CN117334875B - Silicon-carbon composite anode material and preparation method thereof - Google Patents
Silicon-carbon composite anode material and preparation method thereof Download PDFInfo
- Publication number
- CN117334875B CN117334875B CN202311484138.9A CN202311484138A CN117334875B CN 117334875 B CN117334875 B CN 117334875B CN 202311484138 A CN202311484138 A CN 202311484138A CN 117334875 B CN117334875 B CN 117334875B
- Authority
- CN
- China
- Prior art keywords
- silicon
- monomer
- lithium
- anode material
- carbon composite
- 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
- 239000011870 silicon-carbon composite anode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 33
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011268 mixed slurry Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 239000006258 conductive agent Substances 0.000 claims abstract description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 239000011247 coating layer Substances 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 12
- 239000010405 anode material Substances 0.000 abstract description 10
- 238000000227 grinding Methods 0.000 abstract description 10
- 239000002210 silicon-based material Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 5
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229940006116 lithium hydroxide Drugs 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- HUOBWFKCWUVATL-UHFFFAOYSA-N 1-butyl-2-ethenylbenzene Chemical compound CCCCC1=CC=CC=C1C=C HUOBWFKCWUVATL-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- -1 etc.) Chemical compound 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229940006114 lithium hydroxide anhydrous Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
Abstract
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a silicon-carbon composite anode material and a preparation method thereof. The method comprises the following steps: step 1, taking carboxylic acid monomer, aromatic monomer, cyano monomer and crosslinking monomer, and uniformly mixing to obtain a mixture; step 2, adding water into the mixture to react with the solution of the initiator, and preserving heat after the addition of the mixture to obtain a reaction solution; step 3, adding a neutralizing agent into the reaction liquid to adjust the pH value to 7.0-9.0, and filtering to obtain lithium-containing acrylic resin; step 4, dispersing lithium-containing acrylic resin, nano silicon and a conductive agent into water, and then sanding to obtain mixed slurry; and step 5, drying the mixed slurry in sequence, and calcining and grinding the mixed slurry in an inert atmosphere to obtain the silicon-carbon composite anode material. The silicon-carbon composite anode material provided by the method has good conductivity, and can solve the problems of poor cycle performance and low first-turn efficiency caused by volume expansion in the charging and discharging process of the silicon material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a silicon-carbon composite anode material and a preparation method thereof.
Background
Lithium ion batteries are increasingly used in the fields of power, energy storage, 3C digital codes and the like, and the requirements on performance, such as energy density and multiplying power, are also increasingly high. Silicon has ultrahigh theoretical specific capacity (4200 mAh/g) and lower lithium removal potential (< 0.5V), the voltage platform is slightly higher than that of graphite, surface lithium precipitation is difficult to occur during charging, the safety performance is better, the resources are rich, the silicon is regarded as the next-generation negative electrode material with the most potential, and the market permeability is gradually improved. However, because the silicon material has poor conductivity and expands when being charged and discharged, the volume change is up to 300 percent, so that the silicon material bears great mechanical force in charge and discharge cycles and is gradually pulverized and collapsed, the pulverized negative electrode material can contact with electrolyte to react to consume active lithium, a solid electrolyte interface film formed between the silicon-based material and the electrolyte is gradually thickened, and the pulverization and collapse also can influence the connection between the active material and the current collector to be unfavorable for electron transmission, thereby leading to rapid attenuation of the battery capacity and finally leading to low first-turn efficiency and poor cycle performance of the battery. In order to solve the above problems, researchers have attempted to improve the preparation of carbon-silicon composite anode materials by introducing carbon materials into silicon-based anode materials.
