CN103326026A - Method for preparing porous lithium-iron silicate/carbon composite material for positive pole of lithium ion battery - Google Patents
Method for preparing porous lithium-iron silicate/carbon composite material for positive pole of lithium ion battery Download PDFInfo
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Abstract
The invention relates to a method for preparing a porous lithium-iron silicate/carbon composite material for the positive pole of a lithium ion battery. The method comprises the steps of: mixing and dissolving a lithium source compound, a ferrous source compound and a silicon source compound, then, adding dual-template directing agents and a carbon source compound, carrying out ultrasonic dispersion, and then, putting a mixture in a hydrothermal kettle for reaction in an inert gas environment; and after the reaction is ended, washing a product by using deionized water and anhydrous ethanol, and carrying out vacuum drying on the product in a vacuum drying oven, thereby obtaining the composite material. According to the method, the dual-template directing agents are adopted during the synthesis of the material, are uniformly dispersed among reactants through mixing and enable the reactants to produce porous Li2FeSiO4 through self-assembly reaction under hydrothermal conditions, so that a carbon source can be uniformly filled in pores of the porous Li2FeSiO4, and porous Li2FeSiO4/C, namely the composite material for the positive pole of the lithium ion battery, with excellent electrochemical properties is obtained.
Description
Technical field
The invention belongs to technical field, particularly the preparation method of a kind of porous ferric metasilicate lithium/carbon lithium ion battery anode composite material.
Background technology
Since the eighties of last century the nineties, the research of lithium ion battery and application have obtained development at full speed.Because it has that operating voltage is high, capacity is high, cycle performance is good and the advantage such as fail safe is good, application is more and more extensive.
Present lithium ion battery mainly is comprised of positive and negative pole material, electrolyte, barrier film and pack case, and wherein positive electrode is one of main raw material(s) that determines its performance, also is the bottleneck that present performance of lithium ion battery improves.And present positive electrode mainly contains cobalt acid lithium, LiMn2O4, ternary material, LiFePO4 etc., cobalt acid lithium is because the scarcity price of cobalt element is higher, its security performance is relatively poor in addition, the cycle performance of lithium manganate material is relatively relatively poor, there are its multiplying power discharging ability in ternary material and LiFePO 4 material, cause power density little, these materials at present all fully satisfying the market to the demand of power train in vehicle application lithium ion battery.So 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, hydro thermal method, sol-gal process etc. at present, its modified measures is mainly concentrated on control, coating and the doping etc. of crystal grain thinning, pattern.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide the preparation method of a kind of porous ferric metasilicate lithium/carbon lithium ion battery anode composite material, the conductivity of above-mentioned material and the problem of lithium ion mobility have been solved, simultaneously, the present invention is simple for process, is suitable for suitability for industrialized production.
To achieve these goals, the technical solution used in the present invention is:
The preparation method of a kind of porous ferric metasilicate lithium/carbon lithium ion battery anode composite material comprises the steps:
1) with after Li source compound, ferrous iron source compound and the mixing of silicon source compound, add bimodulus plate directed agents and carbon-source cpd, transfer pH to 3-4 with hydrochloric acid after stirring, then ultrasonic dispersion is then put into water heating kettle and is reacted under inert gas environment;
2) after reaction finishes, product with deionized water and absolute ethanol washing, is drying to obtain porous ferric metasilicate lithium/carbon in vacuum drying chamber.
The Li:Fe:Si mol ratio is (1.9-2.1) in the described step 1): (0.95-1.05): 1, bimodulus plate directed agents addition is 30～150% of lithium source, source of iron and silicon source three's gross mass, the carbon-source cpd addition is 1～30% of lithium source, source of iron and silicon source three's gross mass, stir 1～3h, ultrasonic dispersion 10～60min
60～240 ℃ were reacted 4～48 hours under inert gas environment.
Described step 2) the vacuumize parameter is 80～140 ℃ of dryings 10～20 hours in.
Described Li source compound is one or more mixing of lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride, lithium nitrate.
Described ferrous iron source compound is that ferrous sulfate, ferrous oxalate, ferrous carbonate, frerrous chloride, ferrous lactate, ferrous oxide, ferrous acetate, basic carbonate are ferrous, ethylenediamine tetra-acetic acid is ferrous, ferrous nitrate, bifluoride are ferrous, one or more mixing of ferrous phosphate.
Described silicon source compound is silica, tetraethoxysilane, phenyl trichlorosilane, silicon nitride, dimethyldichlorosilane, silicon rubber, diethyl dichlorosilane, dichlorosilane, the diethyl chlorosilane, silicon dioxide, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silica gel, the crosslinked with silicane polypropylene, silicone oil, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, silicon tetrafluoride, silicon tetrachloride, silicon monoxide, one ethyl trichlorosilane, ethyl dichlorosilane, 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, in the tetramethoxy-silicane any or several mixing.
