CN115312718A - Silicon-titanium composite negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Silicon-titanium composite negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN115312718A CN115312718A CN202210907344.5A CN202210907344A CN115312718A CN 115312718 A CN115312718 A CN 115312718A CN 202210907344 A CN202210907344 A CN 202210907344A CN 115312718 A CN115312718 A CN 115312718A
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- 239000002131 composite material Substances 0.000 title claims abstract description 87
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000002156 mixing Methods 0.000 claims abstract description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 46
- 239000010936 titanium Substances 0.000 claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
- 239000002893 slag Substances 0.000 claims abstract description 42
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 39
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011777 magnesium Substances 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000012423 maintenance Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000011946 reduction process Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 8
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 26
- 229910008484 TiSi Inorganic materials 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 239000010406 cathode material Substances 0.000 description 11
- 239000010405 anode material Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 235000010215 titanium dioxide Nutrition 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 6
- 239000002153 silicon-carbon composite material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003139 buffering effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 239000007833 carbon precursor Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- VSTOHTVURMFCGL-UHFFFAOYSA-N [C].O=[Si]=O Chemical compound [C].O=[Si]=O VSTOHTVURMFCGL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 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 description 1
- 241000695274 Processa Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
-
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- 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
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Abstract
The invention provides a silicon-titanium composite negative electrode material, a preparation method thereof and a lithium ion battery, wherein the preparation method comprises the following steps: mixing silicon dioxide, titanium-containing blast furnace slag and magnesium powder, and carrying out magnesium thermal reduction to obtain a silicon-titanium composite negative electrode material; the mass fraction of titanium dioxide in the titanium-containing blast furnace slag is 10-23 wt%; the silicon dioxide, the titanium-containing blast furnace slag andthe mass ratio of the magnesium powder is (8-12) to (6-10). The preparation method of the invention utilizes the titanium-containing blast furnace slag as resources; tiSi generated in the magnesiothermic reduction process 2 The method is favorable for absorbing a large amount of heat generated in the reaction process, prevents the melting and bonding of the nano silicon particles, and improves the dispersibility of the silicon-titanium composite negative electrode material; the lithium ion battery prepared by the silicon-titanium composite negative electrode material has good rate capability; the lithium ion battery prepared by the silicon-titanium composite negative electrode material has good cycle stability; the preparation method has simple process and low preparation cost.
Description
Technical Field
The invention belongs to the technical field of silicon-carbon composite materials, relates to a silicon-titanium composite negative electrode material, and particularly relates to a silicon-titanium composite negative electrode material, a preparation method of the silicon-titanium composite negative electrode material and a lithium ion battery.
Background
The silicon with the nano structure has wide application prospect in the aspects of new energy materials, solar energy, microelectronics, biochemistry, environmental protection and the like. The metallurgical silicon with higher purity can be obtained by the traditional carbothermic reduction, however, the reaction temperature of the traditional carbothermic reduction is often more than 1400 ℃, so that the widely applicable nanoscale silicon material is difficult to obtain. At present, the methods for preparing the nano silicon material mainly comprise chemical or electrochemical etching, rapid cooling, laser ablation, a silicon tetrachloride reduction method and a silane pyrolysis method. The preparation methods generally have the defects of high cost, complex equipment structure, high toxicity and low yield, and are not beneficial to large-scale production and preparation of the nano silicon. Metallothermic silicon is believed to have the potential to overcome the above problems, but there are some problems with conventional metallothermic silicon. For example, in the magnesium thermal or aluminothermic reduction, although porous silicon with a nanostructure can be obtained after reduction, the nanostructure of the porous silicon has poor homogenization degree and dispersibility due to disordered accumulation of silicon atoms in the reduction process and fusion adhesion of the nanostructure, so that the performance of the porous silicon in specific application is influenced.
CN111834610A discloses a preparation method of a lithium ion battery silicon-carbon composite cathode material based on magnesiothermic reduction, which comprises the steps of preparing a high-concentration graphite dispersion liquid by using graphite and a carboxymethyl cellulose (CMC) or hydroxypropyl cellulose (HPC) solution, adding nano silica sol into the graphite dispersion liquid to uniformly disperse the graphite dispersion liquid, then carrying out spray drying on the dispersion liquid to form a graphite/silica composite, carrying out magnesiothermic reduction reaction, and finally adding a styrene-acrylonitrile copolymer emulsion and carrying out high-temperature treatment to obtain the lithium ion battery silicon-carbon composite material.
