CN116344756A - Composite material for lithium ion battery, preparation method and application - Google Patents
Composite material for lithium ion battery, preparation method and application Download PDFInfo
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- CN116344756A CN116344756A CN202111584142.3A CN202111584142A CN116344756A CN 116344756 A CN116344756 A CN 116344756A CN 202111584142 A CN202111584142 A CN 202111584142A CN 116344756 A CN116344756 A CN 116344756A
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- hard carbon
- lithium ion
- composite material
- ion battery
- silicon
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 74
- 239000011159 matrix material Substances 0.000 claims abstract description 65
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 89
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000010703 silicon Substances 0.000 claims description 50
- 229910052710 silicon Inorganic materials 0.000 claims description 50
- 238000007740 vapor deposition Methods 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 28
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010335 hydrothermal treatment Methods 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 15
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000005543 nano-size silicon particle Substances 0.000 claims description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 13
- -1 silane compound Chemical class 0.000 claims description 12
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 12
- 239000005052 trichlorosilane Substances 0.000 claims description 12
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
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- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 9
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
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- 239000005720 sucrose Substances 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims 1
- 238000007599 discharging Methods 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000012159 carrier gas Substances 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 238000005056 compaction Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
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- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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
-
- 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 relates to a composite material for a lithium ion battery, a preparation method and application thereof. The composite material for the lithium ion battery comprises the following components: the porous hard carbon material is prepared from a hard carbon matrix by a hydrothermal method and then carbonized.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a composite material for a lithium ion battery, a preparation method and application thereof.
Background
Silicon has extremely high theoretical reversible capacity as a lithium ion battery anode material, wherein the silicon is up to 4200mAh/g, but the silicon anode material has huge volume effect in the process of lithium intercalation and deintercalation, and damages the anode particle structure in the process of charge and discharge, so that the pulverization is invalid, and the battery cyclicity is reduced. At present, the modification work of the silicon-based material is continuously carried out. Literature (h.li, x.j.h. Mu ang, l.q.chen, z.g.w μ, Y Liang, electric chem.and Solid-State letters, 2,547-549 (1999)), li et al used nanoscale silicon particles to prepare negative electrode materials, which reduced the volume effect, improved the cycling performance of silicon-based negative electrode materials, and maintained a higher reversible capacity (1700 mAh/g).
Currently, the volume effect of a silicon-based negative electrode can be effectively relieved by preparing the silicon-carbon composite material. However, due to the characteristic that nano silicon is easy to agglomerate and difficult to disperse, the nano silicon is unevenly distributed when being compounded with a carbon material, and the advantages of the silicon-carbon material are difficult to fully develop; at the same time, the compaction density is lower, and the energy density is further influenced.
Disclosure of Invention
The embodiment of the invention provides a composite material for a lithium ion battery, a preparation method and application thereof. The nano silicon in the composite material is uniformly distributed in the pores of the spherical porous carbon through vapor deposition. The porous structure can limit the size and uniform dispersion of the deposited nano silicon on one hand, reduce the expansion effect and avoid the problem of electrical contact deterioration caused by silicon powder; on the other hand, the expansion of silicon can be limited, the damage of the expansion of silicon to the composite material is reduced, and the electrochemical performance of the battery is further improved. And under the multi-element compounding, C and N are favorable for improving the cycle performance of the material, and B and P are favorable for improving the multiplying power performance of the material. In addition, the porous carbon with the spherical structure can effectively increase the compaction density of the coated pole piece, thereby improving the energy density of the battery.
In a first aspect, an embodiment of the present invention provides a composite material for a lithium ion battery, where the composite material for a lithium ion battery is: a spherical porous hard carbon material having silicon nanoparticles deposited inside the pores, a silicon-containing gas and one or more gaseous compounds containing any one of C, N, B, P elements decomposing the deposited product; the porous hard carbon material is prepared from a hard carbon matrix by a hydrothermal method and then carbonized.
