CN103247800A - Manufacturing method of positive pole lithium ferrous silicate material of lithium-ion battery - Google Patents
Manufacturing method of positive pole lithium ferrous silicate material of lithium-ion battery Download PDFInfo
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Abstract
The invention relates to a manufacturing method of a positive pole lithium ferrous silicate material of a lithium-ion battery. The method comprises the following steps of: step 1, dissolving a lithium source compound, an iron source compound and a silicon source compound in a solvent, sequentially adding a carbon source compound and a surface active agent, and adjusting pH to 4-6 by organic acid to obtain a Li-Fe-Si-C mixture; and step 2, carrying out supercritical water-bath reaction on the obtained Li-Fe-Si-C mixture, filtering and washing the mixture to be neutral, and finally carrying out spray drying so as to obtain the positive pole lithium ferrous silicate material of the lithium-ion battery. According to the manufacturing method of the positive pole lithium ferrous silicate material of the lithium-ion battery, the positive pole lithium ferrous silicate material prepared by spray drying has uniform particle size and controllable shape, the conductivity of the positive pole lithium ferrous silicate material is effectively improved, and the manufacturing method is simple and convenient to synthetize.
Description
Technical field
The invention belongs to technical field of material, relate to a kind of lithium ion cell positive ferrosilicon silicate of lithium preparation methods.
Background technology
Since the nineties in last century, Sony was released lithium ion battery, lithium ion battery became common recognition widely as the energy of new generation, and lithium ion battery is compared with conventional batteries, its energy density height, self discharge is little, and long service life, particularly environmental sound become the first-selection of green energy resource.Present lithium ion battery is widely used in various aspects such as digital product, electric tool, toy, military power supply, accumulation power supply, being the present emphasis of broad research in the world as the power train in vehicle application power supply wherein, also is the huge development potentiality of lithium ion battery and popularization direction.
Present lithium ion battery mainly is made up of positive and negative pole material, electrolyte, barrier film and pack case, wherein positive electrode is one of main raw material(s) that determines its performance, mainly contain cobalt acid lithium, LiMn2O4, ternary material and LiFePO 4 material etc., the security performance of cobalt acid lithium material is relatively poor, and the cobalt element price is higher, the cycle performance of lithium manganate material is relatively poor relatively, ternary material and LiFePO 4 material multiplying power discharging ability, cause power density little, these materials all can not satisfy market at present fully to the demand of power train in vehicle application lithium ion battery.Therefore seeking new positive electrode is one of present research direction, and the lithium metasilicate material becomes the focus of studying positive electrode after being found with its structure similar to LiFePO4.The main method of production of this material has solid phase method and sol-gal process at present, and the material particle size of solid phase method preparation is inhomogeneous, and crystal grain is bigger, and the process complexity of Prepared by Sol Gel Method, technological parameter is difficult to control.
Summary of the invention
The purpose of this invention is to provide a kind of lithium ion cell positive ferrosilicon silicate of lithium preparation methods, the inhomogeneous problem of material particle size that has solved existing method complex process and prepared.
The technical solution adopted in the present invention is, lithium ion cell positive ferrosilicon silicate of lithium preparation methods is specifically implemented according to following steps:
Step 1 is dissolved in Li source compound, Fe source compound and silicon source compound in the solvent, adds carbon-source cpd and surfactant then successively, uses organic acid for adjusting pH to 4～6 again, obtains the Li-Fe-Si-C mixture;
Step 2, the Li-Fe-Si-C mixture that step 1 is obtained carries out the reaction of overcritical waters, filters, is washed to neutrality then, carries out spray drying at last, namely obtains lithium ion cell positive ferrous metasilicate lithium material.
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 quality of carbon-source cpd is 1～20% of the lithium ion cell positive ferrosilicon silicate of lithium quality of materials that finally obtains; 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.
Overcritical waters is reflected in the reactor and carries out in the step 2; the temperature of reactor is 180～350 ℃; reaction time is 1～24h, and protective atmosphere is the mist of any one or two kinds of above arbitrary volume ratio in carbon monoxide, carbon dioxide, hydrogen, nitrogen and the argon gas.
Spray drying is carried out in spray dryer in the step 2, and baking temperature is 80～220 ℃.