CN106374088A discloses a method for preparing a silicon-carbon composite material by a magnesiothermic reduction method, belonging to the technical field of composite material preparation. The method comprises the following steps: (1) Mixing a silicon dioxide source, an organic carbon source and a solvent, performing ball milling to obtain a homogenate mixture, and drying to obtain a silicon dioxide-carbon precursor composite material; (2) And mixing the silicon dioxide-carbon precursor composite material with magnesium powder to perform a magnesiothermic reduction reaction, collecting a product, performing acid washing, water washing, and drying to obtain the silicon-carbon composite material.
CN105762338A discloses a method for preparing a silicon-carbon negative electrode material of a lithium ion battery by using magnesiothermic reduction, which comprises: preparing a mixed solution of sodium silicate, glucose and sodium chloride; heating and drying to prepare a brown caramel-like precursor; heating to 650 ℃ in Ar atmosphere, and calcining to obtain a sodium silicate/carbon precursor; adding HCl into a sodium silicate/carbon precursor to prepare a mixed solution by utilizing a strong acid-to-weak acid principle, subsequently placing the mixed solution into an oven at 170 ℃ for drying, and washing a sample with water to obtain a silicon dioxide/porous carbon composite material; uniformly mixing the silicon dioxide/porous carbon composite material with magnesium powder and sodium chloride, calcining at 700 ℃, and carrying out acid treatment, water washing and drying to obtain the silicon-carbon composite material.
The currently disclosed silicon-titanium composite negative electrode material and the preparation method thereof have certain defects, and have the problems of poor dispersibility, poor uniformity, poor conductivity, poor rate performance and poor cycle stability of the silicon-titanium composite negative electrode material, and the problems of complex process and high preparation cost of the preparation method of the silicon-titanium composite negative electrode material. Therefore, it is important to develop and design a novel silicon-titanium composite anode material and a preparation method thereof.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a silicon-titanium composite negative electrode material, a preparation method thereof and a lithium ion battery, wherein the preparation method utilizes titanium-containing blast furnace slag as resources; tiSi generated in the process of magnesiothermic reduction 2 Is beneficial to absorbing a large amount of heat generated in the reaction process, prevents the melting and the bonding of the nano silicon particles, and improves the dispersion of the silicon-titanium composite cathode materialSex; the lithium ion battery prepared by the silicon-titanium composite negative electrode material has good rate capability; the lithium ion battery prepared by the silicon-titanium composite negative electrode material has good cycling stability; the preparation method has simple process and low preparation cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a silicon-titanium composite anode material, which comprises the following steps:
mixing silicon dioxide, titanium-containing blast furnace slag and magnesium powder, and carrying out magnesiothermic reduction to obtain a silicon-titanium composite negative electrode material;
the mass fraction of titanium dioxide in the titanium-containing blast furnace slag is 10-23 wt%;
the mass ratio of the silicon dioxide, the titanium-containing blast furnace slag and the magnesium powder is (8-12) to (6-10).
The titanium-containing blast furnace slag belongs to high-yield hazardous waste materials which are difficult to treat, is usually treated by landfill, and has great pollution to the environment; the main component of the titanium-containing blast furnace slag is TiO 2 、Fe、SiO 2 、 MgO、Al 2 O 3 、CaO、MnO、V 2 O 5 、Ga 2 O 3 、Cr 2 O 3 And so on.
The present invention defines a mass ratio of silica to titanium-containing blast furnace slag of (8 to 12) which can be, for example, 8.
The present invention defines a mass ratio of silica to magnesium powder of (8 to 12) and may be, for example, 8.
The preparation method of the invention is used for smelting steelThe produced cheap titanium-containing blast furnace slag is introduced into the magnesiothermic reduction process of silicon dioxide, the titanium-containing blast furnace slag is recycled, the problem of treatment of the titanium-containing blast furnace slag waste is solved, and waste materials are changed into valuable materials; in the magnesium thermal reduction process, the reduction product of titanium dioxide, namely TiSi generated by the reaction of titanium and silicon 2 ，TiSi 2 The generation of the silicon-titanium composite negative electrode material is beneficial to absorbing a large amount of heat generated in the reaction process, the melting and bonding of nano silicon particles are prevented, and the dispersity of the silicon-titanium composite negative electrode material is improved; tiSi 2 The lithium ion battery prepared from the silicon-titanium composite negative electrode material has good rate capability; tiSi 2 The silicon-titanium composite cathode material can serve as an anchor point for buffering the volume change of the silicon material in the electrochemical circulation process, and the lithium ion battery prepared from the silicon-titanium composite cathode material has good circulation stability; the preparation method has simple process and low preparation cost.
Preferably, the mixing further comprises mixing of a reduction aid.
