CN116344785A - Novel composite material for lithium ion battery, preparation method and application - Google Patents
Novel composite material for lithium ion battery, preparation method and application Download PDFInfo
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- CN116344785A CN116344785A CN202111582638.7A CN202111582638A CN116344785A CN 116344785 A CN116344785 A CN 116344785A CN 202111582638 A CN202111582638 A CN 202111582638A CN 116344785 A CN116344785 A CN 116344785A
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- ion battery
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- 239000002131 composite material Substances 0.000 title claims abstract description 106
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 111
- 239000007789 gas Substances 0.000 claims abstract description 101
- 150000003839 salts Chemical class 0.000 claims abstract description 62
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000011159 matrix material Substances 0.000 claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 28
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 48
- 238000007740 vapor deposition Methods 0.000 claims description 45
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- 239000010439 graphite Substances 0.000 claims description 43
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 28
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 26
- 238000004321 preservation Methods 0.000 claims description 25
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 17
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 14
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010335 hydrothermal treatment Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 12
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 claims description 11
- -1 siloxane compound Chemical class 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 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
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 238000004804 winding 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
- 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
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 21
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000007599 discharging Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 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
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 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
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a novel composite material for a lithium ion battery, a preparation method and application thereof. The novel 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 oxygen-containing gas and one or more gaseous compounds containing any one of C, N, B, P elements decomposing the deposited product, the product comprising SiOx particles; x ranges from 0 to 1.5, and the value of x is controlled through molten salt electrolysis; 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 novel composite material for a lithium ion battery, a preparation method and application thereof.
Background
Silicon (Si) is widely recognized as the most attractive candidate negative electrode material for next generation high energy density Lithium Ion Batteries (LIB) because of its advantages of higher theoretical lithium storage capacity, relatively low lithiation voltage, and abundant resources. Thus, great efforts have been made to improve the electrochemical performance thereof. Although some progress has been made in this area, many serious challenges have not been resolved, such as large silicon volume changes during cycling, low intrinsic electronic conductivity, and poor rate capacity.
Currently, the combination of silicon and carbon material can effectively improve the volume effect of silicon, and also increase the conductivity of the composite material and improve the electrochemical performance of the composite material. In patent CN202010148266.6, silicon oxide, a carbon source and a nitrogen source are mixed in water, stirred, heated and evaporated to dryness, and then calcined at a high temperature to obtain a silicon-carbon anode material. However, this method is difficult to disperse well in the carbon material by physical mixing, and thus it is difficult to exert the advantages of the silicon carbon material.
Disclosure of Invention
The embodiment of the invention provides a novel composite material for a lithium ion battery, and a preparation method and application thereof. Compared with the prior art, one or more of nano SiOx and a gaseous compound containing C, N, B, P elements in the composite material are uniformly distributed in pores of spherical porous carbon through vapor deposition, and then the pores are reduced through molten salt electrolysis, so that the range of x in SiOx is controlled. On one hand, the material can limit the size of SiOx and reduced nano silicon and uniformly disperse in a carbon material, so that the expansion effect is reduced, and the problem of electrical contact deterioration caused by SiOx pulverization is avoided; on the other hand, the expansion of SiOx can be limited, the damage of SiOx expansion to the composite material is reduced, and the cycle 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. Meanwhile, the spherical porous carbon 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 novel composite material for a lithium ion battery, where the novel composite material for a lithium ion battery is: a spherical porous hard carbon material having silicon nanoparticles deposited inside the pores and a product of decomposition deposition of a silicon-oxygen-containing gas and one or more gaseous compounds containing any one of C, N, B, P elements; the product comprises SiOx particles; x ranges from 0 to 1.5, and the value of x is controlled through molten salt electrolysis; 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-oxygen-containing gas is a siloxane compound, comprising: a combination of one or more of trimethoxysilane, tetramethoxysilane, triethoxysilane, and tetraethoxysilane;
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 novel 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: introducing a pore-forming air source into the spherical carbonized precursor 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 carbon dioxide and water vapor;
step three: vapor deposition is carried out on the porous hard carbon matrix material to obtain composite material powder; the gas source of the vapor deposition comprises a silicon oxide-containing gas and one or more gaseous compounds containing any element C, N, B, P;
Step four: placing the dried salt into a crucible, and winding and suspending two graphite sheets on the crucible by conductive wires respectively to serve as pre-electrolysis electrodes; argon is introduced, the gas flow rate is 0.5-2L/min, the temperature is raised to 800-900 ℃ at the heating rate of 2-10 ℃/min, and two graphite sheets are placed after heat preservation for half an hour; applying constant voltage of 2.5-3.0V between two graphite sheets for pre-electrolysis for 1-2 hours; after the pre-electrolysis is finished, continuously heating to 900-1000 ℃, and lifting two graphite sheets from molten salt to be suspended; putting composite material powder, applying constant voltage of 2.2-3.0V between two electrodes of molten salt electrolysis, and starting electrolysis for 5-20 hours; and after the electrolysis is finished, taking out the electrolyzed sample, washing with water, placing the sample in a blast drying box, and drying at 50-80 ℃ for 8-20 hours to obtain the novel composite material for the lithium ion battery.
