CN113471418B - Lithium ion battery cathode material ferrous silicate/silicon dioxide/carbon and preparation method thereof - Google Patents
Lithium ion battery cathode material ferrous silicate/silicon dioxide/carbon and preparation method thereof Download PDFInfo
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- CN113471418B CN113471418B CN202110621921.XA CN202110621921A CN113471418B CN 113471418 B CN113471418 B CN 113471418B CN 202110621921 A CN202110621921 A CN 202110621921A CN 113471418 B CN113471418 B CN 113471418B
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- ferroferric oxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 68
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 64
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010406 cathode material Substances 0.000 title claims description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000007773 negative electrode material Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- -1 polytetrafluoroethylene Polymers 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- 239000010410 layer Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000008098 formaldehyde solution Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 239000010431 corundum Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 230000001351 cycling effect Effects 0.000 abstract description 11
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 230000002238 attenuated effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011870 silicon-carbon composite anode material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
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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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- 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
- 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)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a ferrous silicate/silicon dioxide/carbon anode material of a lithium ion battery and a preparation method thereof, belonging to the technical field of new materials and electrochemistry. The lithium ion battery anode material is a three-layer composite material with a hollow structure, wherein the inner core is ferrous silicate, the middle layer is silicon dioxide, and the outermost coating is organic pyrolytic carbon. The preparation method comprises the steps of preparation of ferroferric oxide nano particles, a silicon dioxide coating process, a carbon coating process and a process for removing ferroferric oxide by acid etching. Compared with the prior art, the hollow structure in the material particles prepared by the invention plays a good role in inhibiting the volume expansion of the material in the charge and discharge process, and is beneficial to improving the structural stability of the particles and the electrochemical performance of the electrode. The negative electrode material prepared by the method has excellent cycling stability, the reversible specific capacity is larger than 600mAh/g for the first time, and the capacity is hardly attenuated after 140 circles of cycling.
Description
Technical Field
The invention belongs to the technical field of new materials and electrochemistry, and particularly relates to a lithium ion battery cathode material ferrous silicate/silicon dioxide/carbon and a preparation method thereof.
Background
The current research hot spot of lithium ion battery cathode materials is electrode materials with high specific capacity. Ferrous silicate has begun to be of interest to researchers as an electrode material with a high specific capacity. The theoretical specific capacity of ferrous silicate is 526mAh/g, which is far higher than the theoretical specific capacity (372 mAh/g) of the current commercial graphite negative electrode material, and Si and Fe elements are quite abundant in nature, so that the ferrous silicate is a new-generation lithium ion battery negative electrode material with high specific volume and low cost and great application prospect. However, a higher specific capacity is accompanied by a large volume expansion during lithium intercalation and deintercalation, which causes cracking of ferrous silicate particles during cycling, pole piece falling off, and cycle performance is deteriorated.
Aiming at the problems of ferrous silicate cathode materials, the electrochemical performance of the ferrous silicate cathode materials is mainly improved by nanocrystallizing the ferrous silicate materials and compositing the ferrous silicate materials with other high-electron-conductivity compounds in the current research. The volume effect of ferrous silicate in the charging and discharging process can be effectively reduced by compounding the ferrous silicate material, and meanwhile, an active or inactive buffer matrix with good conductivity and small volume effect can be introduced to prepare the multiphase composite anode material, and the long-term cycling stability of the material is improved by means of volume compensation, conductivity increase and the like.