Preferably, the reduction aid comprises any one or a combination of at least two of sodium chloride, sodium bromide, sodium fluoride, sodium iodide, potassium chloride, potassium bromide, potassium fluoride, and potassium iodide, and typical but non-limiting combinations include a combination of sodium chloride and sodium bromide, a combination of sodium bromide and sodium fluoride, a combination of sodium iodide and potassium chloride, a combination of potassium bromide and potassium fluoride, a combination of sodium chloride and potassium iodide, a combination of sodium chloride, sodium bromide and sodium fluoride, or a combination of sodium chloride, sodium bromide, sodium fluoride and potassium chloride.
Preferably, the mass ratio of the reduction assistant to silica is 100 (8 to 12), and may be, for example, 100.
Preferably, the magnesiothermic reduction is carried out in a reducing atmosphere.
Preferably, the reducing atmosphere is formed by mixing a reducing gas and a protective gas.
Preferably, the reducing gas comprises any one or a combination of at least two of hydrogen, carbon monoxide, hydrogen sulphide, methane, sulphur monoxide, typical but non-limiting combinations comprising a combination of hydrogen and carbon monoxide, a combination of carbon monoxide and hydrogen sulphide, a combination of methane and sulphur monoxide, a combination of hydrogen, carbon monoxide and hydrogen sulphide, or a combination of hydrogen, carbon monoxide, hydrogen sulphide and methane.
Preferably, the protective gas comprises an inert gas and/or nitrogen.
The inert gas comprises any one or the combination of at least two of helium, neon, argon, krypton and xenon.
Preferably, the volume fraction of the reducing gas in the reducing atmosphere is 3-10% by volume of the reducing atmosphere, and the balance is the protective gas.
The volume fraction of the reducing gas in the reducing atmosphere is limited to 3% to 10%, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, but the present invention is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the magnesiothermic reduction comprises sequentially heating and holding.
Preferably, the temperature rise rate is 3-15 ℃/min, and the temperature rise end point temperature is 600-900 ℃.
The present invention limits the rate of temperature rise to 3 to 15 ℃/min, and may be, for example, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min or 15 ℃/min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The temperature at the end of the temperature rise is limited to 600 to 900 ℃ in the present invention, and may be, for example, 600 ℃, 650 ℃,700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the incubation time is 4 to 10 hours, for example 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the preparation method further comprises pickling after the magnesiothermic reduction.
In the present invention, hydrochloric acid and/or sulfuric acid are used for pickling.
Preferably, the preparation of the silica comprises the following steps:
(1) Mixing water, ethanol and ammonia water to obtain a first mixed solution;
(2) Mixing ethanol and ethyl silicate to obtain a second mixed solution;
(3) Mixing the first mixed solution and the second mixed solution, and carrying out solid-liquid separation to obtain silicon dioxide;
the step (1) and the step (2) are not in sequence.
Preferably, the mass ratio of the water, the ethanol and the ammonia water in the step (1) is (40-60): 28-36): 15-20.
The present invention defines that the mass ratio of water to ethanol in step (1) is (40-60) and can be, for example, 40.
The present invention defines that in step (1), the mass ratio of ethanol to ammonia is (28-36) (15-20), and may be, for example, from.
Preferably, the mass ratio of ethanol to ethyl silicate in step (2) is (80-100): for example, 80.
Preferably, in the step (3), the mass ratio of the first mixed liquid to the second mixed liquid is (0.9 to 1.2): 1, and for example, 0.9.
Preferably, the mixing mode in the step (1) comprises stirring, the rotating speed of the stirring is 400-700 r/min, and the time is 1-6 min.
The invention limits the rotation speed of stirring to 400-700 r/min, for example 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, 650r/min or 700r/min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The stirring time is limited to 1-6 min, for example, 1min, 2min, 3min, 4min, 5min or 6min, but the invention is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mixing mode in the step (2) comprises stirring, the rotating speed of the stirring is 400-700 r/min, and the time is 1-6 min.
The invention is limited to stirring speeds of 400 to 700r/min, for example 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, 650r/min or 700r/min, but is not limited to the values listed and other values not listed in this range are equally applicable.
The stirring time is limited to 1-6 min, for example, 1min, 2min, 3min, 4min, 5min or 6min, but the invention is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mixing manner in the step (3) comprises stirring, wherein the rotation speed of the stirring is 400-700 r/min, and the time is 1-6 h.
The invention limits the rotation speed of stirring to 400-700 r/min, for example 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, 650r/min or 700r/min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The stirring time is limited to 1 to 6 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, but the stirring time is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the preparation of the silicon dioxide further comprises water washing and drying which are sequentially carried out after solid-liquid separation.
Preferably, the drying temperature is 60-80 ℃ and the drying time is 10-14 h.
The invention is limited to drying temperatures of 60 to 80 c, for example 60 c, 65 c, 70 c, 75 c or 80 c, but is not limited to the recited values, and other values not recited within this range are equally applicable.