Preferably, the silicon content of the composite material is 1-70 wt%.
Preferably, the particle size of the composite material ranges from 1um to 100um, and the average pore diameter of the pores ranges from 0.1nm to 20nm.
Preferably, the hard carbon matrix of the spherical porous hard carbon material is one or a combination of more of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, phenolic epoxy resin or polyvinyl chloride;
the silicon-containing gas is a silane compound, comprising: a combination of one or more of monosilane, trisilane, dichlorosilane, trichlorosilane, tetrachlorosilane;
the gaseous compound containing the C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
the gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
the gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
In a second aspect, an embodiment of the present invention provides a method for preparing the composite material for a lithium ion battery according to the first aspect, where the preparation method includes:
step one: carrying out hydrothermal treatment on a carbon-containing polymer, washing and filtering until filtrate is transparent and colorless, and drying to obtain a spherical carbonized precursor;
step two: placing the dried spherical carbonized precursor into a reaction device, heating to 700-1300 ℃, and preserving heat for 0.5-15 hours at 700-1300 ℃ to carry out high-temperature carbonization treatment to obtain a hard carbon matrix with the particle size ranging from 1um to 100 um;
step three: introducing a pore-forming air source into the obtained hard carbon matrix at 600-1000 ℃ for 1-10 hours, and carrying out pore-forming treatment on the hard carbon matrix to obtain a porous hard carbon matrix material; wherein the pore-forming gas source is one or the combination of two of oxygen, carbon dioxide and water vapor;
step four: vapor deposition is carried out on the porous hard carbon matrix material to obtain a composite material for the lithium ion battery; the gas source for vapor deposition comprises a silicon-containing gas and one or more gaseous compounds containing any of the elements C, N, B, P.
Preferably, the air flow of the pore-forming air source is 0.5L/min-20L/min;
the protective gas for vapor deposition is one or the combination of two of nitrogen and argon, the flow rate is 1-5L/min, the gas flow rate of the gaseous compound is 0.5-10L/min, and the flow rate of the silicon-containing gas is 0.5-10L/min; the vapor deposition temperature is 500-1500 ℃, and the vapor deposition time is 1-20 hours.
Preferably, the silicon-containing gas is a silane compound, comprising: a combination of one or more of monosilane, trisilane, dichlorosilane, trichlorosilane, tetrachlorosilane;
the gaseous compound containing the C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
the gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
the gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
Preferably, the hydrothermal treatment specifically includes: pressurized heating hydrothermal treatment or non-pressurized heating hydrothermal treatment;
the pressurized and heated hydrothermal treatment is as follows: the method is carried out in a hydrothermal kettle, the pressure is 0.1 MPa-10 MPa, the heating temperature is 150-300 ℃, and the heat preservation time is 2-8 hours;
the heating temperature of the non-pressurized heating hydrothermal treatment is 200-300 ℃, and the heat preservation time is 1-15 hours.
In a third aspect, an embodiment of the present invention provides a negative electrode material of a lithium ion battery, where the negative electrode material of a lithium ion battery includes the composite material for a lithium ion battery according to the first aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium ion battery, including the composite material for a lithium ion battery according to the first aspect.