Described bimodulus plate directed agents is any or several mixing of polyvinyl alcohol-gluconic acid sodium salt, polyethylene glycol-gluconic acid sodium salt, polyethylene glycol oxide-ethylenediamine tetra-acetic acid, kayexalate-ethylenediamine tetra-acetic acid, polyoxyethylene nonylplenyl ether-cetyl trimethyl kelene, softex kw-OTAC, Cetyltrimethylammonium bromide-Qu Latong S-100.
Described carbon source 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 more any molar mixture in the benzene naphthalene grace terpolymer.
Described carbon source is the organic compound that can be decomposed into conductive carbon class material after the pyrolysis.
Because adopted bimodulus plate directed agents among the present invention in the building-up process of material, these bimodulus plate directed agents are distributed between the reactant by mixing, the template direction agent makes itself and reactant generate cellular Li by self-assembling reaction under hydrothermal condition
2FeSiO
4Thereby, make carbon source can be filled in uniformly cellular Li
2FeSiO
4The duct in.Can obtain cellular Li so in building-up process, add bimodulus plate directed agents
2FeSiO
4/ C, the good anode composite material of lithium ion battery of chemical property.
The present invention has the following advantages:
1, the raw material wide material sources are pollution-free, and cost is low;
2, material preparation technique is simple, safe;
3, prepared cellular Li
2FeSiO
4/ C anode composite material of lithium ion battery material has comparatively desirable pore distribution, for the even coating of material with carbon element provides a cover effective solution;
4, positive electrode involved in the present invention can be widely used in comprising all kinds of mobile electronic products and electric vehicle in all kinds of lithium ion batteries.
Description of drawings:
Fig. 1 is the X-ray diffraction style of the prepared ferrosilicon silicate of lithium sample of embodiment 1, adopt the Japanese Rigaku D/MAX-2400 of company type X-ray diffractometer, Cu K α target is radiation source, voltage is 46kV, electric current is 100mA, step-length is 0.02, sweep speed be 10 (°)/min, sweep limits (2 θ) is 3 °～90 °.
Fig. 2 is the ESEM picture of the prepared ferrosilicon silicate of lithium sample of embodiment 1, utilizes the JSM-6700F of NEC company type field emission scanning electron microscope (FESEM) to take.
Fig. 3 is for pressing the first charge-discharge curve chart of the prepared ferrous silicate lithium anode material of embodiment 1.
Embodiment
Describe embodiments of the present invention in detail below in conjunction with embodiment.
With 7.4g lithium carbonate, 18g ferrous nitrate and 22.4mL tetraethoxysilane mixed dissolution in 100mL water, add afterwards 20g polyvinyl alcohol-gluconic acid sodium salt bimodulus plate directed agents and 3g acetylene black, above-mentioned substance stirs and mixed in 1 hour, transfer pH to 3 with hydrochloric acid, then put into water heating kettle behind the ultrasonic dispersion 30min, in the situation that be full of inert gas, 200 ℃ were reacted 24 hours;
After reaction finishes, use respectively deionized water and absolute ethanol washing for several times the above-mentioned product after, 100 ℃ of vacuumizes obtained porous ferric metasilicate lithium/carbon in 10 hours in vacuum drying chamber.
Fig. 1 is the XRD collection of illustrative plates of gained ferrosilicon silicate of lithium, and all diffraction maximums can be corresponding with the characteristic peak of ferrosilicon silicate of lithium, does not observe the diffraction maximum of impurity.Fig. 2 is the stereoscan photograph of gained ferrosilicon silicate of lithium, and synthetic material is porous material, the class spherical morphology.
The gained sample carries out electrochemical property test as follows: with the in mass ratio ratio mixing of 80:10:10 of porous ferric metasilicate lithium/carbon sample powder, conductive black and PVDF (polyvinylidene fluoride), add an amount of organic solvent NMP (1-METHYLPYRROLIDONE), be applied on the aluminium foil 120 ℃ of dry 12h in vacuum drying chamber after fully stirring into even pastel.Cut-off directly be the small pieces of 16mm for anodal, metal lithium sheet is negative pole, the Celgard2400 microporous polypropylene membrane is barrier film, to be dissolved in volume ratio as the 1molL of the EC (ethylene carbonate) of 1:1/DMC (1,2-dimethyl carbonate)
-1LiPF
6Be electrolyte, in being full of the glove box of argon gas, be assembled into CR2032 type button cell.Button cell is placed its chemical property of test on the CT2001A type battery test system.Charge-discharge magnification is C/30, and voltage range is 1.5V-4.8V.Fig. 3 is this material first charge-discharge curve, and as seen from the figure, the charging capacity of the material that is synthesized reaches 187mAh/g, and reversible capacity is 127mAh/g.
