CN103259019A - Preparation method of lithium ferrous silicate composite material - Google Patents
Preparation method of lithium ferrous silicate composite material Download PDFInfo
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- CN103259019A CN103259019A CN2013101476006A CN201310147600A CN103259019A CN 103259019 A CN103259019 A CN 103259019A CN 2013101476006 A CN2013101476006 A CN 2013101476006A CN 201310147600 A CN201310147600 A CN 201310147600A CN 103259019 A CN103259019 A CN 103259019A
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Abstract
The invention relates to a preparation method of a lithium ferrous silicate composite material. The method comprises the following concrete steps of: step 1, sequentially dissolving a lithium source compound, an iron source compound, a silicon source compound and a surface active agent into a solvent, and then adjusting the pH to be 2-6 by organic acid, carrying out low temperature water reaction, washing the product by water, filtering, and carrying out spray drying to obtain precursor; step 2, mixing the obtained precursor and a carbon source compound, and carrying out ball-milling and calcination, and cooling to obtain the lithium ferrous silicate composite material. The preparation method of the lithium ferrous silicate composite material combines a hydrothermal method and spray drying, so that the technology is obviously improved; and the obtained lithium ferrous silicate composite material is controllable in morphology and small and even in particle size, and has better charge-discharge property and cycle performance and higher volume ratio.
Description
Technical field
The invention belongs to technical field of material, relate to a kind of preparation method of ferrosilicon silicate of lithium composite material.
Background technology
Because the ferrous metasilicate lithium material has identical lattice stability effect with LiFePO 4 material, has higher gram volume simultaneously, and element silicon is nontoxic, abundant cheapness, therefore becomes a kind of novel anode material for lithium-ion batteries.The preparation method of ferrous silicate lithium anode composite material mainly contains solid phase method, sol-gal process and hydrothermal synthesis method.The characteristics of solid phase method are that technology is simple, and cost is lower, but the material particle size of its preparation is inhomogeneous, and crystal grain is bigger, and sneaks into impurity easily.The material particle size of sol-gal process and hydrothermal synthesis method preparation is less, better performances, but its control complex process in preparation process, and equipment requires high, be unfavorable for large-scale production, and cost is higher.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of ferrosilicon silicate of lithium composite material, the inhomogeneous problem of ferrosilicon silicate of lithium composite material granularity that has solved existing preparation method's complex process and prepared.
The technical solution adopted in the present invention is, the preparation method of ferrosilicon silicate of lithium composite material specifically implements according to following steps:
Step 1 is dissolved in Li source compound, Fe source compound, silicon source compound and surfactant in the solvent successively successively, uses organic acid for adjusting pH to 2～6 again, carries out low temperature waters reaction after washing, filtration then, obtains presoma finally by crossing spray drying;
Step 2, the presoma that step 1 is obtained mixes back ball milling, calcining with carbon-source cpd, namely obtain the ferrosilicon silicate of lithium composite material after the cooling.
Characteristics of the present invention also are,
In the step 1 in the Li source compound in lithium, the Fe source compound in iron and the silicon source compound mol ratio of silicon be 1.95～2.1:1:1; The mass ratio of surfactant and Li source compound is 0～3:1, and the mol ratio of lithium is 100～500:1 in solvent and the Li source compound.
The low temperature waters is reflected in the reactor and carries out in the step 1, and reaction temperature is 150～200 ℃, and the reaction time is 1～24h; Spray drying is carried out in spray dryer, and baking temperature is 80～220 ℃.
Calcining is specifically implemented according to following steps in the step 2: in inert atmosphere, earlier 300～500 ℃ of insulations 1～6 hour, again 600～900 ℃ of insulations 6～24 hours.
The quality of carbon-source cpd is 1～20% of the lithium ion cell positive ferrosilicon silicate of lithium quality of materials that finally obtains in the step 2.
Li source compound is any one or two kinds of above molar mixture arbitrarily in lithium hydroxide, acetate dihydrate lithium, lithium nitrate, lithium carbonate, lithium chloride, lithium sulfate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4, lithium oxalate, lithium acetate, lithium dihydrogen phosphate, lithium metasilicate, lithium phosphate, lithia, lithium nitrite, lithium molybdate, the lithium vanadate.