The composite material for the lithium ion battery provided by the embodiment of the invention has the advantages that one or more of nano silicon and a gaseous compound containing any one or more elements C, N, B, P are uniformly distributed in pores of spherical porous carbon through vapor deposition. On one hand, the size and uniform dispersion of the deposited nano silicon can be limited, the expansion effect is reduced, and the problem of electrical contact deterioration caused by silicon powder is avoided; on the other hand, the expansion of silicon can be limited, the damage of the expansion of silicon to the composite material is reduced, and the electrochemical performance of the battery is further improved. And under the multi-element compounding, C and N are favorable for improving the cycle performance of the material, and B and P are favorable for improving the multiplying power performance of the material. In addition, the porous carbon with the spherical structure can effectively increase the compaction density of the coated pole piece, thereby improving the energy density of the battery. The composite material for the lithium ion battery provided by the invention can be used in liquid, semi-solid, quasi-solid and all-solid electrolyte lithium ion batteries.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
Fig. 1 is a flowchart of a method for preparing a composite material for a lithium ion battery according to an embodiment of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) image of the composite material for lithium ion batteries prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The invention provides a composite material for a lithium ion battery, in particular to a spherical porous hard carbon material, wherein silicon nano particles, silicon-containing gas and one or more gaseous compounds containing C, N, B, P are deposited in pores, and the products are decomposed and deposited;
the porous hard carbon material is prepared from a hard carbon matrix by a hydrothermal method and then carbonized; the hard carbon matrix is one or a combination of more of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, phenolic epoxy resin or polyvinyl chloride.
The silicon content in the composite material is 1-70 wt%.
The particle size of the composite material ranges from 1um to 100um, and the average pore diameter of the pores ranges from 0.1nm to 20nm.
The preparation method flow of the composite material for the lithium ion battery is shown in figure 1, and comprises the following steps:
step 1: carrying out hydrothermal treatment on a carbon-containing polymer, washing and filtering until filtrate is transparent and colorless, and drying to obtain a spherical carbonized precursor;
specifically, the hydrothermal treatment is specifically: pressurized heating hydrothermal treatment or non-pressurized heating hydrothermal treatment;
the pressurized and heated hydrothermal treatment is as follows: the method is carried out in a hydrothermal kettle, the pressure is 0.1 MPa-10 MPa, the heating temperature is 150-300 ℃, and the heat preservation time is 2-8 hours;
the heating temperature of the non-pressurized heating hydrothermal treatment is 200-300 ℃, and the heat preservation time is 1-15 hours.
Step 2: placing the dried spherical carbonized precursor into a reaction device, heating to 700-1300 ℃, and preserving heat for 0.5-15 hours at 700-1300 ℃ to carry out high-temperature carbonization treatment to obtain a hard carbon matrix with the particle size ranging from 1um to 100 um;
wherein, the reaction device can be specifically selected from common reaction devices such as a high-temperature reaction furnace and the like.
Step 3: introducing a pore-forming air source into the obtained hard carbon matrix at 600-1000 ℃ for 1-10 hours, and carrying out pore-forming treatment on the hard carbon matrix to obtain a porous hard carbon matrix material;
wherein the pore-forming gas source is one or the combination of two of oxygen, carbon dioxide and water vapor; the air flow of the pore-forming air source is 0.5L/min-20L/min.
Step 4: vapor deposition is carried out on the porous hard carbon matrix material to obtain a composite material for the lithium ion battery;
wherein the gas source for vapor deposition comprises a silicon-containing gas and one or more gaseous compounds containing any of the elements C, N, B, P.
The protective gas for vapor deposition is one or the combination of two of nitrogen and argon, the flow rate is 1-5L/min, the gas flow rate of the gaseous compound is 0.5-10L/min, and the flow rate of the silicon-containing gas is 0.5-10L/min; the vapor deposition temperature is 500-1500 ℃, and the vapor deposition time is 1-20 hours.
The silicon-containing gas is a silane compound comprising: a combination of one or more of monosilane, trisilane, dichlorosilane, trichlorosilane, tetrachlorosilane;
the gaseous compound containing C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
the gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
the gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
The composite material for the lithium ion battery, which is prepared by the invention, can be used as a negative electrode material of the lithium ion battery.
In order to better understand the technical scheme provided by the invention, the following specific processes for preparing the composite material for the lithium ion battery by applying the method provided by the embodiment of the invention, and the method and the battery characteristics for applying the composite material for the lithium ion battery to the lithium ion secondary battery are respectively described in a plurality of specific examples.