The drying time is limited to 10-14 h, for example, 10h, 11h, 12h, 13h or 14h, but the drying time is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable embodiment of the production method of the first aspect, the production method includes:
the titanium-containing blast furnace slag and the magnesium powder are mixed according to the mass ratio of 100 (8-12) to 6-12 to 6-10), wherein the mass fraction of the silicon dioxide and the titanium dioxide is 10-23 wt%; heating to 600-900 ℃ at the speed of 3-15 ℃/min in a reducing atmosphere formed by mixing reducing gas and protective gas, and preserving heat for 4-10 h; the volume of the reducing atmosphere is taken as percentage, the volume fraction of the reducing gas in the reducing atmosphere is 3-10%, and the balance is protective gas; and (4) carrying out acid washing to obtain the silicon-titanium composite negative electrode material.
In a second aspect, the invention provides a silicon-titanium composite anode material, which is obtained by the preparation method in the first aspect.
In a third aspect, the invention provides a lithium ion battery, which comprises a positive pole piece, a diaphragm and a negative pole piece which are sequentially stacked, wherein the negative pole piece comprises a current collector and a negative active layer coated on the surface of the current collector, and the negative active layer comprises the silicon-titanium composite negative material in the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method introduces the cheap titanium-containing blast furnace slag generated in the steel smelting process into the magnesiothermic reduction process of silicon dioxide, recycles the titanium-containing blast furnace slag, solves the treatment problem of the titanium-containing blast furnace slag waste, and changes waste into valuable;
(2) In the magnesium thermal reduction process, a reduction product of titanium oxide, namely TiSi generated by the reaction of titanium and silicon 2 ，TiSi 2 The generation of the silicon-titanium composite negative electrode material is beneficial to absorbing a large amount of heat generated in the reaction process, the melting and bonding of nano silicon particles are prevented, and the dispersibility of the silicon-titanium composite negative electrode material is improved;
(3) The TiSi generated in the magnesium thermal reduction process of the invention 2 The lithium ion battery prepared from the silicon-titanium composite negative electrode material has good rate performance;
(4) The TiSi generated in the magnesium thermal reduction process of the invention 2 The silicon-titanium composite cathode material can serve as an anchor point for buffering the volume change of the silicon material in the electrochemical circulation process, and the lithium ion battery prepared from the silicon-titanium composite cathode material has good circulation stability;
(5) The preparation method provided by the invention is simple in process and low in preparation cost.
Drawings
Fig. 1 is an SEM image of a silicon titanium composite anode material in example 1.
Fig. 2 is a graph showing the rate performance test results of the lithium ion battery prepared from the silicon-titanium composite anode material in example 1.
Fig. 3 is a graph showing the test results of the cycle stability test of the lithium ion battery prepared from the silicon titanium composite anode material in example 1.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a silicon-titanium composite anode material, which comprises the following steps:
mixing 16wt% of titanium-containing blast furnace slag and 16wt% of magnesium powder in the mass ratio of 100; heating to 700 ℃ at the speed of 6 ℃/min in a reducing atmosphere formed by mixing hydrogen and argon, and preserving heat for 8 hours; the volume fraction of hydrogen in the reducing atmosphere is 6 percent, and the balance is argon according to the volume of the reducing atmosphere; and (4) pickling with hydrochloric acid to obtain the silicon-titanium composite negative electrode material.
The preparation of the silicon dioxide comprises the following steps:
(1) Stirring the mixture for 4min at the rotating speed of 550r/min, and mixing the water, the ethanol and the ammonia water at the mass ratio of 50;
(2) Stirring the mixture for 3min at the rotating speed of 550r/min, and mixing the ethanol and the ethyl silicate with the mass ratio of 90;
(3) Stirring the first mixed solution and the second mixed solution at the rotation speed of 550r/min for 3h, mixing the first mixed solution and the second mixed solution according to the mass ratio of 1, performing solid-liquid separation, washing with water, and drying at 75 ℃ for 11h to obtain silicon dioxide;
the step (1) and the step (2) are not in sequence.
Example 2
The embodiment provides a preparation method of a silicon-titanium composite negative electrode material, which comprises the following steps:
mixing 13wt% of titanium-containing blast furnace slag and magnesium powder with the mass fraction of sodium chloride, silicon dioxide and titanium dioxide being 100; heating to 700 ℃ at the speed of 9 ℃/min in a reducing atmosphere formed by mixing hydrogen and nitrogen, and preserving heat for 6 hours; the volume of the hydrogen in the reducing atmosphere is 4.5 percent, and the balance is nitrogen; and (4) pickling with hydrochloric acid to obtain the silicon-titanium composite negative electrode material.