The Wang research group of Zhongshan university synthesizes nano Fe with the particle size of 300nm by combining and calcining ethyl orthosilicate, ferrous acetate, acetic acid and other organic solvents as raw materials through a hydrothermal method 2 SiO 4 And (3) particles. The nanometer-sized particle size can effectively release the internal structural stress generated by the volume expansion-contraction effect caused by lithium intercalation and deintercalation in the circulation process, and improve the structural stability of the material. The material was cycled 100 times at a current density of 0.1A/g, still maintaining a reversible specific capacity (RSC Advances,2017,7,4437-4443) of about 600 mAh/g. Zhang et al, university of Ind.Organum, organum, siO 2 Mixing with ferrous oxalate as raw material, ball milling, calcining to obtain carbon-coated ferrous silicate material (Fe 2 SiO 4 /C). Due to the existence of carbon, the volume expansion of ferrous silicate in the charge and discharge process can be effectively buffered, and the structural stability of the material is improved; in addition, the carbon can improve the electron conductivity of the material and accelerate the electrode reactionDynamic process. Fe (Fe) 2 SiO 4 the/C electrode was capable of maintaining about 474mAh/g (Journal of Electroanalytical Chemistry 807 (2017) 29-36) after 100 cycles of charge and discharge at 1C.
The method improves the electrochemical capacity of the material and the electrochemical stability of the material by reducing the particle size of the material particles or improving the electronic conductivity of the material respectively. However, due to the inherent volume expansion of ferrous silicate, it is difficult for the particles to avoid the internal structural stresses existing inside the particles during repeated cycles, resulting in an undesirable long cycle performance of the material. In addition, the densification of the carbon coating of ferrous silicate particles is difficult to achieve at present, the uneven condition of the carbon coating easily causes the difference of the particles everywhere, and the attenuation of the material circulation performance is also caused.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a lithium ion battery anode material ferrous silicate/silicon dioxide/carbon and a preparation method thereof, wherein the inside of particles of the anode material has a hollow structure, has a good inhibition effect on volume expansion of the material in the charge and discharge process, and is beneficial to improving the structural stability of the particles and the electrochemical performance of an electrode. The negative electrode material prepared by the method has excellent cycling stability, the reversible specific capacity is larger than 600mAh/g for the first time, and the capacity is hardly attenuated after 140 circles of cycling.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a lithium ion battery anode material ferrous silicate/silicon dioxide/carbon, which is a three-layer composite material with a hollow structure, wherein the inner core is ferrous silicate, the middle layer is silicon dioxide, and the outermost coating is organic pyrolytic carbon.
Further, the particle size of the core ferrous silicate in the lithium ion battery cathode material is 5-300nm, the thickness of the intermediate layer is 2-100nm, and the thickness of the coating layer is 10-200nm.
The invention also provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
(1) Respectively weighing ferric salt and polyvinylpyrrolidone K30 according to the mass ratio of 1-10:1, dissolving in a solvent, transferring the solution into a stainless steel water heating tank with a polytetrafluoroethylene lining after the solution is completely dissolved, placing the stainless steel water heating tank into a blast oven for heat preservation treatment, and centrifugally washing and drying a reaction product after the reaction is finished to obtain ferroferric oxide nano particles;
(2) Adding the ferroferric oxide nano particles into a mixed solvent of deionized water and ethanol, performing ultrasonic dispersion, adding an ammonia solution, fully stirring and mixing to obtain a ferroferric oxide dispersion liquid, then placing the dispersion liquid into a water bath, dropwise adding organic silicon ester into the dispersion liquid by adopting a peristaltic pump, keeping the mass ratio of the organic silicon ester to the ferroferric oxide nano particles at 3-4:1, continuously preserving heat for a certain time, and then respectively performing centrifugal washing on powder in the dispersion liquid by using deionized water and absolute ethanol, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide compound;
(3) Respectively weighing the ferroferric oxide/silicon dioxide compound, a surfactant, resorcinol and 37% of formaldehyde solution according to the mass ratio of 1:0.02:0.2-0.4:0.11-0.27, ultrasonically dispersing the ferroferric oxide/silicon dioxide in deionized water to obtain ferroferric oxide/silicon dioxide dispersion, then adding the surfactant, resorcinol and ammonia water solution into the dispersion, fully stirring, adding the formaldehyde solution into the mixed solution, continuously stirring for a certain time after the dropwise addition, respectively centrifugally washing powder in the mixed solution by deionized water and absolute ethyl alcohol, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide/organic matter layer compound;
(4) Placing the ferroferric oxide/silicon dioxide/organic matter layer composite in a corundum crucible, placing the corundum crucible in a tubular atmosphere furnace, performing heat preservation treatment under the protection of inert gas, and cooling to room temperature along with the furnace after the reaction is finished to obtain a ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material;
(5) Soaking the ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material in hydrochloric acid solution, and then respectively centrifugally washing powder in the solution by deionized water and absolute ethyl alcohol, and drying to obtain the ferrous silicate/silicon dioxide/carbon composite material.
