CN114122356A - Modified hard carbon negative electrode material with improved performance and preparation method thereof - Google Patents
Modified hard carbon negative electrode material with improved performance and preparation method thereof Download PDFInfo
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- CN114122356A CN114122356A CN202111314245.8A CN202111314245A CN114122356A CN 114122356 A CN114122356 A CN 114122356A CN 202111314245 A CN202111314245 A CN 202111314245A CN 114122356 A CN114122356 A CN 114122356A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 94
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 37
- 239000011247 coating layer Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims description 105
- 239000011248 coating agent Substances 0.000 claims description 80
- 238000000576 coating method Methods 0.000 claims description 80
- 239000007787 solid Substances 0.000 claims description 40
- 239000011261 inert gas Substances 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- 239000011268 mixed slurry Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 claims description 19
- 229910000149 boron phosphate Inorganic materials 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 229920000767 polyaniline Polymers 0.000 claims description 13
- 239000004800 polyvinyl chloride Substances 0.000 claims description 13
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229920001568 phenolic resin Polymers 0.000 claims description 11
- 239000005011 phenolic resin Substances 0.000 claims description 11
- 239000004417 polycarbonate Substances 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 10
- 238000012856 packing Methods 0.000 claims description 10
- 229920001197 polyacetylene Polymers 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920003026 Acene Polymers 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007849 furan resin Substances 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229940116351 sebacate Drugs 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 238000009830 intercalation Methods 0.000 abstract description 9
- 230000002687 intercalation Effects 0.000 abstract description 9
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001291 vacuum drying 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
- H01M4/58—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/604—Polymers containing aliphatic main chain polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a modified hard carbon negative electrode material with improved performance and a preparation method thereof, wherein the modified hard carbon negative electrode material prepared by the preparation method comprises a hard carbon matrix, a first coating layer coated on at least one part of the surface of the hard carbon matrix and a second coating layer coated on at least one part of the surface of the first coating layer; the prepared modified hard carbon negative electrode material has generally high first charge-discharge efficiency, good lithium intercalation and lithium deintercalation performance and excellent cycle capacity retention rate.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a modified hard carbon negative electrode material with improved performance and a preparation method thereof.
Background
The lithium ion battery has the advantages of high specific energy, high working voltage, wide application temperature range, low self-discharge rate, long cycle life, no pollution, good safety performance and the like, and is widely applied to various fields in recent years. The conventional lithium ion battery generally adopts graphite or silicon-carbon as a negative electrode material to ensure that lithium ions are efficiently de-intercalated in a positive electrode and a negative electrode in the battery circulation process.
However, since the graphite material has a high graphitization degree and a high layered structure, the lithium intercalation space is small, so that the lithium intercalation capacity of the graphite is low, and the cycle performance of the graphite is poor, so that the energy density of the battery cannot be further improved greatly, and the use requirement of people is difficult to meet. Therefore, there is a need for improvement of conventional negative electrode materials for lithium ion batteries.
Disclosure of Invention
In view of the above, the present invention is directed to the defects in the prior art, and the main object of the present invention is to provide a modified hard carbon negative electrode material with improved performance and a preparation method thereof, which can increase the lithium intercalation space of a graphite material, thereby increasing the lithium intercalation capacity of the graphite material, improving the cycle performance of a battery, and increasing the energy density of the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a modified hard carbon negative electrode material with improved performance comprises a hard carbon matrix, a first coating layer coated on at least one part of the surface of the hard carbon matrix, and a second coating layer coated on at least one part of the surface of the first coating layer;
the hard carbon matrix comprises a precursor, crystalline flake graphite and boron phosphate, wherein the precursor comprises any one or more of phenolic resin, polycarbonate, epoxy resin, acrylic resin, polyvinyl chloride and polyformaldehyde;
the first coating comprises a first coating and sulfur powder, the first coating comprises any one or more of polystyrene, polyvinyl chloride, polyethylene, polyacrylonitrile, polyaniline, polyacetylene and polyvinylidene chloride, and the molded first coating has-S-C-bond and-S-S-bond;
the second coating layer comprises a second coating, and the second coating comprises any one or more of carboxymethyl cellulose, polyphenylene sulfide, polyvinylidene fluoride, furan resin, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile, polyethylene oxide, polypropylene oxide, polyethylene glycol succinate, polyethylene glycol sebacate, polyethylene glycol imine, polyacetylene, polyaniline, polypyrrole, polyacene, polythiophene, poly m-phenylenediamine, polyimide, polyvinyl pyrrolidone, asphalt and styrene butadiene rubber.
