S1 is planetary ball milling or high-energy ball milling or sand milling.
8. The lithium ion battery negative electrode material prepared by the preparation method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010244312.2A CN111430692B (en) | 2020-03-31 | 2020-03-31 | Lithium ion battery cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010244312.2A CN111430692B (en) | 2020-03-31 | 2020-03-31 | Lithium ion battery cathode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111430692A CN111430692A (en) | 2020-07-17 |
| CN111430692B true CN111430692B (en) | 2022-01-18 |
Family
ID=71550178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010244312.2A Active CN111430692B (en) | 2020-03-31 | 2020-03-31 | Lithium ion battery cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111430692B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114068887A (en) * | 2020-07-31 | 2022-02-18 | 兰溪致德新能源材料有限公司 | Negative electrode material for nonaqueous electrolyte secondary battery and method for producing same |
| CN114447325B (en) * | 2020-11-02 | 2023-07-28 | 北京卫蓝新能源科技有限公司 | Porous carbon material, preparation method thereof, negative electrode and lithium metal battery |
| CN113224380B (en) * | 2021-05-13 | 2023-04-07 | 昆山宝创新能源科技有限公司 | Solid electrolyte material, preparation method thereof and battery |
| CN114094055A (en) * | 2021-11-11 | 2022-02-25 | 杭州电子科技大学 | Preparation method of lithium phosphide electrode |
| CN114447292B (en) * | 2021-12-23 | 2023-12-01 | 东莞市鸿德电池有限公司 | Lithium ion battery negative electrode material and preparation method thereof |
| CN114497505B (en) * | 2022-01-28 | 2024-05-10 | 佛山市德方纳米科技有限公司 | Method and device for continuously preparing positive electrode material by spray drying |
| CN116504983A (en) * | 2023-06-21 | 2023-07-28 | 宜宾锂宝新材料有限公司 | Spinel lithium nickel manganese oxide positive electrode material, preparation method thereof and battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101286560A (en) * | 2008-05-30 | 2008-10-15 | 成都中科来方能源科技有限公司 | Composite cathode material for lithium ion cell and preparing method thereof |
| CN103022446A (en) * | 2012-12-19 | 2013-04-03 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon oxide/carbon cathode material of lithium ion battery and preparation method of material |
| CN106450176A (en) * | 2016-08-24 | 2017-02-22 | 上海颐行高分子材料有限公司 | Preparation method of high-capacity negative electrode material |
| JP2018098018A (en) * | 2016-12-12 | 2018-06-21 | 国立大学法人東北大学 | Negative electrode active material for lithium ion secondary battery and manufacturing method thereof, negative electrode, and battery |
| CN108807884A (en) * | 2018-05-31 | 2018-11-13 | 中国科学院过程工程研究所 | A kind of system and method for lithium ion battery negative material carbon coating modification |
| CN109585797A (en) * | 2017-09-29 | 2019-04-05 | 横店集团东磁股份有限公司 | A kind of coating modification electrode material and preparation method thereof |
| CN110844910A (en) * | 2019-11-19 | 2020-02-28 | 北京卫蓝新能源科技有限公司 | Preparation method of silicon-based negative electrode material of lithium ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493438A (en) * | 2018-04-27 | 2018-09-04 | 天津巴莫科技股份有限公司 | A kind of lithium ion battery SiOxBase composite negative pole material and preparation method thereof |
-
2020
- 2020-03-31 CN CN202010244312.2A patent/CN111430692B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101286560A (en) * | 2008-05-30 | 2008-10-15 | 成都中科来方能源科技有限公司 | Composite cathode material for lithium ion cell and preparing method thereof |
| CN103022446A (en) * | 2012-12-19 | 2013-04-03 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon oxide/carbon cathode material of lithium ion battery and preparation method of material |
| CN106450176A (en) * | 2016-08-24 | 2017-02-22 | 上海颐行高分子材料有限公司 | Preparation method of high-capacity negative electrode material |
| JP2018098018A (en) * | 2016-12-12 | 2018-06-21 | 国立大学法人東北大学 | Negative electrode active material for lithium ion secondary battery and manufacturing method thereof, negative electrode, and battery |