Example 1
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of phenolic resin into a hydrothermal kettle for hydrothermal reaction, wherein the pressure is 10Mpa, the heating temperature is 300 ℃, the heat preservation time is 2 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 1300 ℃, preserving heat for 0.5 hour under nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 0.5L/min for pore-forming, adopting oxygen as a gas source, and preserving the temperature at 600 ℃ for 1 hour to obtain a porous hard carbon matrix;
step 4: nitrogen is used as shielding gas and/or carrier gas, the flow rate is 1L/min, the obtained porous hard carbon matrix is used as a substrate, silicon-containing gas monosilane is used as a silicon source, and compound methane containing C element is introduced into a reaction container in a gas form for vapor deposition, the flow rate of monosilane gas is 0.5L/min, and the flow rate of methane gas is 0.5L/min. The temperature of vapor deposition was 500 ℃, and the time of vapor deposition was 20 hours.
Fig. 2 is an SEM image of the composite material for lithium ion batteries prepared in example 1 of the present invention.
The obtained material was used as a negative electrode material.
The obtained anode material, conductive additive carbon black and adhesive (1:1 sodium cellulose and styrene butadiene rubber) are mixed according to the proportion of 95:2:3, weighing. The slurry preparation was performed in a beater at room temperature. And uniformly coating the prepared slurry on the copper foil. Drying at 50deg.C for 2 hr in a forced air drying oven, cutting into 8×8mm pole pieces, and vacuum drying at 100deg.C for 10 hr in a vacuum drying oven. And transferring the dried pole piece into a glove box for standby use to assemble a battery.
The simulated cell was assembled in a glove box containing a high purity Ar atmosphere using metallic lithium as the counter electrode, 1 mole LiPF 6 The solution in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) was used as an electrolyte to assemble a battery. Constant-current charge and discharge mode test is carried out by using a charge and discharge instrument, the discharge cut-off voltage is 0.005V, the charge cut-off voltage is 1.5V, and the charge and discharge test is C/1At a current density of 0. The results are recorded in table 1.
Example 2
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of phenolic resin into a hydrothermal kettle for hydrothermal reaction, wherein the pressure is 5Mpa, the heating temperature is 300 ℃ and the heat preservation time is 8 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 700 ℃, preserving heat for 15 hours in nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 20L/min for pore-forming, adopting a gas source of a combination of carbon dioxide and water vapor, and preserving the temperature at 1000 ℃ for 10 hours to obtain a porous hard carbon matrix;
step 4: argon is used as shielding gas and/or carrier gas, the flow rate is 1.5L/min, the obtained porous hard carbon matrix is used as a substrate, silicon-containing gas trisilane is used as a silicon source, and ammonia gas containing N element compound is introduced into a reaction container in a gas form for vapor deposition, wherein the trisilane gas flow rate is 0.8L/min, and the ammonia gas flow rate is 0.8L/min. The temperature of vapor deposition was 600 ℃, and the time of vapor deposition was 12.5 hours.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 3
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of epoxy resin into a hydrothermal kettle for hydrothermal reaction, wherein the pressure is 0.5Mpa, the heating temperature is 300 ℃, the heat preservation time is 8 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain a spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 1300 ℃, preserving heat for 1 hour in a nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 20L/min for pore-forming, adopting a gas source of a combination of carbon dioxide and water vapor, and preserving the temperature at 700 ℃ for 10 hours to obtain a porous hard carbon matrix;
step 4: nitrogen is used as shielding gas and/or carrier gas, the flow rate is 2L/min, the obtained porous hard carbon matrix is used as a substrate, silicon-containing gas dichlorosilane is used as a silicon source, and the compound tripropyl borate containing B element is introduced into a reaction container in a gas form for vapor deposition, the flow rate of the dichlorosilane gas is 1L/min, and the flow rate of the gas containing tripropyl borate is 1L/min. The temperature of vapor deposition was 700 ℃, and the time of vapor deposition was 10 hours.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 4