Preferably, the mass of the crystalline flake graphite and the mass of the boron phosphate are respectively 0.5-5% and 0.1-0.5% of the mass of the precursor, the D50 of crystalline flake graphite powder is less than or equal to 5 μm, the mass of the first coating is 1-8% of the mass of the hard carbon matrix, and the mass of the second coating is 1-15% of the mass of the hard carbon matrix.
Preferably, the mass of the crystalline flake graphite and the mass of the boron phosphate are respectively 2% and 0.2% of the mass of the precursor, the mass of the first coating is 6% of the mass of the hard carbon matrix, and the mass of the second coating is 12% of the mass of the hard carbon matrix.
Preferably, the precursor consists of phenolic resin and polycarbonate, and the mass ratio of the phenolic resin to the polycarbonate is 2: 1-1.5.
As a preferable scheme, the first coating is composed of polystyrene, polyvinyl chloride and polyaniline, and the mass ratio of the first coating to the sulfur powder is 1: 1.
preferably, the second coating is composed of carboxymethyl cellulose, polyvinylidene fluoride and polyphenylene sulfide, and the mass ratio of the carboxymethyl cellulose to the polyvinylidene fluoride to the polyphenylene sulfide is 4: 1: 1.
a preparation method of a modified hard carbon negative electrode material with improved performance is used for preparing the modified hard carbon negative electrode material with improved performance for a lithium ion battery, and is characterized by comprising the following steps:
(1) adding the precursor, the crystalline flake graphite powder and the boron phosphate into isopropanol, uniformly stirring, standing at normal temperature for 30-60min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 1-50h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at the heating rate of 2-5 ℃/min, preserving heat for 1h, then heating to 500-1500 ℃ at the heating rate of 0.1-3 ℃/min, preserving heat for 2-24h, and then naturally cooling to room temperature to obtain hard carbon;
(3) carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m;
(4) dissolving the first coating in a solvent, stirring until the first coating is uniformly dispersed to obtain a solution, wherein the solvent is one or more of N-methylpyrrolidone, xylene, toluene and dimethylformamide, adding a hard carbon matrix into the solution, stirring to obtain a mixed slurry, then placing the mixed slurry in a wet packing machine, and drying in an inert gas atmosphere at the drying temperature of 110-200 ℃. Wherein the heating rate can be 1-10 ℃/min to obtain solid powder, then the solid powder is mixed with a certain mass of sulfur powder, and the mixture is subjected to heat treatment for 2-8h in the atmosphere of inert gas, wherein the heat treatment temperature is 250-;
(5) and putting the negative electrode blank and the second coating together into a mixing machine for mixing at the rotation speed of 500-3500r/min for 15-120min, then heating to 500-1000 ℃ at the heating speed of 0.1-10 ℃/min under the protection of inert gas, naturally cooling to 200 ℃, then continuing heating to 800-1500 ℃ at the heating speed of 0.1-10 ℃/min, preserving heat for 2-10h, and naturally cooling to room temperature.
As a preferable scheme, the curing time of the step (1) is 35 h.
Preferably, the drying temperature of the step (4) is 160 ℃, the heating rate is 5 ℃/min, and the mass ratio of the first coating to the solvent is 1: 1.
as a preferable scheme, the heat preservation time of the step (5) is 7 h.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
the hard carbon substrate is selected as the shell material, the hard carbon substrate has a larger interlayer spacing structure, the lithium intercalation space is promoted, the lithium intercalation capacity of the shell material is improved, the first coating layer is matched to coat at least one part of the surface of the hard carbon substrate, the formed first coating layer has an-S-C-bond and an-S-S-bond, the first coating layer has higher elasticity and toughness due to the-C-S-bond, the expansion and contraction of the hard carbon substrate in the lithium intercalation and deintercalation process can be adapted, the loss of active ions caused by the breakage and repair of an SEI film is reduced, the protection effect is achieved, the capacity loss caused by the damage of the surface of a core material is reduced, the first coating layer has higher active ion conduction performance due to the-S-S-bond, and the-S-S-bond is broken and combined with the active ions in the charging process, the carbon-based framework has the advantages that ion migration is carried out, the migration rate is high, active ions are removed, the-S-S-bond is bonded again in the discharging process, the-S-S-bond is only broken and bonded in the charging and discharging processes, the structure of the carbon-based framework is kept unchanged, the protection effect of the first coating layer on the nuclear material is guaranteed, and therefore the cycle performance of the battery can be better improved.