At present, a silicon-carbon composite anode material is obtained by in-situ compounding a silicon material and a carbon source and then carbonizing, a carbon coating layer can be formed on the surface of the silicon-carbon composite anode material, the volume expansion of the silicon-based anode material can be buffered due to the existence of the carbon coating layer, the silicon-based anode material is prevented from being in direct contact with electrolyte, a stable reaction interface is provided, the conductivity of the silicon-based anode material can be improved, and the conductivity of the silicon-based anode material is improved. For example, chinese patent CN111384378B discloses a method for preparing a silicon-carbon negative electrode material by vapor deposition reaction of a gaseous organic carbon source (ethylene, acetylene, etc.), silicon oxide and aluminum powder, which better reduces the expansion rate of the obtained negative electrode material and has better electrochemical performance. For example, the silicon-carbon anode material is obtained by mixing, calcining and carbonizing a carbon source and a silicon source in Chinese patent application CN 111755680A. However, the above method has the following problems: the requirements on equipment are high, and the preparation process is complex; (2) The carbon source used is an organic gas carbon source, and the organic gas is not easy to store, so that the problem of high risk exists.
The first-ring efficiency can be improved by doping lithium in the carbon coating layer, but the existing lithium doping method cannot dope a large amount of lithium, and the uniform doping of lithium cannot be well realized, so that the improvement on the first-ring efficiency of the battery is limited. In addition, the conductivity can be improved by doping the carbon coating layer with nitrogen element, but the uniform doping of nitrogen element in the carbon coating layer cannot be well realized by the existing nitrogen doping method, and the conductivity of the silicon-carbon composite anode material is improved only to a limited extent, such as in Chinese patent CN114824232B.
Disclosure of Invention
In order to solve the problems that the silicon material has poor conductivity, poor first circle efficiency and poor cycle performance caused by volume expansion when used for a battery anode material, the existing preparation process of the silicon-carbon composite anode material is complex, the preparation process has safety problems, the existing preparation method can not well realize the uniform doping of lithium and nitrogen in a carbon coating layer of the silicon-carbon composite anode material, and the like, the invention provides the silicon-carbon composite anode material and the preparation method. The specific technical scheme provided by the invention is as follows:
in a first aspect of the present invention, a method for preparing a silicon-carbon composite anode material is provided, comprising the steps of:
step 1, taking carboxylic acid monomer, aromatic monomer, cyano monomer and crosslinking monomer, and uniformly mixing to obtain a mixture;
step 2, adding water, and then dropwise adding a solution of the mixture and the initiator to react to obtain a reaction solution;
step 3, adding a neutralizing agent into the reaction liquid to adjust the pH value to 7.0-9.0, and filtering to obtain lithium-containing acrylic resin;
step 4, dispersing lithium-containing acrylic resin, nano silicon and a conductive agent into water, and then sanding to obtain mixed slurry;
and step 5, drying the mixed slurry in sequence, and calcining and grinding the mixed slurry in an inert atmosphere to obtain the silicon-carbon composite anode material.
Specifically, the content of carboxylic acid monomer in the mixture in the step 1 is 60-80wt%, the content of cyano monomer is 5-25wt%, the content of aromatic monomer is 5-15wt% and the content of crosslinking monomer is 0.1-1.0wt%;
specifically, the initiator contained in the solution of the initiator in the step 1 is inorganic peroxide, and the inorganic peroxide is at least one of ammonium persulfate, sodium persulfate and potassium persulfate;
specifically, the carboxylic acid monomer in the step 1 is at least one of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid;
specifically, the aromatic monomer in the step 1 is at least one of styrene, 2-methyl styrene, 4-methyl styrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene and 4- (n-quinolyl) styrene;
specifically, the cyano monomer in the step 1 is at least one selected from acrylonitrile and methacrylonitrile;
specifically, the crosslinking monomer in the step 1 is at least one of N-methylolacrylamide, N-hydroxyethyl acrylamide, glycidyl acrylate and glycidyl methacrylate.
Specifically, the amount of the initiator contained in the initiator solution in the step 2 is 0.1-2wt% of the mass of the mixture in the step 1, the content of the initiator in the initiator solution is 0.5-5wt%, and the solvent in the initiator solution is water;
specifically, the dripping time in the step 2 is 1-3h, and the dripping time is controlled to control the dripping speed, wherein the dripping speed can influence the reaction speed, and too large dripping speed can cause too severe reaction and easily cause thermal runaway; too small a dropping rate can affect production efficiency;
specifically, the water in the step 2 is added in an amount which is 3-20 times of the mass of the mixture;
specifically, the temperature of the reaction in the step 2 is 75-90 ℃;
specifically, the time of heat preservation in the step 2 is 1-2 hours.