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-oxygen-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 dried salt comprises: one or more of calcium chloride, magnesium chloride, sodium chloride and potassium chloride;
the silicon-oxygen-containing gas is a siloxane compound, comprising: a combination of one or more of trimethoxysilane, tetramethoxysilane, triethoxysilane, and tetraethoxysilane;
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 for a lithium ion battery, where the negative electrode material for a lithium ion battery includes the novel composite material for a lithium ion battery described in the first aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium ion battery, including the novel composite material for a lithium ion battery according to the first aspect.
According to the novel composite material for the lithium ion battery, one or more of nano SiOx and a gaseous compound containing C, N, B, P elements in the composite material are uniformly distributed in pores of spherical porous carbon through vapor deposition, and then the composite material is reduced through molten salt electrolysis, so that the range of x in SiOx is controlled. On one hand, the material can limit the size of SiOx and reduced nano silicon and uniformly disperse in a carbon material, so that the expansion effect is reduced, and the problem of electrical contact deterioration caused by SiOx pulverization is avoided; on the other hand, the expansion of SiOx can be limited, the damage of SiOx expansion to the composite material is reduced, and the cycle 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. Meanwhile, the spherical porous carbon can effectively increase the compaction density of the coated pole piece, thereby improving the energy density of the battery.
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 flow chart of a method of preparing a novel 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 novel 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 novel composite material for a lithium ion battery, which comprises the following components: a spherical porous hard carbon material having silicon nanoparticles deposited inside the pores and a product of decomposition deposition of a silicon-oxygen-containing gas and one or more gaseous compounds containing any one of C, N, B, P elements; the product comprises SiOx particles; x ranges from 0 to 1.5, and the value of x is controlled through molten salt electrolysis; the porous hard carbon material is prepared from a hard carbon matrix by a hydrothermal method and then carbonized.
The silicon content in the composite material is 1-70wt%.
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 hard carbon matrix is one or a combination of more of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, phenolic epoxy resin or polyvinyl chloride.
The preparation method flow of the novel 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;
step 2: introducing a pore-forming air source into the spherical carbonized precursor 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 carbon dioxide and water vapor;
step 3: vapor deposition is carried out on the porous hard carbon matrix material to obtain composite material powder;
the gas source for vapor deposition comprises a silicon oxide-containing gas and one or more gaseous compounds containing any one of C, N, B, P elements;
step 4: carrying out molten salt electrolysis on the composite material powder to prepare a novel composite material with hollow holes inside;
The method specifically comprises the following steps: placing the dried salt into a crucible, and winding and suspending two graphite sheets on the crucible by conductive wires respectively to serve as pre-electrolysis electrodes; argon is introduced, the gas flow rate is 0.5-2L/min, the temperature is raised to 800-900 ℃ at the heating rate of 2-10 ℃/min, and two graphite sheets are placed after heat preservation for half an hour; applying constant voltage of 2.5-3.0V between two graphite sheets for pre-electrolysis for 1-2 hours; after the pre-electrolysis is finished, continuously heating to 900-1000 ℃, and lifting two graphite sheets from molten salt to be suspended; putting composite material powder, applying constant voltage of 2.2-3.0V between two electrodes of molten salt electrolysis, and starting electrolysis for 5-20 hours; and after the electrolysis is finished, taking out the electrolyzed sample, washing with water, placing the sample in a blast drying box, and drying at 50-80 ℃ for 8-20 hours to obtain the novel composite material for the lithium ion battery.