Li source compound is any one or two kinds of above mixture of mol ratio arbitrarily in lithium hydroxide, acetate dihydrate lithium, lithium nitrate, 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, iron hydroxide, ferrous lactate, penta hydroxy group close iron, ferric nitrate, di-iron trioxide, tri-iron tetroxide, 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 mixture of mol ratios arbitrarily in the ferrous phosphate, ferric carbonate.
The silicon source compound is tetraethoxysilane, silicon nitride, dimethyldichlorosilane, diethyl dichlorosilane, dichlorosilane, the diethyl chlorosilane, silicon dioxide, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silicone oil, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, silicon tetrafluoride, silicon tetrachloride, one ethyl trichlorosilane, ethyl dichlorosilane, positive tetraethyl orthosilicate, 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, the any one or two kinds of above mixture of mol ratio 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; any one or two kinds of above mixture of mol ratio arbitrarily in the benzene naphthalene grace terpolymer.
Solvent is any one or two kinds of above mixture of mol ratio arbitrarily in deionized water, distilled water, ethanol, the acetone; Organic acid is any one or two kinds of above mixture of mol ratio arbitrarily in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, sucrose, the glucose; Surfactant is the mixture of one or more any mol ratios in polyvinyl alcohol, P123, polyethylene glycol, polyethylene glycol oxide, kayexalate, Qu Latong S-100, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide.
The invention has the beneficial effects as follows, lithium ion cell positive ferrosilicon silicate of lithium preparation methods of the present invention, the lithium ion cell positive ferrosilicon silicate of lithium material particle size uniformity for preparing by spray drying, pattern is controlled, effectively raise the conductivity of ferrous silicate lithium anode material, and its preparation method is simple, and is synthetic convenient.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the lithium ion cell positive ferrous metasilicate lithium material for preparing of the embodiment of the invention 1;
Fig. 2 is the electron-microscope scanning figure of the lithium ion cell positive ferrous metasilicate lithium material for preparing of the embodiment of the invention 1;
Fig. 3 is the first charge-discharge figure of the lithium ion cell positive ferrous metasilicate lithium 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.
Lithium ion cell positive ferrosilicon silicate of lithium preparation methods of the present invention, specifically implement according to following steps:
Step 1, Li source compound, Fe source compound and silicon source compound are dissolved in the solvent with 1.95～2.1:1:1 mol ratio by silicon in iron in lithium, the Fe source compound in the Li source compound and the silicon source compound, the mol ratio of lithium is 100～500:1 in solvent and the Li source compound, add carbon-source cpd and surfactant then successively, 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; The mass ratio of surfactant and Li source compound is 0～3:1, uses organic acid for adjusting pH to 4～6 again, obtains the Li-Fe-Si-C mixture;
Step 2; the Li-Fe-Si-C mixture that step 1 is obtained carries out overcritical waters reaction 1～24h in the reactor again; the temperature of reactor is 180～350 ℃; protective atmosphere is the mist of any one or two kinds of above arbitrary volume ratio in carbon monoxide, carbon dioxide, hydrogen, nitrogen and the argon gas; filter, be washed to neutrality then; carry out spray drying at last in spray dryer, baking temperature is 80～220 ℃, namely obtains lithium ion cell positive ferrous metasilicate lithium material.
Li source compound is any one or two kinds of above mixture of mol ratio arbitrarily in lithium hydroxide, acetate dihydrate lithium, lithium nitrate, 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, iron hydroxide, ferrous lactate, penta hydroxy group close iron, ferric nitrate, di-iron trioxide, tri-iron tetroxide, 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 mixture of mol ratios arbitrarily in the ferrous phosphate, ferric carbonate.
The silicon source compound is tetraethoxysilane, silicon nitride, dimethyldichlorosilane, diethyl dichlorosilane, dichlorosilane, the diethyl chlorosilane, silicon dioxide, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silicone oil, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, silicon tetrafluoride, silicon tetrachloride, one ethyl trichlorosilane, ethyl dichlorosilane, positive tetraethyl orthosilicate, 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, the any one or two kinds of above mixture of mol ratio 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; any one or two kinds of above mixture of mol ratio arbitrarily in the benzene naphthalene grace terpolymer.