Further, in the step (1), the ferric salt comprises one or more of ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate and ferric acetylacetonate; the solvent comprises one or more of water, ethanol, glycol, glycerol and n-butanol. The choice of iron salt is based on the fact that it is readily soluble in water or alcohol solvents and forms a homogeneous mixed solution with polyvinylpyrrolidone.
Further, the temperature of the heat preservation treatment in the step (1) is 150-200 ℃, and the heat preservation time is 10-20h. The holding temperature and time in this step are limited to obtain the ferroferric oxide particles having the desired particle size.
Further, in the step (2), the volume ratio of deionized water to ethanol in the mixed solvent of deionized water and ethanol is 1:0.5-5; the ultrasonic dispersion time is more than 2 hours; after ultrasonic dispersion, adding ammonia water solution with the concentration of 0.1mol/L and the volume of 0.5-4mL.
Further, the heating temperature of the water bath kettle in the step (2) is 25-50 ℃. The heating temperature in this step is limited to control the hydrolysis reaction of the organic silicon ester, thereby effectively controlling the SiO 2 Layer thickness.
Further, the dropping speed of the organic silicon ester in the step (2) is 0.1-2mL/min, so that the condensation reaction of the organic silicon ester can be reasonably regulated and controlled, and the thickness of the SiO2 layer can be effectively controlled; the organic silicon ester comprises tetraethoxysilane, trimethyl silicon propionate, trimethyl hydroxy silane, trimethyl methoxy silane or amino propyl triethoxy silane.
Further, the heat preservation time in the step (2) is 1-5h.
Further, the time of the ultrasonic dispersion in the step (3) is at least 2 hours.
Further, the surfactant in the step (3) comprises one or more of cetyltrimethylammonium bromide, polyvinylpyrrolidone and sodium dodecyl sulfate.
Further, the concentration of the ammonia water solution in the step (3) is 0.1mol/L, and the volume is 0.5-500ml; the time of the sufficient stirring is at least 1h.
Further, the dropping speed of the formaldehyde solution in the step (3) is 0.05-2.5mL/min, and stirring is continued for at least 2h after the dropping is completed.
Further, the inert gas in the step (4) comprises one or more of argon, nitrogen and helium.
Further, the temperature of the heat preservation treatment in the step (4) is 400-800 ℃, and the heat preservation time is 0.5-6h.
Further, the concentration of the hydrochloric acid solution in the step (5) is 0.01-1mol/L, and the soaking time is 0.5-60min.
Compared with the prior art, the technical scheme of the invention has the following positive effects or technical advantages:
according to the invention, a certain gap is reserved in the ferrous silicate particles, so that the structural expansion effect of ferrous silicate in the charge-discharge process is relieved, the structural internal stress in the particles caused by repeated volume expansion/contraction is released, and the structural stability of ferrous silicate is improved. In addition, the silicon dioxide and carbon coating layers uniformly and tightly coated on the outer layers of the ferrous silicate particles can not only effectively buffer the volume expansion effect of the ferrous silicate particles, but also well isolate the direct contact between the ferrous silicate and the electrolyte, and reduce the occurrence of side reactions between materials and the electrolyte. The negative electrode material prepared by the method has excellent cycling stability, the reversible specific capacity is larger than 600mAh/g for the first time, and the capacity is hardly attenuated after 140 circles of cycling.