Specifically, the pH is controlled in step 3 because the pH of the unneutralized acrylic resin is low (about 2), the viscosity of the mixed slurry obtained after mixing it with the nano-silicon and conductive agent is low at a low pH, the stability is poor, and the doping amount of lithium is small when the pH is below 7.0; the pH is higher than 9.0, the alkalinity is too strong, and the structural damage of the added nano silicon can be caused during drying and calcining;
specifically, the neutralizer in the step 3 is lithium metal hydroxide, and the lithium metal hydroxide is at least one selected from lithium hydroxide monohydrate and anhydrous lithium hydroxide.
Specifically, in the step 4, the content of the lithium-containing acrylic resin in the mixed slurry is 50-80wt%, the content of the nano silicon is 18-40wt% and the content of the conductive agent is 2-10wt%, and the solid content of the mixed slurry is 10-30wt%.
Specifically, the conductive agent in step 4 is at least one selected from carbon black, conductive graphite, carbon nanotubes and graphene.
Specifically, the particle size of the nano silicon in the step 4 is 20-500nm, and the specific surface area is 10-100m 2 /g。
Specifically, the drying temperature in the step 5 is 25-85 ℃ and the drying time is 8-24 h.
Specifically, the calcining process in step 5 is as follows: firstly, heating to 120-170 ℃ from room temperature, and preserving heat for 1-3 hours; heating from 120-170 ℃ to 650-800 ℃, and preserving heat for 3-5 hours;
specifically, the inert atmosphere in the step 5 is a nitrogen atmosphere or an argon atmosphere.
In a second aspect of the present invention, there is provided a silicon-carbon composite anode material prepared by any one of the methods described above.
In the preparation process, an initiator is decomposed at a certain temperature to generate active free radicals, and a carboxylic acid monomer, an aromatic monomer, a cyano monomer and a crosslinking monomer are initiated to generate an acrylic copolymer through copolymerization, wherein the generated acrylic copolymer contains carboxyl, aromatic, cyano and crosslinking functional groups;
the carboxyl functional group on the acrylic acid copolymer reacts with the lithium neutralizer to obtain lithium-containing acrylic resin, so that lithium can be uniformly dispersed in the lithium-containing acrylic resin, and the doping amount of the lithium in the carbonization layer can be increased and the lithium can be uniformly doped in the carbonization layer;
the lithium-containing acrylic resin is of a linear structure, has better wettability, is beneficial to the dispersion of nano silicon and a conductive agent in the resin, and is beneficial to the improvement of the structural stability of the carbon coating;
in addition, due to the existence of carboxyl, cyano, aromatic and other functional groups, the lithium-containing acrylic resin can be uniformly adsorbed on the surfaces of the nano silicon and the conductive agent, and a uniform and compact carbon coating layer can be formed after high-temperature carbonization, so that the conductivity of the prepared carbon silicon negative electrode material is improved, and the expansion of the silicon material in the carbon silicon negative electrode material is inhibited;
the lithium-containing acrylic resin contains a large number of carboxyl and cyano functional groups, has good bonding performance on nano silicon, contains aromatic functional groups and has good bonding performance on conductive agents, and can be used as a bridge to tightly combine the silicon nano material and the conductive material together, thereby being beneficial to forming a uniform and stable carbon coating layer;
in addition, the existence of crosslinking functional groups (hydroxyl groups or epoxy groups and the like) can generate self-crosslinking, so that the lithium-containing acrylic acid copolymer adsorbed on the surfaces of the nano silicon and the conductive agent can be crosslinked with each other to form a network structure, and the compactness and the structural stability of the carbon coating layer are further improved.