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of phenolic resin into a hydrothermal kettle for hydrothermal reaction, wherein the pressure is 5Mpa, the heating temperature is 300 ℃ and the heat preservation time is 2 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 700 ℃, preserving heat for 1 hour in nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 2L/min for pore-forming, adopting a combination of carbon dioxide as a gas source, and preserving the temperature at 900 ℃ for 10 hours to obtain a porous hard carbon matrix;
step 4: argon is used as shielding gas and/or carrier gas, the flow rate is 2.5L/min, the obtained porous hard carbon matrix is used as a substrate, silicon-containing gas trichlorosilane is used as a silicon source, and a compound phosphorus oxychloride containing P element is introduced into a reaction container in a gas form for vapor deposition, the flow rate of the trichlorosilane gas is 1.25L/min, and the flow rate of the phosphorus oxychloride gaseous compound is 1.25L/min. The temperature of vapor deposition was 800 ℃, and the time of vapor deposition was 8 hours.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 5
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of phenolic resin into a hydrothermal kettle for hydrothermal reaction, wherein the pressure is 5Mpa, the heating temperature is 300 ℃ and the heat preservation time is 8 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 800 ℃, preserving heat for 1 hour in a nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 5L/min for pore-forming, adopting a gas source of water vapor combination, and preserving heat at 800 ℃ for 5 hours to obtain a porous hard carbon matrix;
step 4: nitrogen is used as shielding gas and/or carrier gas, the flow rate is 3L/min, the obtained porous hard carbon matrix is used as a substrate, silicon-containing gas tetrachlorosilane is used as a silicon source, gaseous compounds containing C, N, B and P elements, namely methane, ammonia, trimethyl borate and phosphorus oxychloride, are introduced into a reaction container in the form of gas, vapor deposition is carried out, the flow rate of the tetrachlorosilane gas is 2L/min, and the flow rates of the gaseous compounds of methane, ammonia, trimethyl borate and phosphorus oxychloride are all 0.5L/min. The temperature of vapor deposition was 900 ℃ and the time of vapor deposition was 5 hours.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 6
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of phenolic resin into a hydrothermal kettle for hydrothermal reaction, wherein the pressure is 0.1Mpa, the heating temperature is 300 ℃, the heat preservation time is 8 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 700 ℃, preserving heat for 6 hours in nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 5L/min for pore-forming, adopting a gas source of a combination of carbon dioxide and water vapor, and preserving the temperature at 800 ℃ for 10 hours to obtain a porous hard carbon matrix;
step 4: argon is used as shielding gas and/or carrier gas, the flow rate is 3.5L/min, the obtained porous hard carbon matrix is used as a substrate, monosilane and trisilane which are silicon-containing gases are used as silicon sources, and gaseous compounds containing C, N, B and P elements, namely propylene, urea, tripropyl borate and phosphine, are introduced into a reaction container in the form of gases for vapor deposition, wherein the flow rates of monosilane and trisilane gases are 1.25L/min, and the flow rates of the gases of propylene, urea, tripropyl borate and phosphine gaseous compounds are 0.6L/min. The temperature of vapor deposition was 1000℃and the time of vapor deposition was 4 hours.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 7
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of starch polyvinylidene fluoride into a hydrothermal kettle for hydrothermal reaction, wherein the pressure is 5Mpa, the heating temperature is 300 ℃ and the heat preservation time is 8 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain a spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 700 ℃, preserving heat for 1 hour in nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 5L/min for pore-forming, adopting a gas source of a combination of carbon dioxide and water vapor, and preserving the temperature at 1000 ℃ for 10 hours to obtain a porous hard carbon matrix;
step 4: nitrogen is used as shielding gas and/or carrier gas, the flow rate is 4L/min, the obtained porous hard carbon matrix is used as a substrate, silicon-containing gas monosilane, trisilane and dichlorosilane are used as silicon sources, and compounds propane, hydrazine, diborane and phosphine containing C, N, B and P elements are introduced into a reaction container in a gas form for vapor deposition, the flow rates of monosilane, trisilane and dichlorosilane are all 1.3L/min, and the flow rates of propane, hydrazine, diborane and phosphine are all 0.5L/min. The temperature of vapor deposition was 1100 ℃, and the time of vapor deposition was 2.5 hours.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 8