Solvent is any one or two kinds of above mixture of mol ratio arbitrarily in deionized water, distilled water, ethanol, the acetone; Organic acid is any one or two kinds of above mixture of mol ratio arbitrarily in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, sucrose, the glucose; Surfactant is the mixture of one or more any mol ratios in polyvinyl alcohol, P123, polyethylene glycol, polyethylene glycol oxide, kayexalate, Qu Latong S-100, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide.
Lithium ion cell positive ferrosilicon silicate of lithium preparation methods of the present invention, the lithium ion cell positive ferrosilicon silicate of lithium material particle size uniformity for preparing by spray drying, pattern is controlled, effectively raise the conductivity of ferrous silicate lithium anode material, and its preparation method is simple, and is synthetic convenient.
Embodiment 1
Step 1 is dissolved in 0.02mol lithium acetate, 0.01mol ferrous nitrate, 0.01mol tetraethoxysilane, 2g P123 in the 100ml acetone, adds 4.5g sucrose and 0.5g polyethylene glycol then successively, regulates pH to 5 with oxalic acid again, obtains the Li-Fe-Si-C mixture;
Step 2; the Li-Fe-Si-C mixture that step 1 is obtained moves to overcritical waters reaction 20h in the reactor; the temperature of reactor is 220 ℃; protective atmosphere is carbon monoxide; filter, be washed to neutrality then; carry out spray drying at last in spray dryer, baking temperature is 90 ℃, namely obtains lithium ion cell positive ferrous metasilicate lithium material.
Fig. 1 is the x-ray diffraction pattern of the lithium ion cell positive ferrous metasilicate lithium material for preparing of the embodiment of the invention 1, as can be seen from Figure 1, and the lithium ion cell positive ferrous metasilicate lithium material phasor that embodiment 1 obtains and ferrosilicon silicate of lithium phasor basically identical.
Fig. 2 is the electron-microscope scanning figure of the lithium ion cell positive ferrous metasilicate lithium material for preparing of the embodiment of the invention 1, and as can be seen from Figure 2, the granularity of the lithium ion cell positive ferrous metasilicate lithium material that embodiment 1 obtains is less and even.
The lithium ion cell positive ferrosilicon silicate of lithium material powder that embodiment 1 is obtained, conductive black and polyvinylidene fluoride (PVDF) mix in the ratio of mass ratio 75:15:10, add an amount of N-methyl pyrrolidone (NMP), be applied on the aluminium foil after fully stirring into evenly, 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 ethylene carbonate that volume ratio is 1:1:1 (EC)/1 again, the 1molL-1LiPF6 electrolyte of 2-dimethyl carbonate (DMC)/diethyl carbonate (DEC) is assembled into CR2032 type button cell in being full of the glove box of argon gas.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 lithium ion cell positive ferrous metasilicate lithium material for preparing of the embodiment of the invention 1, as can be seen from Figure 3, the charging capacity of the lithium ion cell positive ferrous metasilicate lithium material that embodiment 1 obtains reaches 143mAh/g, and reversible capacity is 104mAh/g.
Embodiment 2
Step 1 is dissolved in 0.039mol lithium chloride, 0.01mol ferrous sulfate and 0.01mol metasilicic acid in 30ml ethanol and the 30ml acetone soln, adds 0.24g glucose then, uses lemon acid for adjusting pH to 4 again, obtains the Li-Fe-Si-C mixture;
Step 2; the Li-Fe-Si-C mixture that step 1 is obtained moves to and carries out overcritical waters reaction 1h in the reactor; the temperature of reactor is 350 ℃; protective atmosphere is the gaseous mixture of nitrogen and argon gas; filter, be washed to neutrality then; carry out spray drying at last in spray dryer, baking temperature is 80 ℃, namely obtains lithium ion cell positive ferrous metasilicate lithium material.
Embodiment 3
Step 1 is dissolved in 0.042mol lithium acetate, 0.01mol ferrous sulfate and 0.01molTEOS in 80ml deionized water and the 40ml acetone soln, adds the carbon black of 6.3g sucrose and 0.1g then, uses apple acid for adjusting pH to 6 again, obtains the Li-Fe-Si-C mixture;
Step 2; the Li-Fe-Si-C mixture that step 1 is obtained moves to and carries out overcritical waters reaction 24h in the reactor; the temperature of reactor is 180 ℃; protective atmosphere is the gaseous mixture of nitrogen and argon gas; filter, be washed to neutrality then; carry out spray drying at last in spray dryer, baking temperature is 220 ℃, namely obtains lithium ion cell positive ferrous metasilicate lithium material.