Drawings
FIG. 1 is a schematic view of an X-ray diffraction spectrum of a ferrous silicate/silica/carbon composite anode material prepared in example 1 of the present invention.
Fig. 2 is a microscopic morphology of the ferrous silicate/silica/carbon composite anode material prepared in example 1 of the present invention.
FIG. 3 is a graph showing the cycle capacity of the ferrous silicate/silica/carbon composite electrode material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
[ example 1 ]
A preparation method of lithium ion battery cathode material ferrous silicate/silicon dioxide/carbon comprises the following steps:
(1) Respectively weighing ferric trichloride hexahydrate and polyvinylpyrrolidone K30 according to a mass ratio of 4:1, dissolving in ethylene glycol, transferring the solution into a stainless steel water heating tank with a polytetrafluoroethylene lining after the solution is completely dissolved, placing the stainless steel water heating tank into a blast oven, carrying out heat preservation treatment at 180 ℃ for 10 hours, and carrying out centrifugal washing and drying on the reaction product after the reaction is finished to obtain the ferroferric oxide nano particles;
(2) Adding the ferroferric oxide nano particles into V (deionized water) which is a mixed solvent of V (ethanol) =1:3, performing ultrasonic dispersion for 4 hours, adding 2.5mL of 0.1mol/L ammonia water solution, fully stirring and mixing to obtain ferroferric oxide dispersion liquid, then placing the dispersion liquid into a water bath kettle at 40 ℃, dropwise adding tetraethoxysilane into the dispersion liquid at the speed of 1.5mL/min by adopting a peristaltic pump, keeping the mass ratio of the adding amount of tetraethoxysilane to the ferroferric oxide nano particles at 3.7:1, continuously preserving heat for 3.5 hours, and performing centrifugal washing on powder in the dispersion liquid by using deionized water and absolute ethyl alcohol respectively, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide compound;
(3) Respectively weighing the ferroferric oxide/silicon dioxide compound, a surfactant, resorcinol and 37% formaldehyde solution according to the mass ratio of 1:0.02:0.3:0.2, ultrasonically dispersing the ferroferric oxide/silicon dioxide in deionized water for 4 hours to obtain ferroferric oxide/silicon dioxide dispersion, then adding 100mL of cetyltrimethylammonium bromide, resorcinol and 0.1mol/L ammonia water solution into the dispersion, fully stirring for 3 hours, adding the formaldehyde solution into the mixed solution at a dropping acceleration of 1.8mL/min, continuing stirring for 3.5 hours after the dropping, respectively centrifugally washing powder in the mixed solution by deionized water and absolute ethyl alcohol, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide/organic compound layer;
(4) Placing the ferroferric oxide/silicon dioxide/organic matter layer composite into a corundum crucible, placing the corundum crucible into a tubular atmosphere furnace, carrying out heat preservation at 650 ℃ for 4.5 hours under the protection of argon, and cooling to room temperature along with the furnace after the reaction is finished to obtain a ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material;
(5) Soaking the ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material in 0.07mol/L hydrochloric acid solution for 30min, and respectively centrifugally washing and drying powder in the solution by deionized water and absolute ethyl alcohol to obtain the ferrous silicate/silicon dioxide/carbon composite material.
The X-ray diffraction spectrum diagram of the ferrous silicate/silicon dioxide/carbon composite anode material prepared in the embodiment is shown in fig. 1, and it can be clearly seen that the diffraction peak of ferrous silicate is relatively sharp, which indicates that the crystal form of the material is relatively good; and a diffuse inclusion peak occurs in the diffraction angle range of 20 to 25 deg., which corresponds to the amorphous silica and carbon components in the composite material. The microscopic morphology diagram of the material is shown in fig. 2, and it can be clearly seen that the particle size of the composite anode material is about 500nm, the thickness of the ferrous silicate-silicon dioxide-carbon layer is about 300nm, and the inside of the particle has a hollow structure; the cycling capacity graph of the material is shown in fig. 3, and it can be seen that the cycling stability of the cathode material is excellent, the first reversible specific capacity is more than 600mAh/g, and the capacity is hardly attenuated after 140 circles of cycling.