The present invention will be described in detail with reference to specific embodiments in order to more clearly illustrate the structural features and effects of the present invention.
Detailed Description
The invention discloses a modified hard carbon negative electrode material with improved performance, which comprises a hard carbon substrate, a first coating layer coated on at least one part of the surface of the hard carbon substrate, and a second coating layer coated on at least one part of the surface of the first coating layer.
The hard carbon matrix comprises a precursor, crystalline flake graphite and boron phosphate, wherein the precursor comprises any one or more of phenolic resin, polycarbonate, epoxy resin, acrylic resin, polyvinyl chloride and polyformaldehyde; the mass of the flake graphite and the boron phosphate are respectively 0.5-5% and 0.1-0.5% of the mass of the precursor, the D50 of the flake graphite powder is less than or equal to 5 mu m, the mass of the first coating is 1-8% of the mass of the hard carbon matrix, and the mass of the second coating is 1-15% of the mass of the hard carbon matrix.
The first coating comprises a first coating and sulfur powder, the first coating comprises any one or more of polystyrene, polyvinyl chloride, polyethylene, polyacrylonitrile, polyaniline, polyacetylene and polyvinylidene chloride, and the molded first coating has-S-C-bond and-S-S-bond.
The second coating layer comprises a second coating, and the second coating comprises any one or more of carboxymethyl cellulose, polyphenylene sulfide, polyvinylidene fluoride, furan resin, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile, polyethylene oxide, polypropylene oxide, polyethylene glycol succinate, polyethylene glycol sebacate, polyethylene glycol imine, polyacetylene, polyaniline, polypyrrole, polyacene, polythiophene, poly m-phenylenediamine, polyimide, polyvinyl pyrrolidone, asphalt and styrene butadiene rubber.
The invention also discloses a preparation method of the modified hard carbon negative electrode material with improved performance, which is used for preparing the modified hard carbon negative electrode material for the lithium ion battery with improved performance, and comprises the following steps:
(1) adding the precursor, the crystalline flake graphite powder and the boron phosphate into isopropanol, uniformly stirring, standing at normal temperature for 30-60min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 1-50h to obtain a solid precursor.
(2) Under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at the heating rate of 2-5 ℃/min, preserving heat for 1h, then heating to 500-1500 ℃ at the heating rate of 0.1-3 ℃/min, preserving heat for 2-24h, and then naturally cooling to room temperature to obtain the hard carbon.
(3) And carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m.
(4) Dissolving the first coating in a solvent, stirring until the first coating is uniformly dispersed to obtain a solution, wherein the solvent is one or more of N-methylpyrrolidone, xylene, toluene and dimethylformamide, adding a hard carbon matrix into the solution, stirring to obtain a mixed slurry, then placing the mixed slurry in a wet packing machine, and drying in an inert gas atmosphere at the drying temperature of 110-200 ℃. Wherein the heating rate can be 1-10 ℃/min to obtain solid powder, then the solid powder is mixed with a certain mass of sulfur powder, and the mixture is subjected to heat treatment for 2-8h in the atmosphere of inert gas, wherein the heat treatment temperature is 250-450 ℃, and the cathode blank with-S-C-bond and-S-S-bond is obtained.
(5) And putting the negative electrode blank and the second coating together into a mixing machine for mixing at the rotation speed of 500-3500r/min for 15-120min, then heating to 500-1000 ℃ at the heating speed of 0.1-10 ℃/min under the protection of inert gas, naturally cooling to 200 ℃, then continuing heating to 800-1500 ℃ at the heating speed of 0.1-10 ℃/min, preserving heat for 2-10h, and naturally cooling to room temperature.
The invention is illustrated below with specific examples and comparative examples.
Example 1
(1) Adding 66 parts of phenolic resin, 34 parts of polycarbonate, 0.5 part of crystalline flake graphite powder and 0.3 part of boron phosphate into 0.5L of isopropanol, uniformly stirring, standing at normal temperature for 40min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 10h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, then heating to 500 ℃ at the heating rate of 1 ℃/min, preserving heat for 4h, and naturally cooling to room temperature to obtain the hard carbon.
(3) And carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m.