The method has the following beneficial effects:
1. the silicon-carbon composite anode material prepared by the method forms a uniform, compact and stable carbon coating layer on the surface, realizes a large amount of doping of lithium in the carbon coating layer and uniform doping of lithium and nitrogen in the carbon coating layer, well solves the problems of poor first-turn efficiency and poor cycle performance caused by volume expansion when the silicon material is used for a lithium ion battery, and has good conductivity, high first-turn efficiency and good cycle stability;
2. the method is simple and easy to operate, has low requirements on equipment, has high safety in the preparation process, is suitable for mass production, and is beneficial to improving the popularization and the utilization of the silicon-carbon composite anode material.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
Step 1, taking 60 parts of acrylic acid monomer, 15 parts of styrene, 24.9 parts of acrylonitrile and 0.1 part of N-methylol acrylamide, uniformly mixing to obtain a mixture, and taking 0.1 part of potassium persulfate to dissolve in 19 parts of deionized water to obtain a mixed solution B;
step 2, heating 800 parts of deionized water to 90 ℃, simultaneously dropwise adding the mixture and the mixed solution B into the deionized water, finishing dropwise adding within 1 hour, and keeping the temperature for 2 hours after finishing dropwise adding to obtain a reaction solution;
step 3, slowly adding a lithium hydroxide monohydrate solution (the mass concentration is 15%) into the reaction solution until the pH value is adjusted to 7.0, and filtering to obtain lithium-containing acrylic resin;
step 4, dispersing 60 parts of lithium-containing acrylic resin, 35 parts of nano silicon and 5 parts of conductive carbon black (Super P) into 900 parts of water, and then performing sand grinding to obtain mixed slurry;
and 5, drying the mixed slurry at 25 ℃ for 24 hours, calcining under a nitrogen atmosphere, wherein the calcining process is to heat up to 150 ℃ for 2 hours, heat up to 700 ℃ for 3 hours, and then grinding after cooling to room temperature, so as to obtain the silicon-carbon composite anode material.
Example 2
Step 1, taking 70 parts of methacrylic acid monomer, 10 parts of 2-methyl styrene, 19.5 parts of methacrylonitrile and 0.5 part of N-hydroxyethyl acrylamide, uniformly mixing to obtain a mixture, and taking 1 part of sodium persulfate to dissolve in 38 parts of water to obtain a mixed solution B;
step 2, heating 800 parts of deionized water to 80 ℃, simultaneously dropwise adding the mixture and the mixed solution B into the deionized water, finishing dropwise adding within 2 hours, and keeping the temperature for 1 hour after finishing dropwise adding to obtain a reaction solution;
step 3, slowly adding lithium hydroxide solution (the mass concentration is 15%) into the reaction solution until the pH value is adjusted to 8.0, and filtering to obtain lithium-containing acrylic resin;
step 4, 50 parts of lithium-containing acrylic resin, 40 parts of nano silicon, 5 parts of conductive carbon black and 5 parts of conductive graphite are taken to be dispersed into 400 parts of water, and then sand grinding is carried out to obtain mixed slurry;
and 5, drying the mixed slurry at 55 ℃ for 12 hours, calcining under a nitrogen atmosphere, wherein the calcining process is to heat up to 120 ℃ for 3 hours, heat up to 650 ℃ for 5 hours, cool down to room temperature and grind to obtain the silicon-carbon composite anode material.
Example 3
Step 1, taking 80 parts of itaconic acid, 5 parts of 4-methylstyrene, 14 parts of methacrylonitrile and 1 part of glycidyl methacrylate, uniformly mixing to obtain a mixture, and taking 2 parts of ammonium persulfate to dissolve in 38 parts of water to obtain a mixed solution B;
step 2, heating 800 parts of deionized water to 85 ℃, simultaneously dropwise adding the mixture and the mixed solution B into the deionized water, finishing dropwise adding within 2 hours, and keeping the temperature for 1.5 hours after finishing dropwise adding to obtain a reaction solution;
step 3, slowly adding a lithium hydroxide monohydrate solution (the mass concentration is 15%) into the reaction solution until the pH value is adjusted to 9.0, and filtering to obtain lithium-containing acrylic resin;
step 4, dispersing 80 parts of lithium-containing acrylic resin, 18 parts of nano silicon and 2 parts of carbon nano tubes into 900 parts of water, and then performing sand grinding to obtain mixed slurry;
and 5, drying the mixed slurry at 85 ℃ for 8 hours, calcining under a nitrogen atmosphere, wherein the calcining process is to heat up to 170 ℃ for 1 hour, heat up to 800 ℃ for 1 hour, cool down to room temperature and grind to obtain the silicon-carbon composite anode material.