In order to better understand the technical scheme provided by the invention, the following specific processes for preparing the novel 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 novel composite material to the lithium ion secondary battery are respectively described in a plurality of specific examples.
Example 1
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the precursor into a reaction device, introducing gas with the flow rate of 0.5L/min for pore-forming, adopting water vapor as a gas source, and preserving heat at 600 ℃ for 1 hour to obtain a porous hard carbon matrix;
step 3: taking nitrogen as a shielding gas, taking a porous hard carbon matrix as a substrate, taking trimethoxysilane containing silicon oxygen as a silicon source and methane containing a compound of C element, and introducing the trimethoxysilane and the methane into a reaction container in a gas form for vapor deposition to obtain composite material powder; wherein the gas flow rate of trimethoxysilane is 0.5L/min, and the gas flow rate of methane is 0.5L/min. The temperature of vapor deposition was 500 ℃, and the time of vapor deposition was 20 hours.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride is placed in a crucible, and two graphite sheets wound by 0.2mm molybdenum wires are respectively wound by conductive wires and suspended above the crucible to serve as a pre-electrolysis electrode. Argon is introduced, the gas flow rate is 0.5L/min, the temperature is raised to 800 ℃ at the heating rate of 2 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.5V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 900 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 2cm, a constant voltage of 2.2V was applied between the electrodes, and electrolysis was started for 20 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 3 times by using ultrapure water to remove the fused salt attached to the surface of the sample. And drying the cleaned sample at 50 ℃ for 8 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
Fig. 2 is an SEM image of the novel 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 assembly of the simulated battery was performed in a glove box containing a high purity Ar atmosphere using metallic lithium as the counter electrode and a solution of 1 mole LiPF6 in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) as the electrolyte to assemble the battery. The constant current charge and discharge mode test was performed using a charge and discharge meter with a discharge cutoff voltage of 0.005V and a charge cutoff voltage of 1.5V, and the charge and discharge test was performed at a C/10 current density. The test results are recorded in table 1.
Example 2
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the precursor 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 3: argon is used as shielding gas, the flow rate is 1.5L/min, a porous hard carbon matrix is used as a substrate, tetramethoxy silane containing silicon oxygen 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, so that composite material powder is obtained; wherein the flow rate of the tetramethoxysilane gas is 0.8L/min, and the flow rate of the ammonia-containing gas is 0.8L/min. The temperature of vapor deposition was 600 ℃, and the time of vapor deposition was 12.5 hours.
Step 4: molten salt electrolysis: the dried anhydrous sodium chloride is put into a crucible, and two graphite sheets wound by copper wires with the diameter of 0.3mm are respectively wound by conductive wires and suspended on the crucible to serve as a pre-electrolysis electrode. Argon is introduced, the gas flow rate is 1L/min, the temperature is raised to 850 ℃ at the heating rate of 3 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.6V was applied between the two graphite sheets for pre-electrolysis for 2 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 950 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 3cm, a constant voltage of 2.3V was applied between the electrodes, and electrolysis was started for 18 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 4 times by using ultrapure water to remove the fused salt attached to the surface of the sample. And drying at 55 ℃ for 9 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
Example 3
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the hard carbon matrix obtained in the step two 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 heat at 700 ℃ for 10 hours to obtain a porous hard carbon matrix;
step 3: taking nitrogen as a shielding gas, taking a porous hard carbon matrix as a substrate, taking silicon-oxygen-containing gas triethoxysilane as a silicon source, and adding a compound tripropyl borate containing B element into a reaction container in a gas form, and performing vapor deposition to obtain composite material powder; wherein the gas flow rate of triethoxysilane is 1L/min, and the gas flow rate of tripropyl borate is 1L/min. The temperature of vapor deposition was 700 ℃, and the time of vapor deposition was 10 hours.