Fe source compound is that ferrous sulfate, ferrous carbonate, nine water ferric nitrates, frerrous chloride, iron chloride, ironic citrate, ferrous lactate, penta hydroxy group close iron, ferrous oxide, ferrous acetate, basic carbonate is ferrous, ethylenediamine tetra-acetic acid is ferrous, ferrous nitrate, bifluoride are ferrous, any one or two kinds of above molar mixture arbitrarily in the ferrous phosphate, ferric carbonate.
The silicon source compound is silica, tetraethoxysilane, phenyl trichlorosilane, silicon nitride, dimethyldichlorosilane, silicon rubber, diethyl dichlorosilane, dichlorosilane, the diethyl chlorosilane, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silica gel, the crosslinked with silicane polypropylene, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, positive quanmethyl silicate, silicic acid, metasilicic acid, four (1-Methylethyl) esters of silicon acis, hexamethyldisiloxane, heptamethyldisilazane, triethyl-silicane, orthosilicic acid, two silicic acid, methyl silicate, methyl silicate, any one or two kinds of above molar mixture arbitrarily in the tetramethoxy-silicane.
Carbon-source cpd is ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch; petroleum asphalt; polypropylene; polyacrylamide; polyvinyl alcohol; starch; flour; tapioca flour; dehydrated potato powder; corn flour; taro meal; rice meal; carbon dust; bran powder; graphite powder; acetylene black; carbon black; sucrose; citric acid; furfural resin; poly-to benzene; benzene naphthalene dicarboxylic copolymer; benzene anthracene bipolymer; the luxuriant and rich with fragrance bipolymer of benzene; benzene naphthalene terpolymer; benzene naphthalene grace terpolymer; any one or two kinds of above molar mixture arbitrarily in the carbon nano-tube.
Organic acid is one or more any molar mixture in ascorbic acid, ethanedioic acid, adipic acid, malonic acid, mandelic acid, malic acid, lactic acid, citric acid, formaldehyde, acetaldehyde, hutanal, isobutylaldehyde, tetraethyl ethylene glycol, isopropyl alcohol, the ethylene glycol; Surfactant is one or more any molar mixture in P123, polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, Qu Latong S-100, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide; Solvent is any one or two kinds of above mixture of mol ratio arbitrarily in deionized water, distilled water, ethanol, the acetone.
The invention has the beneficial effects as follows, the preparation method of ferrosilicon silicate of lithium composite material of the present invention, by hydro thermal method and spray drying are combined, technology is obviously improved, the ferrosilicon silicate of lithium nano composite material pattern for preparing is controlled, granularity is tiny evenly, has charge-discharge performance preferably, cycle performance and higher Capacity Ratio.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the ferrosilicon silicate of lithium composite material for preparing of the embodiment of the invention 1;
Fig. 2 is the electron-microscope scanning figure of the ferrosilicon silicate of lithium composite material for preparing of the embodiment of the invention 1;
Fig. 3 is the first charge-discharge figure of the ferrosilicon silicate of lithium composite material for preparing of the embodiment of the invention 1.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
The preparation method of ferrosilicon silicate of lithium composite material of the present invention, specifically implement according to following steps:
Step 1 is dissolved in Li source compound, Fe source compound, silicon source compound and surfactant in the solvent successively successively, in the Li source compound in lithium, the Fe source compound in iron and the silicon source compound mol ratio of silicon be 1.95～2.1:1:1; The mass ratio of surfactant and Li source compound is 0～3:1, the mol ratio of lithium is 100～500:1 in solvent and the Li source compound, use organic acid for adjusting pH to 2～6 again, in reactor, carry out then obtaining presoma in 150～200 ℃ of low temperature waters reaction 1～24h after washings, filtration finally by crossing spray drying;
Step 2, the presoma that step 1 is obtained mixes the back ball milling with carbon-source cpd, the quality of carbon-source cpd is 1～20% of the lithium ion cell positive ferrosilicon silicate of lithium quality of materials that finally obtains, then in inert atmosphere, earlier 300～500 ℃ of insulations 1～6 hour, 600～900 ℃ of insulations 6～24 hours, namely obtain the ferrosilicon silicate of lithium composite material after the cooling again.