(4) Dissolving 8 parts of first coating materials in 8 parts of solvent, stirring until the first coating materials are uniformly dispersed to obtain solution, wherein the first coating materials are polyethylene, polyacrylonitrile and polyaniline, the solvent is N-methylpyrrolidone and dimethylbenzene, adding a hard carbon matrix into the solution, stirring to obtain mixed slurry, then placing the mixed slurry into a wet packing machine, and drying in the atmosphere of inert gas at the drying temperature of 120 ℃. Wherein the heating rate can be 1 ℃/min to obtain solid powder, then the solid powder is mixed with 8 parts of sulfur powder, and the mixture is subjected to heat treatment for 2 hours in the atmosphere of inert gas, and the heat treatment temperature is 300 ℃, so that the cathode blank with-S-C-bond and-S-S-bond is obtained.
(5) And putting the negative electrode blank and 15 parts of a second coating together into a mixer for mixing, wherein the second coating is carboxymethylcellulose, polyphenylene sulfide, polyvinylidene fluoride, furan resin and ethyl methyl carbonate, the rotating speed is 500r/min, the time is 60min, then under the protection of inert gas, heating to 800 ℃ at the heating speed of 10 ℃/min, naturally cooling to 200 ℃, then continuing heating to 1000 ℃ at the heating speed of 10 ℃/min, preserving heat for 6h, and naturally cooling to room temperature to obtain a finished product.
Example 2
(1) Adding 57 parts of phenolic resin, 43 parts of polycarbonate, 1.5 parts of crystalline flake graphite powder and 0.1 part of boron phosphate into 0.5L of isopropanol, uniformly stirring, standing at normal temperature for 30min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 1h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, then heating to 1000 ℃ at a heating rate of 0.1 ℃/min, preserving heat for 2h, and naturally cooling to room temperature to obtain the hard carbon.
(3) And carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m.
(4) Dissolving 1 part of first coating material in 1 part of solvent, stirring until the first coating material is uniformly dispersed to obtain a solution, wherein the first coating material is polystyrene, polyvinyl chloride and polyethylene, the solvent is dimethylbenzene, methylbenzene and dimethylformamide, adding a hard carbon matrix into the solution, stirring to obtain mixed slurry, then placing the mixed slurry into a wet packing machine, and drying in an inert gas atmosphere at the drying temperature of 110 ℃. Wherein the heating rate can be 5 ℃/min to obtain solid powder, then the solid powder is mixed with 8 parts of sulfur powder, and the mixture is subjected to heat treatment for 8 hours in the atmosphere of inert gas, and the heat treatment temperature is 250 ℃, so that the cathode blank with-S-C-bond and-S-S-bond is obtained.
(5) And putting the negative electrode blank and 1 part of a second coating together into a mixer for mixing, wherein the second coating is polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile and polyethylene, the rotating speed is 3500r/min, the time is 15min, then heating to 500 ℃ at the heating speed of 0.1 ℃/min under the protection of inert gas, naturally cooling to 200 ℃, then continuously heating to 800 ℃ at the heating speed of 0.1 ℃/min, preserving the heat for 8h, and naturally cooling to room temperature to obtain a finished product.
Example 3
(1) Adding 55 parts of epoxy resin, 45 parts of polyformaldehyde, 2 parts of crystalline flake graphite powder and 0.2 part of boron phosphate into 0.5L of isopropanol, uniformly stirring, standing at normal temperature for 60min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 35h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, then heating to 1000 ℃ at a heating rate of 0.1 ℃/min, preserving heat for 2h, and naturally cooling to room temperature to obtain the hard carbon.
(3) And carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m.
(4) Dissolving 6 parts of first coating materials in 6 parts of solvent, stirring until the first coating materials are uniformly dispersed to obtain solution, wherein the first coating materials are polystyrene, polyvinyl chloride and polyaniline, the solvent is dimethylbenzene, methylbenzene and dimethylformamide, adding a hard carbon matrix into the solution, stirring to obtain mixed slurry, then placing the mixed slurry into a wet packing machine, and drying in an inert gas atmosphere at the drying temperature of 160 ℃. Wherein the heating rate can be 5 ℃/min to obtain solid powder, then the solid powder is mixed with 8 parts of sulfur powder, and the mixture is subjected to heat treatment for 8 hours in the atmosphere of inert gas, and the heat treatment temperature is 250 ℃, so that the cathode blank with-S-C-bond and-S-S-bond is obtained.