Step 4: molten salt electrolysis: the dried anhydrous magnesium chloride is placed into a crucible, and two graphite sheets wound by an iron wire with the diameter of 0.4mm are respectively wound by a conductive wire and suspended on the crucible to serve as a pre-electrolysis electrode. Argon is introduced, the gas flow rate is 2L/min, the temperature is raised to 900 ℃ at the heating rate of 4 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.7V was applied between the two graphite sheets for pre-electrolysis for 2 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 1000 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 4cm, a constant voltage of 2.4V was applied between the electrodes, and electrolysis was started for 18 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 5 times by using ultrapure water to remove the fused salt attached to the surface of the sample. Drying at 60 ℃ for 10 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
Example 4
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the precursor into a reaction device, introducing gas with the flow rate of 2L/min for pore-forming, adopting carbon dioxide as a gas source, and preserving the temperature at 900 ℃ for 10 hours to obtain a porous hard carbon matrix;
step 3: argon is used as a shielding gas, the flow rate is 2.5L/min, a porous hard carbon matrix is used as a substrate, tetraethoxysilane containing silicon oxygen 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, so that composite material powder is obtained; wherein the flow rate of tetraethoxysilane gas is 1.25L/min, and the flow rate of phosphorus oxychloride gas compound gas is 1.25L/min. The temperature of vapor deposition was 800 ℃, and the time of vapor deposition was 8 hours.
Step 4: molten salt electrolysis: the dried anhydrous potassium chloride is placed in a crucible, and two graphite sheets wound by 0.5mm molybdenum wires are respectively wound by conductive wires and suspended above the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 2L/min, the temperature is raised to 850 ℃ at the heating rate of 5 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.8V was applied between the two graphite sheets for pre-electrolysis for 2 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 1000 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 5cm, a constant voltage of 2.5V was applied between the electrodes, and electrolysis was started for 20 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 6 times by using ultrapure water to remove the fused salt attached to the surface of the sample. And drying at 65 ℃ for 12 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
Example 5
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the precursor into a reaction device, introducing gas with the flow rate of 5L/min for pore-forming, adopting water vapor as a gas source, and preserving heat at 800 ℃ for 5 hours to obtain a porous hard carbon matrix;
step 3: taking nitrogen as a shielding gas, taking a porous hard carbon matrix as a substrate, taking trimethoxysilane and tetramethoxysilane containing silicon oxygen as silicon sources, and introducing gaseous compounds methane, ammonia, trimethyl borate and phosphorus oxychloride containing C, N, B and P elements into a reaction container in the form of gases for vapor deposition to obtain composite material powder; wherein, the gas flow rates of trimethoxysilane and tetramethoxysilane are 1L/min, and the gas flow rates of methane, ammonia, trimethyl borate and phosphorus oxychloride are 0.5L/min. The temperature of vapor deposition was 900 ℃ and the time of vapor deposition was 5 hours.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride and sodium chloride are placed in a crucible, and two graphite sheets wound by 0.6mm molybdenum wires are respectively wound by conductive wires and suspended above the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 1L/min, the temperature is raised to 800 ℃ at the heating rate of 6 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.9V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 900 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 6cm, a constant voltage of 2.6V was applied between the electrodes, and electrolysis was started for 15 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 7 times by using ultrapure water to remove the fused salt attached to the surface of the sample. And drying at 70 ℃ for 12 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
Example 6
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the precursor 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 3: argon is used as a shielding gas, the flow rate is 3.5L/min, a porous hard carbon matrix is used as a substrate, trimethoxy silane and triethoxy silane which contain silicon oxygen are used as silicon sources, and gaseous compounds of propylene, urea, tripropyl borate and phosphine which contain C, N, B and P elements are introduced into a reaction container in the form of gases for vapor deposition, so that composite material powder is obtained; wherein, the gas flow rates of trimethoxysilane and triethoxysilane are 1.25L/min, and the gas flow rates 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.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride and potassium chloride are placed in a crucible, and two graphite sheets wound by copper wires with the thickness of 0.7mm are respectively wound by conductive wires and suspended above the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 1L/min, the temperature is raised to 900 ℃ at the heating rate of 6 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.9V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 1000 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 2cm, a constant voltage of 2.7V was applied between the electrodes, and electrolysis was started for 10 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 8 times by using ultrapure water to remove the fused salt attached to the surface of the sample. Drying at 50 ℃ for 16 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