[ example 2 ]
A preparation method of lithium ion battery cathode material ferrous silicate/silicon dioxide/carbon comprises the following steps:
(1) Respectively weighing ferric sulfate and polyvinylpyrrolidone K30 according to the mass ratio of 1:1, dissolving in water, transferring the solution into a stainless steel water heating tank with a polytetrafluoroethylene lining after the solution is completely dissolved, placing the stainless steel water heating tank into a blast oven, carrying out heat preservation treatment at 150 ℃ for 12 hours, and carrying out centrifugal washing and drying on a reaction product after the reaction is finished to obtain the ferroferric oxide nano particles;
(2) Adding the ferroferric oxide nano-particles into V (deionized water) which is a mixed solvent of V (ethanol) =1:0.5, performing ultrasonic dispersion for 2.5h, adding 0.5mL of 0.1mol/L ammonia water solution, fully stirring and mixing to obtain ferroferric oxide dispersion liquid, then placing the dispersion liquid into a water bath kettle at 25 ℃, dropwise adding trimethyl silicon propionate into the dispersion liquid at the dropwise speed of 0.1mL/min by adopting a peristaltic pump, keeping the mass ratio of the adding amount of the trimethyl silicon propionate to the ferroferric oxide nano-particles to be 3:1, continuously preserving heat for 1h, and performing centrifugal washing on powder in the dispersion liquid by using deionized water and absolute ethyl alcohol respectively, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide compound;
(3) Respectively weighing the ferroferric oxide/silicon dioxide compound, a surfactant, resorcinol and 37% formaldehyde solution according to the mass ratio of 1:0.02:0.2:0.11, ultrasonically dispersing the ferroferric oxide/silicon dioxide in deionized water for 2 hours to obtain ferroferric oxide/silicon dioxide dispersion, then adding 0.5mL of polyvinylpyrrolidone, resorcinol and 0.1mol/L ammonia water solution into the dispersion, fully stirring for 1 hour, adding the formaldehyde solution into the mixed solution at a dropwise acceleration of 0.05mL/min, continuing stirring for 2 hours after the dropwise addition, respectively centrifugally washing powder in the mixed solution by using deionized water and absolute ethyl alcohol, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide/organic matter layer compound;
(4) Placing the ferroferric oxide/silicon dioxide/organic matter layer composite into a corundum crucible, placing the corundum crucible into a tubular atmosphere furnace, carrying out heat preservation for 0.5h at 400 ℃ under the protection of nitrogen, and cooling to room temperature along with the furnace after the reaction is finished to obtain a ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material;
(5) Soaking the ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material in 0.01mol/L hydrochloric acid solution for 0.5min, and then respectively centrifugally washing powder in the solution by deionized water and absolute ethyl alcohol, and drying to obtain the ferrous silicate/silicon dioxide/carbon composite material.