(5) And putting the negative electrode blank and 12 parts of a second coating material into a mixer together for mixing, wherein the second coating material is carboxymethyl cellulose, polyvinylidene fluoride and polyphenylene sulfide, and the mass ratio of the second coating material to the first coating material is 4: 1: the rotation speed of 1 is 3500r/min, the time is 120min, then under the protection of inert gas, the temperature is raised to 1000 ℃ at the heating rate of 5 ℃/min, the temperature is naturally cooled to 200 ℃, then the temperature is raised to 1500 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 7h, and the temperature is naturally cooled to the room temperature, thus obtaining the finished product.
Example 4
(1) Adding 30 parts of acrylic resin, 70 parts of polyvinyl chloride, 1.5 parts of crystalline flake graphite powder and 0.1 part of boron phosphate into 0.5L of isopropanol, uniformly stirring, standing at normal temperature for 30min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 1h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, then heating to 1000 ℃ at a heating rate of 0.1 ℃/min, preserving heat for 2h, and naturally cooling to room temperature to obtain the hard carbon.
(3) And carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m.
(4) Dissolving 6 parts of first coating materials in 6 parts of solvent, stirring until the first coating materials are uniformly dispersed to obtain solution, wherein the first coating materials are polyaniline, polyacetylene and polyvinylidene chloride, the solvent is toluene and dimethylformamide, then adding a hard carbon matrix into the solution, stirring to obtain mixed slurry, then placing the mixed slurry into a wet packing machine, and drying in an inert gas atmosphere at the drying temperature of 200 ℃. Wherein the heating rate can be 10 ℃/min to obtain solid powder, then the solid powder is mixed with 8 parts of sulfur powder, and the mixture is subjected to heat treatment for 4 hours in the atmosphere of inert gas, wherein the heat treatment temperature is 450 ℃, and the cathode blank with-S-C-bond and-S-S-bond is obtained.
(5) And putting the negative electrode blank and 10 parts of a second coating together into a mixer for mixing, wherein the second coating is polyethylene oxide, polypropylene oxide, polyethylene glycol succinate, polyethylene glycol sebacate, polyethylene glycol imine and polyacetylene, the rotating speed is 2500r/min, the time is 100min, then under the protection of inert gas, heating to 800 ℃ at the heating speed of 4 ℃/min, naturally cooling to 200 ℃, then continuously heating to 1000 ℃ at the heating speed of 4 ℃/min, preserving heat for 2h, and naturally cooling to room temperature to obtain a finished product.
Example 5
(1) Adding 30 parts of acrylic resin, 40 parts of epoxy resin, 30 parts of polyvinyl chloride, 1.5 parts of crystalline flake graphite powder and 0.1 part of boron phosphate into 0.5L of isopropanol, uniformly stirring, standing at normal temperature for 30min, drying at 45 ℃, naturally cooling to room temperature, and then curing at room temperature for 50h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, then heating to 1000 ℃ at a heating rate of 3 ℃/min, preserving heat for 24h, and naturally cooling to room temperature to obtain the hard carbon.
(3) And carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m.
(4) Dissolving 6 parts of first coating materials in 6 parts of solvent, stirring until the first coating materials are uniformly dispersed to obtain solution, wherein the first coating materials are polyacetylene and polyvinylidene chloride, the solvent is toluene and dimethylformamide, then adding a hard carbon matrix into the solution, stirring to obtain mixed slurry, then placing the mixed slurry into a wet packing machine, and drying in an inert gas atmosphere at the drying temperature of 200 ℃. Wherein the heating rate can be 10 ℃/min to obtain solid powder, then the solid powder is mixed with 8 parts of sulfur powder, and the mixture is subjected to heat treatment for 4 hours in the atmosphere of inert gas, wherein the heat treatment temperature is 450 ℃, and the cathode blank with-S-C-bond and-S-S-bond is obtained.
(5) And putting the negative electrode blank and 10 parts of a second coating together into a mixer for mixing, wherein the second coating is polyaniline, polypyrrole, polyacene, polythiophene, poly-m-phenylenediamine and polyimide, the rotating speed is 2500r/min, the time is 120min, then under the protection of inert gas, heating to 800 ℃ at the heating speed of 4 ℃/min, naturally cooling to 200 ℃, then continuing heating to 1000 ℃ at the heating speed of 4 ℃/min, preserving heat for 10h, and naturally cooling to room temperature to obtain a finished product.