The preparation of the silicon dioxide comprises the following steps:
(1) Stirring at the rotating speed of 600r/min for 3min, and mixing water, ethanol and ammonia water in a mass ratio of 40;
(2) Stirring at the rotating speed of 600r/min for 4min, and mixing the ethanol and the ethyl silicate at the mass ratio of 100;
(3) Stirring the first mixed solution and the second mixed solution at the rotating speed of 500r/min for 5 hours, mixing the first mixed solution and the second mixed solution according to the mass ratio of 0.95 to the first mixed solution, performing solid-liquid separation and washing, and drying at 70 ℃ for 12 hours to obtain silicon dioxide;
the step (1) and the step (2) are not in sequence.
Example 3
The embodiment provides a preparation method of a silicon-titanium composite anode material, which comprises the following steps:
mixing the titanium-containing blast furnace slag and the magnesium powder with the mass fraction of 20wt% in the following mass ratio of 100; in a reducing atmosphere formed by mixing carbon monoxide and nitrogen, heating to 800 ℃ at the speed of 12 ℃/min and preserving heat for 4 hours; the volume fraction of carbon monoxide in the reducing atmosphere is 8 percent, and the balance is nitrogen gas; and (4) sulfuric acid pickling to obtain the silicon-titanium composite negative electrode material.
The preparation method of the titanium dioxide comprises the following steps:
(1) Stirring at the rotating speed of 500r/min for 5min, and mixing water, ethanol and ammonia water in a mass ratio of 60;
(2) Stirring the mixture for 5min at the rotating speed of 500r/min, and mixing the ethanol and the ethyl silicate with the mass ratio of 80;
(3) Stirring the first mixed solution and the second mixed solution at the rotating speed of 600r/min for 4 hours, mixing the first mixed solution and the second mixed solution according to the mass ratio of 1.1, performing solid-liquid separation and washing, and drying at 65 ℃ for 13 hours to obtain silicon dioxide;
the step (1) and the step (2) are not in sequence.
Example 4
The embodiment provides a preparation method of a silicon-titanium composite negative electrode material, which comprises the following steps:
mixing the titanium-containing blast furnace slag and the magnesium powder with the mass fractions of potassium chloride, silicon dioxide and titanium dioxide of 100; heating to 600 ℃ at the speed of 3 ℃/min in a reducing atmosphere formed by mixing hydrogen sulfide and helium, and preserving heat for 10 hours; the volume of the reducing atmosphere is taken as percentage, the volume fraction of hydrogen sulfide in the reducing atmosphere is 10%, and the balance is helium; and (4) sulfuric acid pickling to obtain the silicon-titanium composite negative electrode material.
The preparation of the silicon dioxide comprises the following steps:
(1) Stirring for 6min at the rotating speed of 400r/min, and mixing water, ethanol and ammonia water according to the mass ratio of 60;
(2) Stirring at the rotating speed of 400r/min for 6min, and mixing ethanol and ethyl silicate at the mass ratio of 80;
(3) Stirring the first mixed solution and the second mixed solution at the rotating speed of 400r/min for 6 hours, mixing the first mixed solution and the second mixed solution according to the mass ratio of 0.9, performing solid-liquid separation and washing, and drying at 60 ℃ for 14 hours to obtain silicon dioxide;
the step (1) and the step (2) are not in sequence.
Example 5
The embodiment provides a preparation method of a silicon-titanium composite negative electrode material, which comprises the following steps:
mixing 10wt% of titanium-containing blast furnace slag and magnesium powder with the mass ratio of 100; heating to 900 ℃ at the speed of 15 ℃/min in a reducing atmosphere formed by mixing hydrogen and neon, and preserving heat for 4 hours; the volume of hydrogen in the reducing atmosphere is 3 percent, and the balance is neon; and (4) pickling with hydrochloric acid to obtain the silicon-titanium composite negative electrode material.
The preparation of the silicon dioxide comprises the following steps:
(1) Stirring at the rotating speed of 700r/min for 1min, and mixing water, ethanol and ammonia water in a mass ratio of 40;
(2) Stirring at the rotating speed of 700r/min for 1min, and mixing ethanol and ethyl silicate at the mass ratio of 100;
(3) Stirring the mixture at the rotating speed of 700r/min for 1 hour to mix the first mixed solution and the second mixed solution with the mass ratio of 1.2, carrying out solid-liquid separation and washing, and drying at the temperature of 80 ℃ for 10 hours to obtain the silicon dioxide.
Example 6
The embodiment provides a preparation method of a silicon-titanium composite negative electrode material, which is the same as that in the embodiment 1 except that the mass ratio of silicon dioxide to titanium-containing blast furnace slag is 5.
Example 7
The embodiment provides a preparation method of a silicon-titanium composite negative electrode material, which is the same as that in the embodiment 1 except that the mass ratio of silicon dioxide to titanium-containing blast furnace slag is 12.