Example 7
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the precursor 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 3: taking nitrogen as a shielding gas, the flow rate is 4L/min, a porous hard carbon matrix is taken as a substrate, and trimethoxy silane, tetramethoxy silane and triethoxy silane which contain silicon oxygen are taken as silicon sources, and compounds propane, hydrazine, diborane and phosphine which contain C, N, B and P elements are introduced into a reaction container in a gas form for vapor deposition, so as to obtain composite material powder; wherein, the gas flow rates of trimethoxy silane, tetramethoxy silane and triethoxy silane are all 1.3L/min, and the gas 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.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride and magnesium chloride are placed in a crucible, and two graphite sheets wound by an iron wire with the diameter of 0.8mm are respectively wound by a conductive wire and suspended on the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 1L/min, the temperature is raised to 800 ℃ at the heating rate of 8 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.5V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 900 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 4cm, a constant voltage of 2.8V was applied between the electrodes, and electrolysis was started for 8 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 5 times by using ultrapure water to remove the fused salt attached to the surface of the sample. And drying at 60 ℃ for 14 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
Example 8
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the precursor 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 3: argon is used as a shielding gas, the flow rate is 4.5L/min, a porous hard carbon matrix is used as a substrate, trimethoxy silane, tetramethoxy silane and tetraethoxy silane which contain silicon oxygen are used as silicon sources, and ethanol, nitrogen, trimethyl borate and phosphorus oxychloride which contain C, N, B and P elements are used as compounds, and the compounds are introduced into a reaction container in the form of gas for vapor deposition, so that composite material powder is obtained; wherein, the gas flow rates of trimethoxysilane, tetramethoxysilane and tetraethoxysilane are all 1.7L/min, and the gas flow rates of 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.
Step 4: molten salt electrolysis: and (3) placing the dried anhydrous sodium chloride and magnesium chloride into a crucible, and winding two graphite sheets wound by 0.2-1mm molybdenum wires by conductive wires and suspending the graphite sheets on the crucible to serve as a pre-electrolysis electrode. Argon is introduced, the gas flow rate is 2L/min, the temperature is raised to 900 ℃ at the heating rate of 5 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.5V was applied between the two graphite sheets for pre-electrolysis for 1.5 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 1000 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 5cm, a constant voltage of 2.5V was applied between the electrodes, and electrolysis was started for 7 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 5 times by using ultrapure water to remove the fused salt attached to the surface of the sample. Drying at 60 ℃ for 18 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
Example 9
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the precursor into a reaction device, introducing gas with the flow rate of 5L/min for pore-forming, adopting water vapor as a gas source, and preserving heat at 1000 ℃ for 10 hours to obtain a porous hard carbon matrix;
step 3: taking nitrogen as a shielding gas, the flow rate is 5L/min, a porous hard carbon matrix is taken as a substrate, tetramethoxysilane, triethoxysilane and tetraethoxysilane which contain silicon oxygen are taken as silicon sources, and compounds ethylene, propane, urea, melamine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride which contain C, N, B and P elements are introduced into a reaction container in a gas form for vapor deposition, so that composite material powder is obtained; wherein, the gas flow rates of tetramethoxysilane, triethoxysilane and tetraethoxysilane are all 2.7L/min, and the gas flow rates of ethylene, propane, urea, melamine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride gaseous compounds are all 1L/min. The temperature of vapor deposition was 1400℃and the time of vapor deposition was 1.25 hours.