Embodiment 4
Step 1 is dissolved in 0.02mol lithium acetate, 0.01mol ferrous nitrate, 0.01mol tetraethoxysilane, 2g P123 in the 100ml acetone, adds the carbon black of 0.02g then successively, regulates pH to 5 with oxalic acid again, obtains the Li-Fe-Si-C mixture;
Step 2; the Li-Fe-Si-C mixture that step 1 is obtained moves to overcritical waters reaction 20h in the reactor; the temperature of reactor is 220 ℃; protective atmosphere is carbon monoxide; filter, be washed to neutrality then; carry out spray drying at last in spray dryer, baking temperature is 130 ℃, namely obtains lithium ion cell positive ferrous metasilicate lithium material.
Embodiment 5
Step 1 is dissolved in 0.039mol lithium chloride, 0.01mol ferrous sulfate and 0.01mol metasilicic acid in 30ml ethanol and the 30ml acetone soln, adds 0.24g glucose then, uses lemon acid for adjusting pH to 5 again, obtains the Li-Fe-Si-C mixture;
Step 2; the Li-Fe-Si-C mixture that step 1 is obtained moves to and carries out overcritical waters reaction 4h in the reactor; the temperature of reactor is 320 ℃; protective atmosphere is the gaseous mixture of nitrogen and argon gas; filter, be washed to neutrality then; carry out spray drying at last in spray dryer, baking temperature is 180 ℃, namely obtains lithium ion cell positive ferrous metasilicate lithium material.
Surfactant is polyethylene glycol among the embodiment 1, also can be the mixture of one or more any mol ratios in polyvinyl alcohol, P123, polyethylene glycol, polyethylene glycol oxide, kayexalate, Qu Latong S-100, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide.
Li source compound is lithium chloride among the embodiment 5, also can be any one or two kinds of above mixture of mol ratio arbitrarily in lithium hydroxide, acetate dihydrate lithium, lithium nitrate, 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 ferrous sulfate among the embodiment 5, also can be for ferrous sulfate, ferrous carbonate, nine water ferric nitrates, frerrous chloride, iron chloride, ironic citrate, iron hydroxide, ferrous lactate, penta hydroxy group close iron, ferric nitrate, di-iron trioxide, tri-iron tetroxide, 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 mixture of mol ratios arbitrarily in the ferrous phosphate, ferric carbonate.
The silicon source compound is metasilicic acid among the embodiment 5, also can be tetraethoxysilane, silicon nitride, dimethyldichlorosilane, diethyl dichlorosilane, dichlorosilane, the diethyl chlorosilane, silicon dioxide, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silicone oil, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, silicon tetrafluoride, silicon tetrachloride, one ethyl trichlorosilane, ethyl dichlorosilane, positive tetraethyl orthosilicate, 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, the any one or two kinds of above mixture of mol ratio arbitrarily in the tetramethoxy-silicane.
Carbon-source cpd is glucose among the embodiment 5, 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; any one or two kinds of above mixture of mol ratio arbitrarily in the benzene naphthalene grace terpolymer.
Solvent is the mixture of 30ml ethanol and 30ml acetone among the embodiment 5, also can be any one or two kinds of above mixture of mol ratio arbitrarily in deionized water, distilled water, ethanol, the acetone.
Organic acid is citric acid among the embodiment 5, also can be any one or two kinds of above mixture of mol ratio arbitrarily in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, sucrose, the glucose;
Protective atmosphere is the mist of nitrogen and argon gas among the embodiment 5, also can be the mist of any one or two kinds of above arbitrary volume ratio in carbon monoxide, carbon dioxide, hydrogen, nitrogen and the argon gas.
Claims (9)
1. lithium ion cell positive ferrosilicon silicate of lithium preparation methods is characterized in that, specifically implements according to following steps:
Step 1 is dissolved in Li source compound, Fe source compound and silicon source compound in the solvent, adds carbon-source cpd and surfactant then successively, uses organic acid for adjusting pH to 4～6 again, obtains the Li-Fe-Si-C mixture;
Step 2, the Li-Fe-Si-C mixture that step 1 is obtained carries out the reaction of overcritical waters, filters, is washed to neutrality then, carries out spray drying at last, namely obtains lithium ion cell positive ferrous metasilicate lithium material.