Example 8
The embodiment provides a preparation method of a silicon-titanium composite negative electrode material, which is the same as that in the embodiment 1 except that the mass ratio of sodium chloride to silicon dioxide is 100.
Example 9
The embodiment provides a preparation method of a silicon-titanium composite negative electrode material, which is the same as that in the embodiment 1 except that the mass ratio of sodium chloride to silicon dioxide is 100.
Comparative example 1
This comparative example provides a method for producing a silicon anode material, which is the same as that of example 1 except that the titanium-containing blast furnace slag is omitted.
Performing field emission scanning electron microscope test on the silicon-titanium composite negative electrode material in the embodiment 1 to obtain an SEM image as shown in FIG. 1;
conductivity tests were performed on the silicon titanium composite negative electrode materials in examples 1 to 9 and the silicon negative electrode material in comparative example 1, and the obtained conductivities are shown in table 1;
the lithium ion battery is prepared by using the silicon-titanium composite negative electrode materials in the examples 1-9 and the silicon negative electrode material in the comparative example 1, and the preparation method comprises the following steps:
the silicon-titanium composite negative electrode material or the silicon negative electrode material, acetylene black and sodium alginate are weighed according to the mass ratio of 60;
the rate capability test of the lithium ion battery is carried out, and the test method comprises the following steps: in a voltage interval of 3.0-0.01V, the lithium ion battery is charged and discharged at different multiplying powers, and the discharge average capacity C1 of the lithium ion battery obtained by testing and preparing at a current density of 0.21A/g and the discharge average capacity C2 of the lithium ion battery at a current density of 8.4A/g are shown in a table 1;
the rate performance test result of the lithium ion battery prepared from the silicon-titanium composite negative electrode material in example 1 is shown in fig. 2;
the lithium ion battery is subjected to a cycle stability test, and the test method comprises the following steps: in a voltage range of 3.0-0.01V, the lithium ion battery is charged and discharged at a current density of 0.84A/g, and after 200 cycles, the specific capacity and the coulombic efficiency of the lithium ion battery are shown in Table 1;
the test results of the cycle stability test of the lithium ion battery prepared by using the silicon-titanium composite negative electrode material in example 1 are shown in fig. 3.
TABLE 1
From Table 1 and FIGS. 1 to 3, it can be seen that:
(1) The silicon-titanium composite negative electrode materials obtained in the embodiments 1 to 5 have good dispersibility and higher conductivity, and the lithium ion battery prepared from the silicon-titanium composite negative electrode materials has excellent rate capability and high cycle stability; the preparation method introduces cheap titanium-containing blast furnace slag generated in the steel smelting process into silicon dioxideIn the magnesium thermal reduction process, the titanium-containing blast furnace slag is recycled, the problem of treatment of the titanium-containing blast furnace slag waste is solved, and waste is changed into valuable; in the magnesium thermal reduction process, the reduction product of titanium dioxide, namely TiSi generated by the reaction of titanium and silicon 2 ， TiSi 2 The generation of the silicon-titanium composite negative electrode material is beneficial to absorbing a large amount of heat generated in the reaction process, the melting and bonding of nano silicon particles are prevented, and the dispersibility of the silicon-titanium composite negative electrode material is improved; tiSi 2 The lithium ion battery prepared from the silicon-titanium composite negative electrode material has good rate performance; tiSi 2 The silicon-titanium composite cathode material can serve as an anchor point for buffering the volume change of the silicon material in the electrochemical circulation process, and the lithium ion battery prepared from the silicon-titanium composite cathode material has good circulation stability; the preparation method has simple process and low preparation cost;
(2) As can be seen from the comparison between example 1 and examples 6 and 7, the mass ratio of the silicon dioxide to the titanium-containing blast furnace slag can affect the performance of the silicon-titanium composite anode material and the lithium ion battery; when the mass ratio of the silicon dioxide to the titanium-containing blast furnace slag is lower, the conductivity is improved, the discharge level average capacity at the current density of 0.21A/g is reduced, the discharge level average capacity at the current density of 8.4A/g is reduced, the specific capacity after 200 cycles is reduced, and the coulombic efficiency after 200 cycles is reduced, namely TiSi generated in the magnesium thermal process 2 Too much, the capacity of the whole material is reduced, and TiSi is added 2 The excess results in material agglomeration, so that the cycle reversibility becomes poor; when the mass ratio of the silicon dioxide to the titanium-containing blast furnace slag is higher, the conductivity is reduced, the discharge level average capacity at the current density of 0.21A/g is reduced, the discharge level average capacity at the current density of 8.4A/g is reduced, the specific capacity after 200 cycles is reduced, and the coulombic efficiency after 200 cycles is reduced, which is caused by that TiSi in the material is higher 2 The content of (b) is reduced, and the effect of improving the overall conductivity of the material is reduced, so that the electrochemical performance is deteriorated.