Example 4
Step 1, taking 80 parts of acrylic acid monomer, 14.9 parts of styrene, 5 parts of acrylonitrile and 0.1 part of N-methylol acrylamide, uniformly mixing to obtain a mixture, and taking 0.5 part of ammonium persulfate to dissolve in 38 parts of water to obtain a mixed solution B;
step 2, heating 800 parts of deionized water to 75 ℃, simultaneously dropwise adding the mixture and the mixed solution B into the deionized water, finishing dropwise adding within 3 hours, and keeping the temperature for 2 hours after finishing dropwise adding to obtain a reaction solution;
step 3, adding lithium hydroxide solution (the mass concentration is 15%) into the reaction solution until the pH value is adjusted to 8.0, and filtering to obtain lithium-containing acrylic resin;
step 4, dispersing 60 parts of lithium-containing acrylic resin, 30 parts of nano silicon and 10 parts of conductive carbon black into 100 parts of water, and then performing sanding to obtain mixed slurry;
and 5, drying the mixed slurry at 25 ℃ for 12 hours, calcining under a nitrogen atmosphere, wherein the calcining process is to heat up to 150 ℃ for 2 hours, heat up to 700 ℃ for 3 hours, and then grinding after cooling to room temperature, so as to obtain the silicon-carbon composite anode material.
Comparative example 1
Step 1, taking 60 parts of acrylic acid monomer, 15 parts of styrene, 24.9 parts of acrylonitrile and 0.1 part of N-methylol acrylamide, uniformly mixing to obtain a mixture, and taking 0.1 part of potassium persulfate to dissolve in 19 parts of deionized water to obtain a mixed solution B;
step 2, heating 800 parts of deionized water to 90 ℃, simultaneously dropwise adding the mixture and the mixed solution B into the deionized water, finishing dropwise adding within 1 hour, and keeping the temperature for 2 hours after finishing dropwise adding to obtain a reaction solution;
step 3, slowly adding sodium carbonate solution (the mass concentration is 15%) into the reaction solution until the pH value is adjusted to 7.0, and filtering to obtain sodium-containing acrylic resin;
step 4, dispersing 60 parts of sodium-containing acrylic resin, 35 parts of nano silicon and 5 parts of conductive carbon black into 900 parts of water, and then performing sand grinding to obtain mixed slurry;
and 5, drying the mixed slurry at 25 ℃ for 24 hours, calcining under a nitrogen atmosphere, wherein the calcining process is to heat up to 150 ℃ for 2 hours, heat up to 700 ℃ for 3 hours, and then grinding after cooling to room temperature, so as to obtain the silicon-carbon composite anode material.
Comparative example 2
Step 1, taking 60 parts of acrylic acid monomer, 15 parts of styrene and 25 parts of acrylonitrile, uniformly mixing to obtain a mixture, and taking 0.1 part of potassium persulfate to dissolve in 19 parts of deionized water to obtain a mixed solution B;
step 2, heating 800 parts of deionized water to 90 ℃, simultaneously dropwise adding the mixture and the mixed solution B into the deionized water, finishing dropwise adding within 1 hour, and keeping the temperature for 2 hours after finishing dropwise adding to obtain a reaction solution;
step 3, slowly adding a lithium hydroxide monohydrate solution (the mass concentration is 15%) into the reaction solution until the pH value is adjusted to 7.0, and filtering to obtain lithium-containing acrylic resin;
step 4, dispersing 60 parts of lithium-containing acrylic resin, 35 parts of nano silicon and 5 parts of conductive carbon black into 900 parts of water, and then performing sanding to obtain mixed slurry;
and 5, drying the mixed slurry at 25 ℃ for 24 hours, calcining under a nitrogen atmosphere, wherein the calcining process is to heat up to 150 ℃ for 2 hours, heat up to 700 ℃ for 3 hours, and then grinding after cooling to room temperature, so as to obtain the silicon-carbon composite anode material.