[ example 3 ]
A preparation method of lithium ion battery cathode material ferrous silicate/silicon dioxide/carbon comprises the following steps:
(1) Respectively weighing ferric nitrate and polyvinylpyrrolidone K30 according to the mass ratio of 10:1, dissolving in ethanol, transferring the solution into a stainless steel water heating tank with a polytetrafluoroethylene lining after the solution is completely dissolved, placing the stainless steel water heating tank into a blast oven, carrying out heat preservation treatment at 200 ℃ for 20 hours, and carrying out centrifugal washing and drying on a reaction product after the reaction is finished to obtain the ferroferric oxide nano particles;
(2) Adding the ferroferric oxide nano particles into V (deionized water) which is a mixed solvent of V (ethanol) =1:5, carrying out ultrasonic dispersion for 3h, adding 4mL of 0.1mol/L ammonia water solution, fully stirring and mixing to obtain ferroferric oxide dispersion liquid, then placing the dispersion liquid into a water bath kettle at 50 ℃, dropwise adding trimethylhydroxysilane into the dispersion liquid at the dropwise speed of 2mL/min by adopting a peristaltic pump, keeping the mass ratio of the addition amount of the trimethylhydroxysilane to the ferroferric oxide nano particles at 4:1, continuously preserving heat for 5h, and respectively carrying out centrifugal washing on powder in the dispersion liquid by using deionized water and absolute ethyl alcohol, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide compound;
(3) Respectively weighing the ferroferric oxide/silicon dioxide compound, a surfactant, resorcinol and 37% formaldehyde solution according to the mass ratio of 1:0.02:0.4:0.27, ultrasonically dispersing the ferroferric oxide/silicon dioxide in deionized water for 4 hours to obtain ferroferric oxide/silicon dioxide dispersion, then adding 500mL of sodium dodecyl sulfate, resorcinol and 0.1mol/L ammonia water solution into the dispersion, fully stirring for 2.5 hours, adding the formaldehyde solution into the mixed solution at a dropping acceleration of 2.5mL/min, continuing stirring for 3.5 hours after the dropping, and centrifugally washing powder in the mixed solution by deionized water and absolute ethyl alcohol respectively, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide/organic compound layer;
(4) Placing the ferroferric oxide/silicon dioxide/organic matter layer composite in a corundum crucible, placing the corundum crucible in a tubular atmosphere furnace, carrying out heat preservation at 800 ℃ for 6 hours under the protection of helium, and cooling to room temperature along with the furnace after the reaction is finished to obtain a ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material;
(5) Soaking the ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material in 1mol/L hydrochloric acid solution for 60min, and respectively centrifugally washing and drying powder in the solution by deionized water and absolute ethyl alcohol to obtain the ferrous silicate/silicon dioxide/carbon composite material.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The preparation method of the lithium ion battery cathode material ferrous silicate/silicon dioxide/carbon is characterized by comprising the following steps:
(1) Respectively weighing ferric salt and polyvinylpyrrolidone K30 according to the mass ratio of 1-10:1, dissolving in a solvent, transferring the solution into a stainless steel water heating tank with a polytetrafluoroethylene lining after the solution is completely dissolved, placing the stainless steel water heating tank into a blast oven for heat preservation treatment, and centrifugally washing and drying a reaction product after the reaction is finished to obtain ferroferric oxide nano particles;
(2) Adding the ferroferric oxide nano particles into a mixed solvent of deionized water and ethanol, performing ultrasonic dispersion, adding an ammonia solution, fully stirring and mixing to obtain a ferroferric oxide dispersion liquid, then placing the dispersion liquid into a water bath, dropwise adding organic silicon ester into the dispersion liquid by adopting a peristaltic pump, keeping the mass ratio of the organic silicon ester to the ferroferric oxide nano particles at 3-4:1, continuously preserving heat for a certain time, and then respectively performing centrifugal washing on powder in the dispersion liquid by using deionized water and absolute ethanol, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide compound;
(3) Respectively weighing the ferroferric oxide/silicon dioxide compound, a surfactant, resorcinol and 37% of formaldehyde solution according to the mass ratio of 1:0.02:0.2-0.4:0.11-0.27, ultrasonically dispersing the ferroferric oxide/silicon dioxide in deionized water to obtain ferroferric oxide/silicon dioxide dispersion, then adding the surfactant, resorcinol and ammonia water solution into the dispersion, fully stirring, adding the formaldehyde solution into the mixed solution, continuously stirring for a certain time after the dropwise addition, respectively centrifugally washing powder in the mixed solution by deionized water and absolute ethyl alcohol, and drying to obtain an intermediate product ferroferric oxide/silicon dioxide/organic matter layer compound;
(4) Placing the ferroferric oxide/silicon dioxide/organic matter layer compound into a corundum crucible, placing into a tubular atmosphere furnace, and performing heat preservation treatment under the protection of one or more gases of argon, nitrogen and helium, wherein the temperature of the heat preservation treatment is 400-800 DEG C o C, keeping the temperature for 0.5-6h, and cooling to room temperature along with a furnace after the reaction is finished to obtain the ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material;
(5) Soaking the ferroferric oxide/ferrous silicate/silicon dioxide/carbon composite material in hydrochloric acid solution, and respectively centrifugally washing powder in the solution by deionized water and absolute ethyl alcohol, and drying to obtain the ferrous silicate/silicon dioxide/carbon composite material;
the lithium ion battery anode material is a three-layer composite material with a hollow structure, wherein the inner core is ferrous silicate, the middle layer is silicon dioxide, and the outermost coating is organic pyrolytic carbon.