Example 6
(1) Adding 20 parts of acrylic resin, 35 parts of epoxy resin, 45 parts of polyvinyl chloride, 3 parts of crystalline flake graphite powder and 0.2 part of boron phosphate into 0.5L of isopropanol, uniformly stirring, standing at normal temperature for 45min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 50h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, then heating to 1500 ℃ at a heating rate of 3 ℃/min, preserving heat for 20h, and naturally cooling to room temperature to obtain the hard carbon.
(3) And carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m.
(4) Dissolving 6 parts of first coating materials in 6 parts of solvent, stirring until the first coating materials are uniformly dispersed to obtain a solution, wherein the first coating materials are polyethylene, polyacetylene and polyvinylidene chloride, the solvent is toluene and dimethylformamide, then adding a hard carbon matrix into the solution, stirring to obtain mixed slurry, then placing the mixed slurry into a wet packing machine, and drying in an inert gas atmosphere at the drying temperature of 200 ℃. Wherein the heating rate can be 10 ℃/min to obtain solid powder, then the solid powder is mixed with 8 parts of sulfur powder, and the mixture is subjected to heat treatment for 6 hours in the atmosphere of inert gas, and the heat treatment temperature is 350 ℃, so that the cathode blank with-S-C-bond and-S-S-bond is obtained.
(5) And putting the negative electrode blank and 10 parts of a second coating together into a mixer for mixing, wherein the second coating is poly-m-phenylenediamine, polyimide, polyvinylpyrrolidone, asphalt and styrene butadiene rubber, the rotating speed is 2000r/min, the time is 90min, then under the protection of inert gas, the temperature is increased to 850 ℃ at the heating rate of 6 ℃/min, the temperature is naturally cooled to 200 ℃, then the temperature is increased to 1000 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 9h, and the temperature is naturally cooled to room temperature to obtain a finished product.
Comparative example 1
(1) Adding 66 parts of phenolic resin, 34 parts of polycarbonate, 0.5 part of crystalline flake graphite powder and 0.3 part of boron phosphate into 0.5L of isopropanol, uniformly stirring, standing at normal temperature for 40min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 10h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, then heating to 500 ℃ at the heating rate of 1 ℃/min, preserving heat for 4h, and naturally cooling to room temperature to obtain the hard carbon.
(3) And performing ball milling or crushing on the hard carbon to obtain a hard carbon finished product with the granularity of 1-60 mu m.
Comparative example 2
(1) Adding 66 parts of phenolic resin, 34 parts of polycarbonate, 0.5 part of crystalline flake graphite powder and 0.3 part of boron phosphate into 0.5L of isopropanol, uniformly stirring, standing at normal temperature for 40min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 10h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, then heating to 500 ℃ at the heating rate of 1 ℃/min, preserving heat for 4h, and naturally cooling to room temperature to obtain the hard carbon.
(3) And carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m.
(4) Dissolving 8 parts of first coating materials in 8 parts of solvent, stirring until the first coating materials are uniformly dispersed to obtain solution, wherein the first coating materials are polyethylene, polyacrylonitrile and polyaniline, the solvent is N-methylpyrrolidone and dimethylbenzene, adding a hard carbon matrix into the solution, stirring to obtain mixed slurry, then placing the mixed slurry into a wet packing machine, and drying in the atmosphere of inert gas at the drying temperature of 120 ℃. Wherein the heating rate can be 1 ℃/min to obtain solid powder, then the solid powder is mixed with 8 parts of sulfur powder, and the mixture is subjected to heat treatment for 2 hours in the atmosphere of inert gas, and the heat treatment temperature is 300 ℃, so that the hard carbon finished product with-S-C-bond and-S-S-bond is obtained.
Electrochemical performance test
The electrochemical performance of the modified hard carbon negative electrode material is tested, and the half-cell testing method comprises the following steps: uniformly mixing a modified hard carbon negative electrode material sample, N-methyl pyrrolidone containing 6-7% of polyvinylidene fluoride and conductive carbon black according to the proportion of 91.6:6.6:1.8, and coatingAnd (3) putting the coated pole piece on a copper foil into a vacuum drying oven at the temperature of 110 ℃ for drying for 4 hours for later use. The simulated cell assembly was carried out in a glove box filled with argon and 1mol/L LiPF as electrolyte6+ EC: DEC: DMC 1: 1:1 (volume ratio), and the metal lithium sheet is a counter electrode. The simulation battery is mainly used for testing the first charging specific capacity, the first discharging specific capacity and the first charging and discharging efficiency of the simulation battery. Testing specific capacity the simulated battery is firstly discharged from 0.005V to 2.5V on a battery detection system at a current of 0.1C, and the discharge capacity is recorded, wherein the specific capacity is the discharge capacity/the quality of the negative electrode material; first charge-discharge efficiency test the simulated battery was charged to 0.005V at a constant current of 0.5mA on a battery test system, then the battery was discharged to 2.5V at a constant current of 0.2mA, 50 cycles of charge-discharge tests were performed according to the above method, and the first discharge capacity, the first charge capacity, the 50 th discharge capacity, and the 50 th charge capacity were recorded.