Embodiment 2
3.7g lithium carbonate, 9g ferrous nitrate and 11.2mL tetraethoxysilane mixed dissolution are added 15g kayexalate-ethylenediamine tetra-acetic acid and 2g acetylene black behind 100mL water, above-mentioned substance stirs 3h and mixes, transfer pH to 4 with hydrochloric acid, then put into water heating kettle behind the ultrasonic dispersion 30min, in the situation that be full of inert gas, 200 ℃ were reacted 24 hours;
After reaction finishes, use respectively deionized water and absolute ethanol washing for several times the above-mentioned product after, be put into that 100 ℃ of vacuumizes obtained porous ferric metasilicate lithium/carbon in 10 hours in the vacuum drying chamber;
Under nitrogen protection, porous ferric metasilicate lithium/carbon is joined in the 100mL alcohol-water solution, keep the final volume of pure water than being 10:1, mixer stirs and adds proper ammonia control pH value of solution after 60 minutes in the 8-9 scope, then the TEOS that adds 67mL, lithium iron phosphate/carbon wherein: the TEOS mol ratio is 1:3, and reaction is 8 hours under the room temperature;
Test its chemical property according to the method for embodiment 1, the first circulating and reversible capacity of gained positive electrode is 125mAh/g.
Embodiment 3
2.98g lithium carbonate, 5.67g ferrous oxalate, 2.3g silicon dioxide are mixed in the 100mL water, the 16g softex kw that adds again-OTAC bimodulus plate directed agents and 3g glucose, above-mentioned substance mixes, put into water heating kettle behind the ultrasonic dispersion 30min, in the situation that be full of inert gas, 200 ℃ were reacted 24 hours;
After reaction finishes, use respectively deionized water and absolute ethanol washing for several times the above-mentioned product after, be put into that 130 ℃ of vacuumizes obtained porous ferric metasilicate lithium/carbon in 10 hours in the vacuum drying chamber.
Test its chemical property according to the method for embodiment 1, the first circulating and reversible capacity of gained positive electrode is 131mAh/g.
Embodiment 4
1.79g lithium hydroxide, 5.4g ferrous oxalate, 2.3g silicon dioxide and 1.5g citric acid are mixed in the 100mL water, the 4g Cetyltrimethylammonium bromide that adds again-Qu Latong S-100 bimodulus plate directed agents and 1g glucose, above-mentioned substance mixes, put into water heating kettle behind the ultrasonic dispersion 30min, in the situation that be full of inert gas, 240 ℃ were reacted 24 hours;
After reaction finishes, use respectively deionized water and absolute ethanol washing for several times the above-mentioned product after, be put into that 120 ℃ of vacuumizes obtained porous ferric metasilicate lithium/carbon in 18 hours in the vacuum drying chamber.
Test its chemical property according to the method for embodiment 1, the first circulating and reversible capacity of gained positive electrode is 143mAh/g.
Embodiment 5
Press embodiment 1, only hydrothermal temperature changes 240 ℃ into, and the first circulating and reversible capacity of gained positive electrode is 127mAh/g.
Embodiment 6
Embodiment 7
(mass ratio is the lithium oxalate of 1:1:1 with Li source compound, lithium acetate, lithium chloride), (mass ratio is the silicon tetrafluoride of 1:1:1 for ferrous iron source compound (mass ratio is that the basic carbonate of 1:2 is ferrous ferrous with ethylenediamine tetra-acetic acid) and silicon source compound, silicon tetrachloride, silicon monoxide) be to be scattered in the water after 1.9:0.95:1 mixes to dissolve by the Li:Fe:Si mol ratio, add the lithium source, the carbon-source cpd polypropylene of the bimodulus plate directed agents polyoxyethylene nonylplenyl ether of source of iron and silicon source three's gross mass 80%-cetyl trimethyl kelene and three's gross mass 30%, after stirring the 2h mixing, transfer pH to 3 with hydrochloric acid, then ultrasonic dispersion 20min puts into water heating kettle, and 120 ℃ were reacted 25 hours under inert gas environment.
2) after reaction finished, with product deionized water and absolute ethanol washing, 100 ℃ of vacuumizes namely got porous ferric metasilicate lithium/carbon in 15 hours in vacuum drying chamber.