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of starch polyvinylidene fluoride into a hydrothermal kettle for hydrothermal reaction, wherein the pressure is 5Mpa, the heating temperature is 300 ℃ and the heat preservation time is 6 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain a spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 700 ℃, preserving heat for 5 hours in nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 5L/min for pore-forming, adopting a gas source of a combination of carbon dioxide and water vapor, and preserving the temperature at 900 ℃ for 5 hours to obtain a porous hard carbon matrix;
step 4: argon is used as shielding gas and/or carrier gas, the flow rate is 4.5L/min, the obtained porous hard carbon matrix is used as a substrate, silicon-containing gas monosilane, trisilane and trichlorosilane are used as silicon sources, and the compounds containing C, N, B and P elements, namely ethanol, nitrogen, trimethyl borate and phosphorus oxychloride, are introduced into a reaction container in a gas form to carry out vapor deposition, the flow rates of monosilane, trisilane and phosphorus oxychloride are all 1.7L/min, and the flow rates of the ethanol, nitrogen, trimethyl borate and phosphorus oxychloride are all 1.25L/min. The temperature of vapor deposition was 1200 ℃, and the time of vapor deposition was 2 hours.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 9
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of glucose into a hydrothermal kettle for hydrothermal reaction, heating at the pressure of 2Mpa and the temperature of 300 ℃ for 8 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain a spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 900 ℃, preserving heat for 1 hour in a nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 5L/min for pore-forming, adopting a gas source of water vapor combination, and preserving heat at 1000 ℃ for 10 hours to obtain a porous hard carbon matrix;
step 4: nitrogen is used as shielding gas and/or carrier gas, the flow rate is 5L/min, the obtained porous hard carbon matrix is used as a substrate, silicon-containing gases including trisilane, dichlorosilane and trichlorosilane are used as silicon sources, and compounds including C, N, B and P elements including ethylene, propane, urea, melamine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride are introduced into a reaction vessel in a gas form for vapor deposition, the flow rates of trisilane, dichlorosilane and trichlorosilane are 2.7L/min, and the flow rates of ethylene, propane, urea, melamine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride are 1L/min. The temperature of vapor deposition was 1400℃and the time of vapor deposition was 1.25 hours.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
Example 10
The embodiment provides a preparation method of a composite material for a lithium ion battery, which comprises the following steps:
step 1: adding 200g of glucose into a hydrothermal kettle for hydrothermal reaction, heating at the pressure of 5Mpa and the temperature of 300 ℃ for 6 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain a spherical carbonized precursor;
step 2: placing the obtained spherical carbonized precursor into a reaction furnace, heating to 900 ℃, preserving heat for 1 hour in a nitrogen atmosphere, discharging, cleaning until filtrate is neutral, and drying to obtain a hard carbon matrix;
step 3: putting the obtained hard carbon matrix into a reaction device, introducing gas with the flow rate of 5L/min for pore-forming, adopting a gas source of water vapor combination, and preserving the temperature at 900 ℃ for 5 hours to obtain a porous hard carbon matrix;
step 4: argon is used as shielding gas and/or carrier gas, the flow rate is 5L/min, the obtained porous hard carbon matrix is used as a substrate, silicon-containing gases including dichlorosilane, trichlorosilane and tetrachlorosilane are used as silicon sources, and compounds including C, N, B and P, such as acetylene, propane, ammonia, hydrazine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride, are introduced into a reaction vessel in the form of gas, and vapor deposition is carried out, wherein the flow rates of the gases including dichlorosilane, trichlorosilane and tetrachlorosilane are 3.3L/min, and the flow rates of the gases including acetylene, propane, ammonia, hydrazine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride are 1.3L/min. The temperature of vapor deposition was 1500 ℃, and the time of vapor deposition was 1 hour.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
For better comparison, we prepared a comparative sample as follows.