2. The method for preparing the lithium ion battery cathode material ferrous silicate/silicon dioxide/carbon according to claim 1, wherein the particle size of the core ferrous silicate in the lithium ion battery cathode material is 5-300nm, the thickness of the middle layer is 2-100nm, and the thickness of the coating layer is 10-200 nm; the content of ferrous silicate is 50-90 wt%, the content of silicon dioxide is 1-10%, and the content of organic pyrolytic carbon is 1-10%.
3. The method for preparing ferrous silicate/silicon dioxide/carbon as claimed in claim 1, wherein the iron salt in the step (1) comprises one or more of ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate and ferric acetylacetonate; the solvent comprises one or more of water, ethanol, glycol, glycerol and n-butanol.
4. The method as claimed in claim 1The preparation method of the lithium ion battery cathode material ferrous silicate/silicon dioxide/carbon is characterized in that the temperature of the heat preservation treatment in the step (1) is 150-200 o And C, the heat preservation time is 10-20h.
5. The method for preparing lithium ion battery anode material ferrous silicate/silicon dioxide/carbon according to claim 1, wherein the volume ratio of deionized water to ethanol in the mixed solvent of deionized water and ethanol in the step (2) is 1:0.5-5; the time of the ultrasonic dispersion is greater than 2h; after ultrasonic dispersion, the concentration of the ammonia water solution is 0.1mol/L, and the volume is 0.5-4mL.
6. The method for preparing lithium ion battery anode material ferrous silicate/silicon dioxide/carbon according to claim 1, wherein the heating temperature of the water bath kettle in the step (2) is 25-50% o C, performing operation; the dripping speed of the organic silicon ester is 0.1-2 mL/min; the organic silicon ester comprises tetraethoxysilane, trimethyl silicon propionate, trimethyl hydroxy silane, trimethyl methoxy silane or amino propyl triethoxy silane; the heat preservation time is 1-5h.
7. The method of preparing a lithium ion battery negative electrode material ferrous silicate/silica/carbon according to claim 1, wherein the time of ultrasonic dispersion in step (3) is at least 2h; the surfactant comprises one or more of cetyltrimethylammonium bromide, polyvinylpyrrolidone and sodium dodecyl sulfate; the concentration of the ammonia water solution is 0.1mol/L, and the volume is 0.5-500ml; the time of sufficient agitation is at least 1 h; the dropping speed of the formaldehyde solution is 0.05-2.5mL/min, and stirring is continued for at least 2h after the dropping is completed.
8. The method for preparing lithium ion battery anode material ferrous silicate/silicon dioxide/carbon according to claim 1, wherein the concentration of the hydrochloric acid solution in the step (5) is 0.01-1mol/L, and the soaking time is 0.5-60min.
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