Step 4: molten salt electrolysis: the dried anhydrous sodium chloride and potassium chloride are placed in a crucible, and two graphite sheets wound by 0.9mm molybdenum wires are respectively wound by conductive wires and suspended above the crucible to serve as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 2L/min, the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 2.8V was applied between the two graphite sheets for pre-electrolysis for 1 hour. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 900 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 6cm, a constant voltage of 2.8V was applied between the electrodes, and electrolysis was started for 6 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 6 times by using ultrapure water to remove the fused salt attached to the surface of the sample. Drying at 75 ℃ for 18 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
Example 10
The embodiment provides a novel composite material for a lithium ion battery, which comprises the following components:
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: putting the precursor into a reaction device, introducing gas with the flow rate of 5L/min for pore-forming, adopting water vapor as a gas source, and preserving heat at 900 ℃ for 5 hours to obtain a porous hard carbon matrix;
step 3: taking argon as a shielding gas, taking a porous hard carbon matrix as a substrate, taking trimethoxysilane, triethoxysilane and tetraethoxysilane containing silicon oxygen as silicon sources, and introducing acetylene, propane, ammonia, hydrazine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride containing C, N, B and P elements into a reaction container in a gas form for vapor deposition to obtain composite material powder; wherein, the gas flow rates of trimethoxysilane, triethoxysilane and tetraethoxysilane are all 3.3L/min, and the gas flow rates of acetylene, propane, ammonia, hydrazine, tripropyl borate, boron tribromide, phosphine and phosphorus oxychloride gaseous compounds are all 1.3L/min. The temperature of vapor deposition was 1500 ℃, and the time of vapor deposition was 1 hour.
Step 4: molten salt electrolysis: the dried anhydrous calcium chloride, sodium chloride and potassium chloride were placed in a crucible, and two graphite sheets wound with 1mm molybdenum wire were wound with conductive wires and suspended on the crucible, respectively, as pre-electrolysis electrodes. Argon is introduced, the gas flow rate is 2L/min, the temperature is increased by 900 ℃ at the heating rate of 10 ℃/min, and after half an hour of heat preservation, two graphite sheets are placed. A constant voltage of 3.0V was applied between the two graphite sheets for pre-electrolysis for 2 hours. And (3) after the pre-electrolysis is finished, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, continuously heating the crucible to 1000 ℃, lifting the pre-electrolysis electrode upwards from the molten salt to be suspended, and putting the composite material powder prepared in the step (3). The distance between the electrodes was 6cm, a constant voltage of 3.0V was applied between the electrodes, and electrolysis was started for 5 hours. After the electrolysis is completed, taking out the electrolyzed sample, and performing ultrasonic washing for 8 times by using ultrapure water to remove the fused salt attached to the surface of the sample. And drying at 80 ℃ for 20 hours to obtain the small-size high-dispersion silicon-oxygen-carbon composite material, namely the novel composite material for the lithium ion battery.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
For better comparison, we prepared a comparative sample as follows.
Comparative example 1
Step 1: adding 200g of nano silica 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 a spherical silicon-containing carbonized precursor;
step 2: and (3) mixing the samples obtained in the step (I), then placing the mixture into a reaction device, heating to 700 ℃ at a speed of 3 ℃/min, and preserving heat for 6 hours under nitrogen atmosphere for carbonization to obtain the silicon-carbon composite material for comparison.
The electrochemical properties of the assembled button cell were evaluated by the test described in example 1, and are reported in table 1.
TABLE 1
As can be seen from comparison of comparative examples and examples, the novel composite lithium storage material for the lithium ion battery provided by the invention has higher specific capacity and initial efficiency. By using the hard carbon material with penetrating pores, more nano silica particles can be deposited in the hard carbon matrix, and simultaneously the capacity and first effect of the material can be further improved by regulating and controlling the deposition time, temperature, gas flow rate and molten salt electrolysis time. The invention scientifically sets the gas flow rate and the temperature in the preparation process, and avoids the phenomenon that silane is decomposed too fast due to the too high gas flow rate and the too high temperature and is directly deposited on the surface of the carbon matrix, thereby influencing the performance of the battery. Meanwhile, incomplete decomposition of silane caused by too low temperature is avoided, and the capacity of the battery is prevented from being influenced. By further electrolysis, part of silicon oxide particles can be reduced into nano silicon particles, so that the buffer space is further increased, and the specific capacity of the material is improved by utilizing the silicon particles. The invention scientifically sets the molten salt electrolysis time in the preparation, and when the molten salt electrolysis time is shorter, the silicon oxide content is more, so that the charging specific capacity is smaller and the coulomb efficiency is lower. When the electrolysis time exceeds a certain time, the volume expansion of the silicon is more obvious due to the more content of the silicon, so that the coulomb efficiency of the silicon starts to be reduced, and when the volume effect of the silicon exceeds a reserved buffer space, the structure of the composite material is damaged, and the coulomb efficiency and the cycle stability are influenced.