Comparative example 1
The comparative example provides a preparation method of a common silicon-carbon-containing composite material, which comprises the following steps:
step 1: adding 200g of nano silicon particles and 500g of phenolic resin powder into a hydrothermal kettle for hydrothermal reaction, heating at the pressure of 5Mpa and the temperature of 300 ℃ for 8 hours, discharging, washing and filtering until filtrate is transparent and colorless, and drying to obtain spherical silicon-containing carbonized precursor;
step 2: and (3) placing the spherical silicon-containing carbonized precursor into a reaction device, heating to 900 ℃ at a speed of 3 ℃/min, and preserving heat for 6 hours in a nitrogen atmosphere for carbonization to obtain the silicon-carbon composite material for comparison.
The electrochemical properties of the assembled button cell were evaluated under the same test conditions as in example 1, and are recorded in table 1.
TABLE 1
As can be seen from comparison of the comparative examples and the examples, the composite material for the lithium ion battery provided by the invention has higher specific capacity and initial efficiency. By using the hard carbon material with the through holes, more nano silicon particles can be deposited in the hard carbon matrix, so that the hard carbon matrix has higher capacity and compaction density, and the first effect of the material can be further improved by regulating the deposition time, temperature and gas flow rate. When the gas flow rate and the temperature are too high, silane can be decomposed too quickly and directly deposited on the surface of the carbon matrix, so that the performance of the battery is affected. Too low a temperature may result in incomplete decomposition of the silane, affecting the capacity of the battery.
The composite material for the lithium ion battery provided by the embodiment of the invention has the advantages that one or more of nano silicon and a gaseous compound containing any one or more elements C, N, B, P are uniformly distributed in pores of spherical porous carbon through vapor deposition. On one hand, the size and uniform dispersion of the deposited nano silicon can be limited, the expansion effect is reduced, and the problem of electrical contact deterioration caused by silicon powder is avoided; on the other hand, the expansion of silicon can be limited, the damage of the expansion of silicon to the composite material is reduced, and the electrochemical performance of the battery is further improved. And, through multielement recombination, the specific capacity and the first cycle efficiency are further improved. In addition, the porous carbon with the spherical structure can effectively increase the compaction density of the coated pole piece, thereby improving the energy density of the battery. The composite anode material provided by the invention can be used in liquid, semi-solid, quasi-solid and all-solid electrolyte lithium ion batteries.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The composite material for the lithium ion battery is characterized in that the composite material for the lithium ion battery comprises the following components: a spherical porous hard carbon material having silicon nanoparticles deposited inside the pores, a silicon-containing gas and one or more gaseous compounds containing any one of C, N, B, P elements decomposing the deposited product; the porous hard carbon material is prepared from a hard carbon matrix by a hydrothermal method and then carbonized.
2. The composite of claim 1, wherein the silicon content of the composite is 1wt% to 70wt%.
3. The composite material of claim 1, wherein the composite material has a particle size in the range of 1um to 100um and an average pore size of 0.1nm to 20nm.