(3) As can be seen from the comparison between example 1 and examples 8 and 9, the mass ratio of the reduction assistant to the silicon dioxide affects the performance of the silicon-titanium composite negative electrode material and the lithium ion battery; when the mass of the reduction assistant and the silicaWhen the specific ratio is lower, the conductivity is reduced, the level average capacity under the current density of 0.21A/g is reduced, the level average capacity under the current density of 8.4A/g is reduced, the specific capacity after 200 cycles is reduced, and the coulombic efficiency after 200 cycles is reduced, which is caused by the lower amount of the reduction auxiliary agent 2 Reduction is insufficient while TiSi is present 2 The formation of (a) is also reduced, and the conductivity of the whole material is also reduced; when the mass ratio of the reducing additive to the silicon dioxide is higher, the conductivity is reduced, the discharge level average capacity at the current density of 0.21A/g is reduced, the discharge level average capacity at the current density of 8.4A/g is reduced, the specific capacity after 200 cycles is reduced, and the coulombic efficiency after 200 cycles is reduced, which is caused by excessive reducing additive, the heat release in the magnesium thermal process is excessive, so that the material is seriously agglomerated, and the performance of the material is deteriorated;
(4) The comparison between the example 1 and the comparative example 1 shows that the addition of the titanium-containing blast furnace slag is beneficial to improving the performances of the silicon-titanium composite negative electrode material and the lithium ion battery; after the titanium-containing blast furnace slag is added, the obtained silicon-titanium composite negative electrode material has large conductivity, large average capacity of discharging level at 0.21A/g current density, large average capacity of discharging level at 8.4A/g current density, large specific capacity after 200 cycles and high coulombic efficiency after 200 cycles, because TiSi generated in the magnesiothermic reduction process is added into the titanium-containing blast furnace slag 2 The lithium ion battery prepared from the silicon-titanium composite negative electrode material has good conductivity, and the conductivity of the silicon-titanium composite negative electrode material is improved, so that the lithium ion battery prepared from the silicon-titanium composite negative electrode material has good rate capability; tiSi 2 The silicon-titanium composite cathode material can be used as an anchor point for buffering the volume change of the silicon material in the electrochemical circulation process, and the lithium ion battery prepared from the silicon-titanium composite cathode material has good circulation stability.
In conclusion, the preparation method introduces the cheap titanium-containing blast furnace slag generated in the steel smelting process into the magnesiothermic reduction process of silicon dioxide, so that the titanium-containing blast furnace slag is recycled, the problem of treatment of the titanium-containing blast furnace slag waste is solved, and waste materials are changed into valuable materials; in the magnesium thermal reduction process, the reduction product of titanium dioxide, namely TiSi generated by the reaction of titanium and silicon 2 ，TiSi 2 Is generated in favor of absorbing the product generated in the reaction processA large amount of heat prevents the melting and bonding of nano silicon particles, and improves the dispersibility of the silicon-titanium composite negative electrode material; the TiSi generated in the magnesium thermal reduction process of the invention 2 The lithium ion battery prepared from the silicon-titanium composite negative electrode material has good rate capability; the TiSi generated in the magnesium thermal reduction process of the invention 2 The silicon-titanium composite cathode material can serve as an anchor point for buffering the volume change of the silicon material in the electrochemical circulation process, and the lithium ion battery prepared from the silicon-titanium composite cathode material has good circulation stability; the preparation method provided by the invention is simple in process and low in preparation cost.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The preparation method of the silicon-titanium composite negative electrode material is characterized by comprising the following steps of:
mixing silicon dioxide, titanium-containing blast furnace slag and magnesium powder, and carrying out magnesium thermal reduction to obtain a silicon-titanium composite negative electrode material;
the mass fraction of titanium dioxide in the titanium-containing blast furnace slag is 10-23 wt%;
the mass ratio of the silicon dioxide, the titanium-containing blast furnace slag and the magnesium powder is (8-12) to (6-10).
2. The method of claim 1, wherein the mixing further comprises mixing a reducing agent;
preferably, the reduction auxiliary agent comprises any one or a combination of at least two of sodium chloride, sodium bromide, sodium fluoride, sodium iodide, potassium chloride, potassium bromide, potassium fluoride or potassium iodide;
preferably, the mass ratio of the reduction assistant to the silicon dioxide is 100 (8-12).