First charge-discharge efficiency is first discharge capacity/first charge capacity × 100%.
The cycle capacity retention rate was 50 th discharge capacity/first discharge capacity × 100%
The test results are shown in table 1.
TABLE 1
The test data in the table show that the first charge-discharge efficiency of the six embodiments of the invention is generally higher than that of the two comparative examples, and the test data proves that the finished products finally obtained by the six embodiments have good lithium intercalation and lithium removal performances and excellent cycle capacity retention rate.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (10)
1. A modified hard carbon negative electrode material with improved performance is characterized in that: the coating comprises a hard carbon substrate, a first coating layer coated on at least one part of the surface of the hard carbon substrate, and a second coating layer coated on at least one part of the surface of the first coating layer.
2. The modified hard carbon negative electrode material with improved performance of claim 1, wherein: the hard carbon matrix comprises a precursor, crystalline flake graphite and boron phosphate, wherein the precursor comprises any one or more of phenolic resin, polycarbonate, epoxy resin, acrylic resin, polyvinyl chloride and polyformaldehyde;
the first coating comprises a first coating and sulfur powder, the first coating comprises any one or more of polystyrene, polyvinyl chloride, polyethylene, polyacrylonitrile, polyaniline, polyacetylene and polyvinylidene chloride, and the molded first coating has-S-C-bond and-S-S-bond;
the second coating layer comprises a second coating, and the second coating comprises any one or more of carboxymethyl cellulose, polyphenylene sulfide, polyvinylidene fluoride, furan resin, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile, polyethylene oxide, polypropylene oxide, polyethylene glycol succinate, polyethylene glycol sebacate, polyethylene glycol imine, polyacetylene, polyaniline, polypyrrole, polyacene, polythiophene, poly m-phenylenediamine, polyimide, polyvinyl pyrrolidone, asphalt and styrene butadiene rubber.
3. The modified hard carbon negative electrode material with improved performance of claim 2, wherein: the mass of the flake graphite and the boron phosphate are respectively 0.5-5% and 0.1-0.5% of the mass of the precursor, the D50 of the flake graphite powder is less than or equal to 5 mu m, the mass of the first coating is 1-8% of the mass of the hard carbon matrix, and the mass of the second coating is 1-15% of the mass of the hard carbon matrix.
4. The modified hard carbon negative electrode material with improved performance of claim 2, wherein: the mass of the crystalline flake graphite and the mass of the boron phosphate are respectively 2% and 0.2% of the mass of the precursor, the mass of the first coating is 6% of the mass of the hard carbon matrix, and the mass of the second coating is 12% of the mass of the hard carbon matrix.
5. The modified hard carbon negative electrode material with improved performance of claim 2, wherein: the precursor consists of phenolic resin and polycarbonate, and the mass ratio of the phenolic resin to the polycarbonate is 2: 1-1.5.
6. The modified hard carbon negative electrode material with improved performance of claim 2, wherein: the first coating is composed of polystyrene, polyvinyl chloride and polyaniline, and the mass ratio of the first coating to the sulfur powder is 1: 1-4: 1.
7. the modified hard carbon negative electrode material with improved performance of claim 2, wherein: the second cladding material is composed of carboxymethyl cellulose, polyvinylidene fluoride and polyphenylene sulfide, and the mass ratio of the carboxymethyl cellulose to the polyvinylidene fluoride to the polyphenylene sulfide is 4: 1:1.