Comparative example 3
Step 1, dispersing 60 parts of market purchased polyacrylic resin (Mw=450,000) in 800 parts of deionized water, heating to 90 ℃, slowly adding a lithium hydroxide monohydrate solution (the mass concentration is 15%) until the pH is regulated to 7.0, and filtering to obtain the commercial lithium-containing acrylic resin;
step 2, dispersing 60 parts of commercial lithium-containing acrylic resin, 35 parts of nano silicon and 5 parts of conductive carbon black into 900 parts of water, and then performing sanding to obtain mixed slurry;
and step 3, drying the mixed slurry at 25 ℃ for 24 hours, calcining under a nitrogen atmosphere, wherein the calcining process is to heat up to 150 ℃ for 2 hours, heat up to 700 ℃ for 3 hours, cool down to room temperature and grind to obtain the silicon-carbon composite anode material.
The properties of the silicon carbon composite anode materials obtained in examples and comparative examples were tested, and the test results are shown in table 1.
Uniformly dispersing the silicon-carbon composite anode material obtained in the examples and the comparative examples, conductive carbon black (Super P) and PAA binder (Yindile LA 136D) in deionized water according to a mass ratio of 93:2:5, controlling the solid content of slurry to be 45%, coating the slurry on a copper foil current collector by adopting a mature process, and obtaining an anode piece after vacuum drying, rolling and cutting. The prepared negative electrode plate is assembled into a button cell for electrochemical performance detection according to the button cell preparation process familiar to the technical personnel in the industry, and the test results are shown in table 2.
Table 1 performance test of silicon carbon composite anode materials prepared in examples and comparative examples
| Sample of | Sheet resistivity (Ω mm) | Lithium doping amount (%) |
| Example 1 | 3.9 | 0.5 |
| Example 2 | 4.2 | 0.3 |
| Example 3 | 4.5 | 0.6 |
| Example 4 | 4.0 | 0.4 |
| Comparative example 1 | 4.4 | 0 |
| Comparative example 2 | 4.2 | 0.4 |
| Comparative example 3 | 8.3 | 0.5 |
As can be seen from Table 1, the silicon-carbon composite anode material prepared by the method has better conductivity and higher doping amount of lithium element. Comparative example 3 carbon coating layer has poor conductivity because no nitrogen element is introduced, so that the sheet resistivity is high.
Table 2 results of electrochemical performance test of silicon-carbon composite anode materials in examples and comparative examples
As can be seen from Table 2, the silicon-carbon anode material prepared by the method has higher first-time capacity, high first-time efficiency and higher cycle capacity retention rate. In comparative example 1, no lithium-containing neutralizer is used for neutralization, no lithium element is contained in the carbon coating layer, and negative electrode active material and electrolyte can undergo side reaction in the first charge and discharge process to cause lithium loss, and undoped lithium cannot supplement the lithium loss in the first charge and discharge process, so that the first capacity is low and the first cycle efficiency is low; in the comparative example 2, the acrylic resin does not contain a crosslinking functional group, so that a carbon coating layer formed after carbonization of the acrylic resin is loose, the effect of inhibiting the volume expansion of a silicon material in a silicon-carbon negative electrode material in the charge-discharge process is relatively poor, and the coated carbon layer is easy to collapse under stress, so that the cycle performance is relatively poor; comparative example 3 since the commercial acrylic resin contained only the carboxyl functional group, nitrogen was not introduced into the carbon coating layer, and conductivity was poor, so that the conductivity of the electrode sheet was low, and in addition, the carbon coating layer formed by the commercial acrylic resin containing no crosslinking functional group was poor in structural stability, so that the cycle performance was also relatively poor.