3. The production method according to claim 1 or 2, characterized in that the magnesiothermic reduction is performed in a reducing atmosphere;
preferably, the reducing atmosphere is formed by mixing a reducing gas and a protective gas;
preferably, the reducing gas comprises any one of hydrogen, carbon monoxide, hydrogen sulfide, methane, sulfur monoxide or a combination of at least two of the foregoing;
preferably, the protective gas comprises an inert gas and/or nitrogen;
preferably, the volume fraction of the reducing gas in the reducing atmosphere is 3-10% by volume of the reducing atmosphere, and the balance is the protective gas.
4. The production method according to any one of claims 1 to 3, wherein the magnesiothermic reduction comprises a temperature rise and a temperature maintenance which are sequentially performed;
preferably, the heating rate is 3-15 ℃/min, and the temperature of the heating end point is 600-900 ℃;
preferably, the time for heat preservation is 4-10 h.
5. The method according to any one of claims 1 to 4, further comprising pickling after the magnesiothermic reduction.
6. The method according to any one of claims 1 to 5, wherein the preparation of the silica comprises the steps of:
(1) Mixing water, ethanol and ammonia water to obtain a first mixed solution;
(2) Mixing ethanol and ethyl silicate to obtain a second mixed solution;
(3) Mixing the first mixed solution and the second mixed solution, and carrying out solid-liquid separation to obtain silicon dioxide;
the step (1) and the step (2) are not in sequence.
7. The preparation method according to claim 6, wherein the mass ratio of the water, the ethanol and the ammonia water in the step (1) is (40-60) to (28-36) to (15-20);
preferably, the mass ratio of the ethanol to the ethyl silicate in the step (2) is (80-100) to (6-12);
preferably, the mass ratio of the first mixed liquid to the second mixed liquid in the step (3) is (0.9-1.2): 1;
preferably, the mixing mode in the step (1) comprises stirring, wherein the stirring speed is 400-700 r/min, and the stirring time is 1-6 min;
preferably, the mixing mode in the step (2) comprises stirring, wherein the stirring speed is 400-700 r/min, and the stirring time is 1-6 min;
preferably, the mixing mode in the step (3) comprises stirring, wherein the rotating speed of the stirring is 400-700 r/min, and the time is 1-6 h;
preferably, the preparation of the silicon dioxide also comprises water washing and drying which are sequentially carried out after solid-liquid separation;
preferably, the drying temperature is 60-80 ℃ and the drying time is 10-14 h.
8. The production method according to any one of claims 1 to 7, characterized by comprising:
mixing (8-12) of (6-10) of reduction auxiliary agent, 10-23 wt% of titanium-containing blast furnace slag and magnesium powder of silicon dioxide and titanium dioxide in the mass ratio of 100; heating to 600-900 ℃ at the speed of 3-15 ℃/min in a reducing atmosphere formed by mixing reducing gas and protective gas, and preserving heat for 4-10 h; the volume of the reducing atmosphere is taken as percentage, the volume fraction of the reducing gas in the reducing atmosphere is 3-10%, and the balance is protective gas; and (4) carrying out acid washing to obtain the silicon-titanium composite negative electrode material.
9. A silicon-titanium composite negative electrode material, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. A lithium ion battery is characterized by comprising a positive pole piece, a diaphragm and a negative pole piece which are sequentially stacked, wherein the negative pole piece comprises a current collector and a negative active layer coated on the surface of the current collector, and the negative active layer comprises the silicon-titanium composite negative pole material of claim 9.
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| CN106941172A (en) * | 2017-04-26 | 2017-07-11 | 清华大学 | Silicon/titanium dioxide lithium ion battery cathode and preparation method thereof |
| CN109888265A (en) * | 2019-01-28 | 2019-06-14 | 南京师范大学 | Silicotitanium interference networks material derived from a kind of hydrogel and its preparation method and application |
| CN110218874A (en) * | 2019-07-03 | 2019-09-10 | 昆明理工大学 | A method of recycling in scrap silicon titanium in silicon and titanium-contained slag simultaneously using metallic aluminium |
| CN113013397A (en) * | 2019-12-20 | 2021-06-22 | 四川大学 | Method for preparing titanium-silicon alloy cathode material by utilizing silicon waste and titanium-containing slag |
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| CN106941172A (en) * | 2017-04-26 | 2017-07-11 | 清华大学 | Silicon/titanium dioxide lithium ion battery cathode and preparation method thereof |
| CN109888265A (en) * | 2019-01-28 | 2019-06-14 | 南京师范大学 | Silicotitanium interference networks material derived from a kind of hydrogel and its preparation method and application |
| CN110218874A (en) * | 2019-07-03 | 2019-09-10 | 昆明理工大学 | A method of recycling in scrap silicon titanium in silicon and titanium-contained slag simultaneously using metallic aluminium |
| CN113013397A (en) * | 2019-12-20 | 2021-06-22 | 四川大学 | Method for preparing titanium-silicon alloy cathode material by utilizing silicon waste and titanium-containing slag |
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