Li source compound is any one or two kinds of above molar mixture arbitrarily in lithium hydroxide, acetate dihydrate lithium, lithium nitrate, lithium carbonate, lithium chloride, lithium sulfate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4, lithium oxalate, lithium acetate, lithium dihydrogen phosphate, lithium metasilicate, lithium phosphate, lithia, lithium nitrite, lithium molybdate, the lithium vanadate.
Fe source compound is that ferrous sulfate, ferrous carbonate, nine water ferric nitrates, frerrous chloride, iron chloride, ironic citrate, ferrous lactate, penta hydroxy group close iron, ferrous oxide, ferrous acetate, basic carbonate is ferrous, ethylenediamine tetra-acetic acid is ferrous, ferrous nitrate, bifluoride are ferrous, any one or two kinds of above molar mixture arbitrarily in the ferrous phosphate, ferric carbonate.
The silicon source compound is silica, tetraethoxysilane, phenyl trichlorosilane, silicon nitride, dimethyldichlorosilane, silicon rubber, diethyl dichlorosilane, dichlorosilane, the diethyl chlorosilane, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silica gel, the crosslinked with silicane polypropylene, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, positive quanmethyl silicate, silicic acid, metasilicic acid, four (1-Methylethyl) esters of silicon acis, hexamethyldisiloxane, heptamethyldisilazane, triethyl-silicane, orthosilicic acid, two silicic acid, methyl silicate, methyl silicate, any one or two kinds of above molar mixture arbitrarily in the tetramethoxy-silicane.
Carbon-source cpd is ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch; petroleum asphalt; polypropylene; polyacrylamide; polyvinyl alcohol; starch; flour; tapioca flour; dehydrated potato powder; corn flour; taro meal; rice meal; carbon dust; bran powder; graphite powder; acetylene black; carbon black; sucrose; citric acid; furfural resin; poly-to benzene; benzene naphthalene dicarboxylic copolymer; benzene anthracene bipolymer; the luxuriant and rich with fragrance bipolymer of benzene; benzene naphthalene terpolymer; benzene naphthalene grace terpolymer; any one or two kinds of above molar mixture arbitrarily in the carbon nano-tube.
Organic acid is one or more any molar mixture in ascorbic acid, ethanedioic acid, adipic acid, malonic acid, mandelic acid, malic acid, lactic acid, citric acid, formaldehyde, acetaldehyde, hutanal, isobutylaldehyde, tetraethyl ethylene glycol, isopropyl alcohol, the ethylene glycol.
Surfactant is one or more any molar mixture in P123, polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, Qu Latong S-100, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide.
Solvent is any one or two kinds of above mixture of mol ratio arbitrarily in deionized water, distilled water, ethanol, the acetone.
The preparation method of ferrosilicon silicate of lithium composite material of the present invention, by hydro thermal method and spray drying are combined, technology is obviously improved, the ferrosilicon silicate of lithium nano composite material pattern for preparing is controlled, granularity is tiny evenly, has charge-discharge performance preferably, cycle performance and higher Capacity Ratio.
Embodiment 1
Step 1, successively 0.01mol lithium carbonate, 0.02mol ferrous sulfate, 0.02mol tetraethoxysilane and 2g polyethylene glycol are dissolved in the 60ml deionized water successively, use lemon acid for adjusting pH to 4 again, in reactor, carry out low temperature waters reaction 12h after washing, filtration at 180 ℃ then, obtain presoma finally by crossing spray drying;
Step 2, the presoma that step 1 is obtained mixes back ball milling 24h with 0.48g glucose, in inert atmosphere, earlier at 450 ℃ of insulation 2h, at 750 ℃ of insulations of high temperature 10h, namely obtain the ferrosilicon silicate of lithium composite material after the cooling more then.