Claims (5)
1. The preparation method of the silicon-carbon composite anode material is characterized by comprising the following steps of:
step 1, taking carboxylic acid monomer, aromatic monomer, cyano monomer and crosslinking monomer, and uniformly mixing to obtain a mixture;
step 2, adding water into the mixture to react with the solution of the initiator, and preserving heat after the addition of the mixture to obtain a reaction solution;
step 3, adding a neutralizing agent into the reaction liquid to adjust the pH value to 7.0-9.0, and filtering to obtain lithium-containing acrylic resin;
step 4, dispersing lithium-containing acrylic resin, nano silicon and a conductive agent into water, and then sanding to obtain mixed slurry;
step 5, the mixed slurry is dried, calcined and ground in an inert atmosphere in sequence, and the silicon-carbon composite anode material is obtained; the silicon-carbon composite anode material comprises a carbon coating layer, wherein lithium and nitrogen are uniformly doped in the carbon coating layer;
wherein the carboxylic acid monomer in the step 1 is at least one of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid;
the aromatic monomer in the step 1 is at least one of styrene, 2-methyl styrene, 4-methyl styrene, 2- (N-butyl) styrene and 4- (N-butyl) styrene, the cyano monomer is at least one of acrylonitrile and methacrylonitrile, and the crosslinking monomer is at least one of N-methylolacrylamide, N-hydroxyethyl acrylamide, glycidyl acrylate and glycidyl methacrylate;
the neutralizer in the step 3 is lithium metal hydroxide;
the content of lithium-containing acrylic resin in the mixed slurry in the step 4 is 50-80wt%, the content of nano silicon is 18-40wt% and the content of the conductive agent is 2-10wt%.
2. The method for preparing a silicon-carbon composite anode material according to claim 1, wherein the content of carboxylic acid monomer in the mixture in step 1 is 60-80wt%, the content of cyano monomer is 5-25wt%, the content of aromatic monomer is 5-15wt% and the content of crosslinking monomer is 0.1-1.0wt%.
3. The method for preparing a silicon-carbon composite anode material according to claim 1, wherein the initiator is contained in the solution of the initiator in the step 2 in an amount of 0.1-2wt% based on the mass of the mixture in the step 1.
4. The method for preparing a silicon-carbon composite anode material according to claim 1, wherein the solid content of the mixed slurry in the step 4 is 10-30wt%.
5. A silicon-carbon composite anode material prepared by the method of any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311484138.9A CN117334875B (en) | 2023-11-09 | 2023-11-09 | Silicon-carbon composite anode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311484138.9A CN117334875B (en) | 2023-11-09 | 2023-11-09 | Silicon-carbon composite anode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117334875A CN117334875A (en) | 2024-01-02 |
| CN117334875B true CN117334875B (en) | 2024-03-26 |
Family
ID=89293358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311484138.9A Active CN117334875B (en) | 2023-11-09 | 2023-11-09 | Silicon-carbon composite anode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117334875B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109860596A (en) * | 2018-12-27 | 2019-06-07 | 上海三瑞高分子材料股份有限公司 | A kind of lithium battery silicon-based anode slurry and preparation method thereof |
| CN110828805A (en) * | 2019-11-14 | 2020-02-21 | 郑州中科新兴产业技术研究院 | Nitride-doped silicon-based composite material and preparation method thereof |
| CN113066972A (en) * | 2021-03-19 | 2021-07-02 | 厦门高容新能源科技有限公司 | Lithium-supplementing silicon material, preparation method thereof, electrode containing lithium-supplementing silicon material and battery |
| JP2022062804A (en) * | 2020-10-09 | 2022-04-21 | 株式会社村田製作所 | Composite material and lithium ion secondary battery |
| CN115440982A (en) * | 2022-09-19 | 2022-12-06 | 郑州中科新兴产业技术研究院 | High-performance silicon-carbon negative electrode material for lithium battery and preparation method thereof |
| CN116314658A (en) * | 2023-01-17 | 2023-06-23 | 中钢集团鞍山热能研究院有限公司 | Preparation method of silicon-carbon composite material containing nitrogen coated carbon layer |