2. lithium ion cell positive ferrosilicon silicate of lithium preparation methods 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 quality of carbon-source cpd is 1～20% of the lithium ion cell positive ferrosilicon silicate of lithium quality of materials that finally obtains; 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. lithium ion cell positive ferrosilicon silicate of lithium preparation methods according to claim 1 and 2; it is characterized in that; overcritical waters is reflected in the reactor and carries out in the described step 2; the temperature of reactor is 180～350 ℃; reaction time is 1～24h, and protective atmosphere is the mist of any one or two kinds of above arbitrary volume ratio in carbon monoxide, carbon dioxide, hydrogen, nitrogen and the argon gas.
4. lithium ion cell positive ferrosilicon silicate of lithium preparation methods according to claim 3 is characterized in that spray drying is carried out in the described step 2 in spray dryer, and baking temperature is 80～220 ℃.
5. lithium ion cell positive ferrosilicon silicate of lithium preparation methods according to claim 4, it is characterized in that described Li source compound is any one or two kinds of above mixture of mol ratio arbitrarily in lithium hydroxide, acetate dihydrate lithium, lithium nitrate, 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.
6. lithium ion cell positive ferrosilicon silicate of lithium preparation methods according to claim 5, 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, iron hydroxide, ferrous lactate, penta hydroxy group close iron, ferric nitrate, di-iron trioxide, tri-iron tetroxide, 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 mixture of mol ratios arbitrarily in the ferrous phosphate, ferric carbonate.
7. lithium ion cell positive ferrosilicon silicate of lithium preparation methods according to claim 6, it is characterized in that described silicon source compound is tetraethoxysilane, silicon nitride, dimethyldichlorosilane, diethyl dichlorosilane, dichlorosilane, the diethyl chlorosilane, silicon dioxide, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silicone oil, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, silicon tetrafluoride, silicon tetrachloride, one ethyl trichlorosilane, ethyl dichlorosilane, positive tetraethyl orthosilicate, 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, the any one or two kinds of above mixture of mol ratio arbitrarily in the tetramethoxy-silicane.
8. lithium ion cell positive ferrosilicon silicate of lithium preparation methods according to claim 7, 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; any one or two kinds of above mixture of mol ratio arbitrarily in the benzene naphthalene grace terpolymer.
9. lithium ion cell positive ferrosilicon silicate of lithium preparation methods according to claim 8 is characterized in that, described solvent is any one or two kinds of above mixture of mol ratio arbitrarily in deionized water, distilled water, ethanol, the acetone; Described organic acid is any one or two kinds of above mixture of mol ratio arbitrarily in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, sucrose, the glucose; Described surfactant is the mixture of one or more any mol ratios in polyvinyl alcohol, P123, polyethylene glycol, polyethylene glycol oxide, kayexalate, Qu Latong S-100, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide.
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| CN112429752A (en) * | 2020-12-07 | 2021-03-02 | 贵州红星电子材料有限公司 | Method for recovering lithium iron phosphorus from waste lithium iron phosphate positive electrode material |
| CN113793924A (en) * | 2021-08-25 | 2021-12-14 | 浙江工业大学 | By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material |
| CN116002650A (en) * | 2022-12-28 | 2023-04-25 | 浙江钠创新能源有限公司 | Preparation method of composite ferric sodium pyrophosphate polyanion type positive electrode material and application of composite ferric sodium pyrophosphate polyanion type positive electrode material in sodium ion battery |
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| CN112429752A (en) * | 2020-12-07 | 2021-03-02 | 贵州红星电子材料有限公司 | Method for recovering lithium iron phosphorus from waste lithium iron phosphate positive electrode material |
| CN112429752B (en) * | 2020-12-07 | 2023-01-03 | 贵州红星电子材料有限公司 | Method for recovering lithium iron phosphorus from waste lithium iron phosphate positive electrode material |
| CN113793924A (en) * | 2021-08-25 | 2021-12-14 | 浙江工业大学 | By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material |
| CN116002650A (en) * | 2022-12-28 | 2023-04-25 | 浙江钠创新能源有限公司 | Preparation method of composite ferric sodium pyrophosphate polyanion type positive electrode material and application of composite ferric sodium pyrophosphate polyanion type positive electrode material in sodium ion battery |
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