Fig. 1 is the x-ray diffraction pattern of the ferrosilicon silicate of lithium composite material for preparing of the embodiment of the invention 1, and as can be seen from Figure 1, main peak is the diffraction maximum of ferrosilicon silicate of lithium composite material among Fig. 1, and what illustrate that embodiment 1 prepares is the ferrosilicon silicate of lithium composite material.
Fig. 2 is the electron-microscope scanning figure of the ferrosilicon silicate of lithium composite material for preparing of the embodiment of the invention 1, as can be seen from Figure 2, and the epigranular unanimity of the ferrosilicon silicate of lithium composite material that embodiment 1 prepares.
The ferrosilicon silicate of lithium composite powder that embodiment 1 is prepared, CNT and PVDF (polyvinylidene fluoride) mix in the ratio of mass ratio 75:15:10, add an amount of NMP (N-methyl pyrrolidone), be applied on the aluminium foil after fully stirring into evenly, 1 dry 12h in the vacuum drying chamber under 120 ° of C then, be cut to the small pieces of 15.5mm diameter after the taking-up as positive plate, metal lithium sheet with the 15.8mm diameter is negative pole, with diameter 16mm, the Celgard2400 microporous polypropylene membrane of thickness 20um is barrier film, add the EC that volume ratio is 1:1:1 (ethylene carbonate)/DMC (1 again, the 2-dimethyl carbonate)/the DEC(diethyl carbonate) 1molL-1LiPF6 electrolyte, in being full of the glove box of argon gas, be assembled into CR2032 type button cell, place U.S. Arbin battery testing to test its chemical property cashier's office in a shop button cell, charge-discharge magnification is 0.1C, and voltage range is 1.5V-4.8V.Fig. 3 is the first charge-discharge figure of the ferrosilicon silicate of lithium composite material for preparing of the embodiment of the invention 1, and as shown in Figure 3, the charging capacity of the ferrosilicon silicate of lithium composite material that embodiment 1 prepares reaches 158mAh/g, and reversible capacity is 122mAh/g.
Embodiment 2
Step 1, successively 0.039 lithium acetate, 0.02mol ferrous sulfate, 0.02mol sodium metasilicate are dissolved in the mixture of 30ml ethanol and 40ml acetone successively, regulate pH to 2 with ascorbic acid again, in reactor, carry out low temperature waters reaction 24h after washing, filtration at 150 ℃ then, obtain presoma finally by crossing spray drying;
Step 2, the presoma that step 1 is obtained mixes back ball milling 24h with the 0.0322g electrically conductive graphite, in inert atmosphere, earlier at 300 ℃ of insulation 6h, at 600 ℃ of insulations of high temperature 24h, namely obtain the ferrosilicon silicate of lithium composite material after the cooling more then.
Embodiment 3
Step 1, successively 0.042mol lithium sulfate, 0.02mol nine water ferric nitrates, 0.02mol tetraethoxysilane and 12.84gP123 are dissolved in the mixture of 50ml ethanol and 170ml deionized water successively, regulate pH to 6 with ascorbic acid again, in reactor, carry out low temperature waters reaction 1h after washing, filtration at 200 ℃ then, obtain presoma finally by crossing spray drying;
Step 2, the presoma that step 1 is obtained mixes back ball milling 24h with the 0.644g carbon nano-tube, in inert atmosphere, earlier at 500 ℃ of insulation 1h, at 900 ℃ of insulations of high temperature 6h, namely obtain the ferrosilicon silicate of lithium composite material after the cooling more then.
Li source compound is lithium sulfate among the embodiment 3, also can be any one or two kinds of above molar mixture arbitrarily in lithium hydroxide, acetate dihydrate lithium, lithium nitrate, lithium carbonate, lithium chloride, lithium sulfate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4, lithium oxalate, lithium acetate, lithium dihydrogen phosphate, lithium metasilicate, lithium phosphate, lithia, lithium nitrite, lithium molybdate, the lithium vanadate.