According to the novel composite material for the lithium ion battery, one or more of nano SiOx and a gaseous compound containing C, N, B, P elements in the composite material are uniformly distributed in pores of spherical porous carbon through vapor deposition, and then the composite material is reduced through molten salt electrolysis, so that the range of x in SiOx is controlled. On one hand, the material can limit the size of SiOx and reduced nano silicon and uniformly disperse in a carbon material, so that the expansion effect is reduced, and the problem of electrical contact deterioration caused by SiOx pulverization is avoided; on the other hand, the expansion of SiOx can be limited, the damage of SiOx expansion to the composite material is reduced, and the cycle performance of the battery is further improved. And, through multielement recombination, the specific capacity and the first cycle efficiency are further improved. Meanwhile, the spherical porous carbon can effectively increase the compaction density of the coated pole piece, thereby improving the energy density of the battery.
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 novel composite material for the lithium ion battery is characterized in that: a spherical porous hard carbon material having silicon nanoparticles deposited inside the pores and a product of decomposition deposition of a silicon-oxygen-containing gas and one or more gaseous compounds containing any one of C, N, B, P elements; the product comprises SiOx particles; x ranges from 0 to 1.5, and the value of x is controlled through molten salt electrolysis; 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-oxygen-containing gas is a siloxane compound, comprising: a combination of one or more of trimethoxysilane, tetramethoxysilane, triethoxysilane, and tetraethoxysilane;
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 novel composite material for a lithium ion battery according to any one of claims 1 to 4, wherein the preparation method comprises the following steps:
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: introducing a pore-forming air source into the spherical carbonized precursor 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 carbon dioxide and water vapor;
step three: vapor deposition is carried out on the porous hard carbon matrix material to obtain composite material powder; the gas source of the vapor deposition comprises a silicon oxide-containing gas and one or more gaseous compounds containing any element C, N, B, P;
Step four: placing the dried salt into a crucible, and winding and suspending two graphite sheets on the crucible by conductive wires respectively to serve as pre-electrolysis electrodes; argon is introduced, the gas flow rate is 0.5-2L/min, the temperature is raised to 800-900 ℃ at the heating rate of 2-10 ℃/min, and two graphite sheets are placed after heat preservation for half an hour; applying constant voltage of 2.5-3.0V between two graphite sheets for pre-electrolysis for 1-2 hours; after the pre-electrolysis is finished, continuously heating to 900-1000 ℃, and lifting two graphite sheets from molten salt to be suspended; putting composite material powder, applying constant voltage of 2.2-3.0V between two electrodes of molten salt electrolysis, and starting electrolysis for 5-20 hours; and after the electrolysis is finished, taking out the electrolyzed sample, washing with water, placing the sample in a blast drying box, and drying at 50-80 ℃ for 8-20 hours to obtain the novel composite material for the lithium ion battery.
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-oxygen-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 of claim 5, wherein the dried salt comprises: one or more of calcium chloride, magnesium chloride, sodium chloride and potassium chloride;
the silicon-oxygen-containing gas is a siloxane compound, comprising: a combination of one or more of trimethoxysilane, tetramethoxysilane, triethoxysilane, and tetraethoxysilane;
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 of a lithium ion battery, characterized in that the negative electrode material of the lithium ion battery comprises the novel composite material for the lithium ion battery according to any one of the claims 1-4.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the novel composite material for a lithium ion battery according to any one of the above claims 1-4.
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