| CN117003952A (en) * | 2022-04-27 | 2023-11-07 | 深圳市研一新材料有限责任公司 | Dry electrode binder and preparation method and application thereof |
-
2023
- 2023-11-09 CN CN202311484138.9A patent/CN117334875B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109860596A (en) * | 2018-12-27 | 2019-06-07 | 上海三瑞高分子材料股份有限公司 | A kind of lithium battery silicon-based anode slurry and preparation method thereof |
| CN110828805A (en) * | 2019-11-14 | 2020-02-21 | 郑州中科新兴产业技术研究院 | Nitride-doped silicon-based composite material and preparation method thereof |
| JP2022062804A (en) * | 2020-10-09 | 2022-04-21 | 株式会社村田製作所 | Composite material and lithium ion secondary battery |
| CN113066972A (en) * | 2021-03-19 | 2021-07-02 | 厦门高容新能源科技有限公司 | Lithium-supplementing silicon material, preparation method thereof, electrode containing lithium-supplementing silicon material and battery |
| CN117003952A (en) * | 2022-04-27 | 2023-11-07 | 深圳市研一新材料有限责任公司 | Dry electrode binder and preparation method and application thereof |
| CN115440982A (en) * | 2022-09-19 | 2022-12-06 | 郑州中科新兴产业技术研究院 | High-performance silicon-carbon negative electrode material for lithium battery and preparation method thereof |
| CN116314658A (en) * | 2023-01-17 | 2023-06-23 | 中钢集团鞍山热能研究院有限公司 | Preparation method of silicon-carbon composite material containing nitrogen coated carbon layer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117334875A (en) | 2024-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111048769B (en) | Double-layer coated silicon-based composite anode material and preparation method thereof | |
| CN106711461A (en) | Spherical porous silicon/carbon composite material as well as preparation method and application thereof | |
| CN109004220B (en) | Boric acid compound modified lithium ion battery silicon cathode and preparation method thereof | |
| CN108470884B (en) | Lithium ion battery electrode prepared from water-based binder | |
| CN111682173A (en) | Composite material of multi-heteroatom co-doped carbon shell coated silicon and preparation method thereof | |
| CN108321438B (en) | Full-graphite lithium-sulfur battery and preparation method thereof | |
| CN111697218A (en) | Silicon-carbon negative electrode material and preparation method thereof | |
| CN112110448A (en) | Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof | |
| CN1339838A (en) | Carbon negative electrode material of lithium ion cell and its preparing method and use | |
| CN115714170B (en) | Preparation method of high-energy-density quick-charge anode material | |
| CN111430712A (en) | Preparation method of novel silicon-based negative electrode binder of lithium ion battery | |
| CN110265653B (en) | Preparation method of layered silicon-carbon material for battery cathode | |
| CN115295802A (en) | Adhesive, preparation method thereof and application thereof in lithium ion battery | |
| CN110752361B (en) | Preparation method of modified silicon-based negative electrode material of lithium battery | |
| CN117334875B (en) | Silicon-carbon composite anode material and preparation method thereof | |
| WO2014044039A1 (en) | Composition silicate anode material, lithium battery and preparation method for the same, and communication device | |
| CN113745519B (en) | Silicon-based negative electrode material with artificial SEI film and preparation method and application thereof | |
| CN111834611A (en) | Preparation method of uniformly dispersed silicon-carbon composite negative electrode material based on magnesiothermic reduction | |
| WO2022204978A1 (en) | Negative electrode material, negative electrode sheet, electrochemical apparatus and electronic apparatus | |
| CN113735127A (en) | Negative electrode material, preparation method thereof, negative plate and lithium ion battery | |
| CN107959007B (en) | Preparation method of graphene-silicon-coated lithium ion battery negative electrode material | |
| CN114156471A (en) | Graphite negative electrode material and preparation method and application thereof | |
| CN112397701A (en) | Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof | |
| CN117525372B (en) | Lithium battery anode material based on metal organic framework material | |
| CN114039042B (en) | Silicon oxide negative electrode material with artificial SEI film, and preparation method and application thereof |
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 |