Fe source compound is nine water ferric nitrates among the embodiment 3, also can be for ferrous sulfate, ferrous carbonate, nine water ferric nitrates, frerrous chloride, iron chloride, ironic citrate, ferrous lactate, penta hydroxy group close iron, ferrous oxide, ferrous acetate, basic carbonate is ferrous, ethylenediamine tetra-acetic acid is ferrous, ferrous nitrate, bifluoride are ferrous, any one or two kinds of above molar mixture arbitrarily in the ferrous phosphate, ferric carbonate.
The silicon source compound is tetraethoxysilane among the embodiment 3, also can be silica, tetraethoxysilane, phenyl trichlorosilane, silicon nitride, dimethyldichlorosilane, silicon rubber, diethyl dichlorosilane, dichlorosilane, the diethyl chlorosilane, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silica gel, the crosslinked with silicane polypropylene, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, positive quanmethyl silicate, silicic acid, metasilicic acid, four (1-Methylethyl) esters of silicon acis, hexamethyldisiloxane, heptamethyldisilazane, triethyl-silicane, orthosilicic acid, two silicic acid, methyl silicate, methyl silicate, any one or two kinds of above molar mixture arbitrarily in the tetramethoxy-silicane.
Carbon-source cpd is carbon nano-tube among the embodiment 3, also can be ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch; petroleum asphalt; polypropylene; polyacrylamide; polyvinyl alcohol; starch; flour; tapioca flour; dehydrated potato powder; corn flour; taro meal; rice meal; carbon dust; bran powder; graphite powder; acetylene black; carbon black; sucrose; citric acid; furfural resin; poly-to benzene; benzene naphthalene dicarboxylic copolymer; benzene anthracene bipolymer; the luxuriant and rich with fragrance bipolymer of benzene; benzene naphthalene terpolymer; benzene naphthalene grace terpolymer; any one or two kinds of above molar mixture arbitrarily in the carbon nano-tube.
Organic acid is ascorbic acid among the embodiment 3, also can be one or more any molar mixture in ascorbic acid, ethanedioic acid, adipic acid, malonic acid, mandelic acid, malic acid, lactic acid, citric acid, formaldehyde, acetaldehyde, hutanal, isobutylaldehyde, tetraethyl ethylene glycol, isopropyl alcohol, the ethylene glycol.
Surfactant is P123 among the embodiment 3, also can be one or more any molar mixture in P123, polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, Qu Latong S-100, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide.
Solvent is the mixture of 50ml ethanol and 170ml deionized water among the embodiment 3, also can be any one or two kinds of above mixture of mol ratio arbitrarily in deionized water, distilled water, ethanol, the acetone.
Claims (10)
1. the preparation method of ferrosilicon silicate of lithium composite material is characterized in that, specifically implements according to following steps:
Step 1 is dissolved in Li source compound, Fe source compound, silicon source compound and surfactant in the solvent successively successively, uses organic acid for adjusting pH to 2～6 again, carries out low temperature waters reaction after washing, filtration then, obtains presoma finally by crossing spray drying;
Step 2, the presoma that step 1 is obtained mixes back ball milling, calcining with carbon-source cpd, namely obtain the ferrosilicon silicate of lithium composite material after the cooling.
2. the preparation method of ferrosilicon silicate of lithium composite material according to claim 1 is characterized in that, in the described step 1 in the Li source compound in lithium, the Fe source compound in iron and the silicon source compound mol ratio of silicon be 1.95～2.1:1:1; The mass ratio of surfactant and Li source compound is 0～3:1, and the mol ratio of lithium is 100～500:1 in solvent and the Li source compound.
3. the preparation method of ferrosilicon silicate of lithium composite material according to claim 1 and 2 is characterized in that, the low temperature waters is reflected in the reactor and carries out in the described step 1, and reaction temperature is 150～200 ℃, and the reaction time is 1～24h; Spray drying is carried out in spray dryer, and baking temperature is 80～220 ℃.
4. the preparation method of ferrosilicon silicate of lithium composite material according to claim 3, it is characterized in that, calcining is specifically implemented according to following steps in the described step 2: in inert atmosphere, earlier 300～500 ℃ of insulations 1～6 hour, again 600～900 ℃ of insulations 6～24 hours.