4. The composite material according to claim 1, wherein the hard carbon matrix of the spherical porous hard carbon material is one or a combination of several of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, novolac epoxy resin or polyvinyl chloride;
the silicon-containing gas is a silane compound, comprising: a combination of one or more of monosilane, trisilane, dichlorosilane, trichlorosilane, tetrachlorosilane;
the gaseous compound containing the C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
the gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
the gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
5. A method for preparing the composite material for a lithium ion battery according to any one of claims 1 to 4, wherein the preparation method comprises the steps of:
step one: carrying out hydrothermal treatment on a carbon-containing polymer, washing and filtering until filtrate is transparent and colorless, and drying to obtain a spherical carbonized precursor;
step two: placing the dried spherical carbonized precursor into a reaction device, heating to 700-1300 ℃, and preserving heat for 0.5-15 hours at 700-1300 ℃ to carry out high-temperature carbonization treatment to obtain a hard carbon matrix with the particle size ranging from 1um to 100 um;
step three: introducing a pore-forming air source into the obtained hard carbon matrix at 600-1000 ℃ for 1-10 hours, and carrying out pore-forming treatment on the hard carbon matrix to obtain a porous hard carbon matrix material; wherein the pore-forming gas source is one or the combination of two of oxygen, carbon dioxide and water vapor;
step four: vapor deposition is carried out on the porous hard carbon matrix material to obtain a composite material for the lithium ion battery; the gas source for vapor deposition comprises a silicon-containing gas and one or more gaseous compounds containing any of the elements C, N, B, P.
6. The method according to claim 5, wherein the air flow rate of the pore-forming air source is 0.5L/min to 20L/min;
the protective gas for vapor deposition is one or the combination of two of nitrogen and argon, the flow rate is 1-5L/min, the gas flow rate of the gaseous compound is 0.5-10L/min, and the flow rate of the silicon-containing gas is 0.5-10L/min; the vapor deposition temperature is 500-1500 ℃, and the vapor deposition time is 1-20 hours.
7. The method according to claim 5, wherein the silicon-containing gas is a silane compound, comprising: a combination of one or more of monosilane, trisilane, dichlorosilane, trichlorosilane, tetrachlorosilane;
the gaseous compound containing the C element comprises: one or more of acetylene, methane, propylene, ethylene, propane, and gaseous ethanol;
the gaseous compound containing N element comprises: one or more of nitrogen, ammonia, urea, and melamine;
the gaseous compound containing B element comprises: one or more of diborane, trimethyl borate, tripropyl borate, and boron tribromide;
the gaseous compound containing the P element comprises: phosphine and/or phosphorus oxychloride.
8. The preparation method according to claim 5, wherein the hydrothermal treatment is specifically: pressurized heating hydrothermal treatment or non-pressurized heating hydrothermal treatment;
the pressurized and heated hydrothermal treatment is as follows: the method is carried out in a hydrothermal kettle, the pressure is 0.1 MPa-10 MPa, the heating temperature is 150-300 ℃, and the heat preservation time is 2-8 hours;
the heating temperature of the non-pressurized heating hydrothermal treatment is 200-300 ℃, and the heat preservation time is 1-15 hours.
9. A negative electrode material for a lithium ion battery, characterized in that the negative electrode material for a lithium ion battery comprises the composite material for a lithium ion battery according to any one of claims 1 to 4.
10. A lithium ion battery, characterized in that it comprises a composite material for a lithium ion battery according to any one of the preceding claims 1-4.
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| CN116895747A (en) * | 2023-07-11 | 2023-10-17 | 广东凯金新能源科技股份有限公司 | Phosphorus-doped silicon-carbon composite material, preparation method thereof and secondary battery |
| CN117096330A (en) * | 2023-10-20 | 2023-11-21 | 宁德时代新能源科技股份有限公司 | Silicon-carbon composite material, preparation method thereof, secondary battery and electricity utilization device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116895747A (en) * | 2023-07-11 | 2023-10-17 | 广东凯金新能源科技股份有限公司 | Phosphorus-doped silicon-carbon composite material, preparation method thereof and secondary battery |
| CN117096330A (en) * | 2023-10-20 | 2023-11-21 | 宁德时代新能源科技股份有限公司 | Silicon-carbon composite material, preparation method thereof, secondary battery and electricity utilization device |
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