| CN109585797A (en) * | 2017-09-29 | 2019-04-05 | 横店集团东磁股份有限公司 | A kind of coating modification electrode material and preparation method thereof |
| CN108807884A (en) * | 2018-05-31 | 2018-11-13 | 中国科学院过程工程研究所 | A kind of system and method for lithium ion battery negative material carbon coating modification |
| CN110844910A (en) * | 2019-11-19 | 2020-02-28 | 北京卫蓝新能源科技有限公司 | Preparation method of silicon-based negative electrode material of lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111430692A (en) | 2020-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111430692B (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN110844910B (en) | Preparation method of silicon-based negative electrode material of lithium ion battery | |
| WO2021134199A1 (en) | Silicon-based negative electrode material for secondary battery, preparation method therefor, and secondary battery | |
| CN112421048A (en) | Method for preparing graphite-coated nano-silicon lithium battery negative electrode material at low cost | |
| JP2022515463A (en) | Silicon oxygen composite negative electrode material, its preparation method and lithium ion battery | |
| CN106252651B (en) | A kind of porous composite negative pole material of lithium ion battery and preparation method thereof | |
| CN111009647B (en) | Lithium borosilicate alloy cathode active material of lithium secondary battery, cathode, preparation and application thereof | |
| WO2023124574A1 (en) | Titanium and zirconium co-doped, carbon-coated lithium iron phosphate material, preparation method therefor and use thereof | |
| EP4394937A1 (en) | Iron-based composite phosphate positive electrode material and preparation method therefor, positive plate and sodium ion battery | |
| CN112599743B (en) | Carbon-coated nickel cobaltate multi-dimensional assembled microsphere negative electrode material and preparation method thereof | |
| CN113690417B (en) | Negative electrode composite material and preparation method and application thereof | |
| CN111710848A (en) | Silica composite negative electrode material, preparation method thereof and lithium ion battery | |
| US20240105937A1 (en) | Preparation method of high-rate lithium iron phosphate positive electrode material | |
| CN109273700A (en) | A kind of silicon based composite material and its preparation method and application | |
| CN112436148A (en) | Having TiO2Mesoporous silica negative electrode material with/C composite coating layer and preparation method thereof | |
| CN118145649A (en) | Preparation method and application of composite silicon-based anode material | |
| CN110797525A (en) | Silica composite and film with protective structure and preparation method and application thereof | |
| CN107342409B (en) | A kind of high-performance anthracite/silicon monoxide/phosphorus composite negative pole material and preparation method thereof | |
| CN117855434A (en) | Pre-magnesium silicon oxide anode material of lithium ion battery and preparation method thereof | |
| CN111747449A (en) | Superfine MoO uniformly bridged inside flaky carbon matrix2Electrode material of nano particles and preparation method and application thereof | |
| CN108878823B (en) | Preparation method of metal olivine coated nano silicon | |
| CN114105145B (en) | Carbon-coated three-dimensional porous silicon anode material and preparation method and application thereof | |
| CN115924878A (en) | Positive electrode material sodium iron phosphate for sodium ion battery and preparation method thereof | |
| CN116314647A (en) | Pre-lithiated silicon oxide anode material and simple preparation method thereof | |
| CN107394130A (en) | The LFP raw powder's production technologies that a kind of three-dimensional porous graphene is modified |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 108, 1st Floor, Building 4, No. 91 Pu'an Road, Doudian, Fangshan District, Beijing 102402 Patentee after: Beijing Weilan New Energy Technology Co.,Ltd. Country or region after: China Address before: No.1 Qihang West Street, Doudian Town, Fangshan District, Beijing Patentee before: BEIJING WELION NEW ENERGY TECHNOLOGY Co.,Ltd. Country or region before: China |