5. the preparation method of ferrosilicon silicate of lithium composite material according to claim 4 is characterized in that, the quality of carbon-source cpd is 1～20% of the lithium ion cell positive ferrosilicon silicate of lithium quality of materials that finally obtains in the described step 2.
6. the preparation method of ferrosilicon silicate of lithium composite material according to claim 5, it is characterized in that described Li source compound is any one or two kinds of above molar mixture arbitrarily in lithium hydroxide, acetate dihydrate lithium, lithium nitrate, lithium carbonate, lithium chloride, lithium sulfate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4, lithium oxalate, lithium acetate, lithium dihydrogen phosphate, lithium metasilicate, lithium phosphate, lithia, lithium nitrite, lithium molybdate, the lithium vanadate.
7. the preparation method of ferrosilicon silicate of lithium composite material according to claim 6, it is characterized in that described Fe source compound is that ferrous sulfate, ferrous carbonate, nine water ferric nitrates, frerrous chloride, iron chloride, ironic citrate, ferrous lactate, penta hydroxy group close iron, ferrous oxide, ferrous acetate, basic carbonate is ferrous, ethylenediamine tetra-acetic acid is ferrous, ferrous nitrate, bifluoride are ferrous, any one or two kinds of above molar mixture arbitrarily in the ferrous phosphate, ferric carbonate.
8. the preparation method of ferrosilicon silicate of lithium composite material according to claim 7, it is characterized in that described silicon source compound is silica, tetraethoxysilane, phenyl trichlorosilane, silicon nitride, dimethyldichlorosilane, silicon rubber, diethyl dichlorosilane, dichlorosilane, the diethyl chlorosilane, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silica gel, the crosslinked with silicane polypropylene, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, positive quanmethyl silicate, silicic acid, metasilicic acid, four (1-Methylethyl) esters of silicon acis, hexamethyldisiloxane, heptamethyldisilazane, triethyl-silicane, orthosilicic acid, two silicic acid, methyl silicate, methyl silicate, any one or two kinds of above molar mixture arbitrarily in the tetramethoxy-silicane.
9. the preparation method of ferrosilicon silicate of lithium composite material according to claim 8, it is characterized in that described carbon-source cpd is ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch; petroleum asphalt; polypropylene; polyacrylamide; polyvinyl alcohol; starch; flour; tapioca flour; dehydrated potato powder; corn flour; taro meal; rice meal; carbon dust; bran powder; graphite powder; acetylene black; carbon black; sucrose; citric acid; furfural resin; poly-to benzene; benzene naphthalene dicarboxylic copolymer; benzene anthracene bipolymer; the luxuriant and rich with fragrance bipolymer of benzene; benzene naphthalene terpolymer; benzene naphthalene grace terpolymer; any one or two kinds of above molar mixture arbitrarily in the carbon nano-tube.
10. the preparation method of ferrosilicon silicate of lithium composite material according to claim 9, it is characterized in that described organic acid is one or more any molar mixture in ascorbic acid, ethanedioic acid, adipic acid, malonic acid, mandelic acid, malic acid, lactic acid, citric acid, formaldehyde, acetaldehyde, hutanal, isobutylaldehyde, tetraethyl ethylene glycol, isopropyl alcohol, the ethylene glycol; Described surfactant is one or more any molar mixture in P123, polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, Qu Latong S-100, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide; Described solvent is any one or two kinds of above mixture of mol ratio arbitrarily in deionized water, distilled water, ethanol, the acetone.
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| CN110800142A (en) * | 2017-12-08 | 2020-02-14 | 株式会社Lg化学 | Negative active material for lithium secondary battery and method for preparing same |
| US11296312B2 (en) | 2017-12-08 | 2022-04-05 | Lg Energy Solution, Ltd. | Negative electrode active material for lithium secondary battery and method for preparing the same |
| CN110800142B (en) * | 2017-12-08 | 2022-08-05 | 株式会社Lg新能源 | Negative active material for lithium secondary battery and method for preparing same |
| US11664487B2 (en) | 2017-12-08 | 2023-05-30 | Lg Energy Solution, Ltd. | Negative electrode active material for lithium secondary battery and method for preparing the same |
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