8. A method for preparing a modified hard carbon negative electrode material with improved performance for use in a lithium ion battery according to any one of claims 1 to 7, comprising the steps of:
(1) adding the precursor, the crystalline flake graphite powder and the boron phosphate into isopropanol, uniformly stirring, standing at normal temperature for 30-60min, drying at 45 ℃, naturally cooling to room temperature, and curing at room temperature for 1-50h to obtain a solid precursor;
(2) under the protection of nitrogen or inert gas, heating the solid precursor obtained in the step (1) to 400 ℃ at the heating rate of 2-5 ℃/min, preserving heat for 1h, then heating to 500-1500 ℃ at the heating rate of 0.1-3 ℃/min, preserving heat for 2-24h, and then naturally cooling to room temperature to obtain hard carbon;
(3) carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m;
(4) dissolving the first coating in a solvent, stirring until the first coating is uniformly dispersed to obtain a solution, wherein the solvent is one or more of N-methylpyrrolidone, xylene, toluene and dimethylformamide, adding a hard carbon matrix into the solution, stirring to obtain a mixed slurry, then placing the mixed slurry in a wet packing machine, drying in an inert gas atmosphere at the drying temperature of 110-;
(5) and putting the negative electrode blank and the second coating together into a mixing machine for mixing at the rotation speed of 500-3500r/min for 15-120min, then heating to 500-1000 ℃ at the heating speed of 0.1-10 ℃/min under the protection of inert gas, naturally cooling to 200 ℃, then continuing heating to 800-1500 ℃ at the heating speed of 0.1-10 ℃/min, preserving heat for 2-10h, and naturally cooling to room temperature.
9. The method for preparing the modified hard carbon negative electrode material with improved performance according to claim 8, wherein the method comprises the following steps: the curing time of the step (1) is 35 h; the heat preservation time of the step (5) is 7 h.
10. The method for preparing the modified hard carbon negative electrode material with improved performance according to claim 8, wherein the method comprises the following steps: the drying temperature of the step (4) is 160 ℃, the heating speed is 5 ℃/min, and the mass ratio of the first coating to the solvent is 1: 1.
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| CN117199506A (en) * | 2023-11-08 | 2023-12-08 | 宁德时代新能源科技股份有限公司 | Battery monomer, preparation method thereof, battery and power utilization device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881869A (en) * | 2012-09-26 | 2013-01-16 | 东莞市翔丰华电池材料有限公司 | Modified hard carbon negative electrode material for lithium ion battery and preparation method for modified hard carbon negative electrode material |
| CN102969481A (en) * | 2012-12-11 | 2013-03-13 | 武汉大学 | Sulfur/carbon composite material for lithium-sulfur secondary battery and preparation method thereof |
| CN107919472A (en) * | 2017-12-12 | 2018-04-17 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of negative material of resistance to elevated temperatures, its preparation method and the purposes in lithium ion battery |
| WO2019194554A1 (en) * | 2018-04-04 | 2019-10-10 | 주식회사 엘지화학 | Negative electrode active material for lithium secondary battery, manufacturing method therefor, lithium secondary battery negative electrode comprising same, and lithium secondary battery |
| CN112310359A (en) * | 2019-07-29 | 2021-02-02 | 宁德时代新能源科技股份有限公司 | Negative electrode active material and secondary battery |
| CN113328067A (en) * | 2020-02-29 | 2021-08-31 | 溧阳天目先导电池材料科技有限公司 | Hard carbon negative electrode material with multilayer core-shell structure and preparation method and application thereof |
-
2021
- 2021-11-08 CN CN202111314245.8A patent/CN114122356A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881869A (en) * | 2012-09-26 | 2013-01-16 | 东莞市翔丰华电池材料有限公司 | Modified hard carbon negative electrode material for lithium ion battery and preparation method for modified hard carbon negative electrode material |
| CN102969481A (en) * | 2012-12-11 | 2013-03-13 | 武汉大学 | Sulfur/carbon composite material for lithium-sulfur secondary battery and preparation method thereof |
| CN107919472A (en) * | 2017-12-12 | 2018-04-17 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of negative material of resistance to elevated temperatures, its preparation method and the purposes in lithium ion battery |
| WO2019194554A1 (en) * | 2018-04-04 | 2019-10-10 | 주식회사 엘지화학 | Negative electrode active material for lithium secondary battery, manufacturing method therefor, lithium secondary battery negative electrode comprising same, and lithium secondary battery |
| CN112310359A (en) * | 2019-07-29 | 2021-02-02 | 宁德时代新能源科技股份有限公司 | Negative electrode active material and secondary battery |
| CN113328067A (en) * | 2020-02-29 | 2021-08-31 | 溧阳天目先导电池材料科技有限公司 | Hard carbon negative electrode material with multilayer core-shell structure and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117199506A (en) * | 2023-11-08 | 2023-12-08 | 宁德时代新能源科技股份有限公司 | Battery monomer, preparation method thereof, battery and power utilization device |
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