Embodiment 8
Press embodiment 7, Li source compound is changed into lithium nitrate and the lithium oxalate of mass ratio 1:1, the ferrous iron source compound changes ferrous oxide, ferrous acetate, bifluoride ferrous iron and the ferrous phosphate of mass ratio 1:1:1:1 into, and the silicon source compound changes ethyl dichlorosilane, tetraethyl orthosilicate and the silicic acid of quality 1:2:1 into.The Li:Fe:Si mol ratio is 2.1:1.05:1.
Li source compound among the present invention, ferrous iron source compound, silicon source compound, carbon-source cpd and bimodulus plate directed agents all can have multiple choices, and the selection of particular compound is still belonged to protection scope of the present invention.
Claims (9)
1. the preparation method of porous ferric metasilicate lithium/carbon lithium ion battery anode composite material is characterized in that, comprises the steps:
1) with after Li source compound, ferrous iron source compound and the mixing of silicon source compound, add bimodulus plate directed agents and carbon-source cpd, transfer pH to 3-4 with hydrochloric acid after stirring, then ultrasonic dispersion is then put into water heating kettle and is reacted under inert gas environment;
2) after reaction finishes, product with deionized water and absolute ethanol washing, is drying to obtain porous ferric metasilicate lithium/carbon in vacuum drying chamber.
2. described preparation method according to claim 1, it is characterized in that, the Li:Fe:Si mol ratio is (1.9-2.1) in the described step 1): (0.95-1.05): 1, bimodulus plate directed agents addition is 30～150% of lithium source, source of iron and silicon source three's gross mass, the carbon-source cpd addition is 1～30% of lithium source, source of iron and silicon source three's gross mass, stir 1～3h, ultrasonic dispersion 10～60min, 60～240 ℃ were reacted 4～48 hours under inert gas environment.
3. described preparation method according to claim 1 is characterized in that described step 2) in the vacuumize parameter be 80～140 ℃ of dryings 10～20 hours.
4. described preparation method according to claim 1 is characterized in that, described Li source compound is one or more mixing of lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride, lithium nitrate.
5. described preparation method according to claim 1, it is characterized in that, described ferrous iron source compound is that ferrous sulfate, ferrous oxalate, ferrous carbonate, frerrous chloride, ferrous lactate, ferrous oxide, ferrous acetate, basic carbonate are ferrous, ethylenediamine tetra-acetic acid is ferrous, ferrous nitrate, bifluoride are ferrous, one or more mixing of ferrous phosphate.
6. described preparation method according to claim 1, 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, silicon dioxide, silafluofene, fluorosioloxane rubber, ammonium fluosilicate, silica gel, the crosslinked with silicane polypropylene, silicone oil, methyl phenyl silicone rubber, methyl triethoxysilane, methyl vinyl silicone rubber, polysiloxanes, silicon nitrile rubber, silicochloroform, chlorotriethyl silane, silicon tetrafluoride, silicon tetrachloride, silicon monoxide, one ethyl trichlorosilane, ethyl dichlorosilane, 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, in the tetramethoxy-silicane any or several mixing.
7. described preparation method according to claim 1, it is characterized in that, described bimodulus plate directed agents is any or several mixing of polyvinyl alcohol-gluconic acid sodium salt, polyethylene glycol-gluconic acid sodium salt, polyethylene glycol oxide-ethylenediamine tetra-acetic acid, kayexalate-ethylenediamine tetra-acetic acid, polyoxyethylene nonylplenyl ether-cetyl trimethyl kelene, softex kw-OTAC, Cetyltrimethylammonium bromide-Qu Latong S-100.
8. described preparation method according to claim 1, it is characterized in that, described carbon source 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 more any molar mixture in the benzene naphthalene grace terpolymer.
9. preparation method according to claim 1 is characterized in that, described carbon source is the organic compound that can be decomposed into conductive carbon class material after the pyrolysis.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104009226A (en) * | 2014-05-13 | 2014-08-27 | 昆明理工大学 | Method for synthesis of lithium iron silicate/graphene composite positive electrode material |
| CN104538623A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Preparation method for sphere-like lithium nickel manganese oxide positive electrode material |
| CN105406037A (en) * | 2015-11-02 | 2016-03-16 | 国家纳米科学中心 | Porous lithium iron silicate and preparation method and application thereof |
| CN105428624A (en) * | 2015-12-08 | 2016-03-23 | 山东精工电子科技有限公司 | Method for preparing lithium ferrous silicate/carbon composite cathode material by alcohol-assisted hydrothermal method |
| CN106229512A (en) * | 2016-08-12 | 2016-12-14 | 中南大学 | A kind of battery preparation method of 3-D ordered multiporous silicate/C composite |
| CN106848282A (en) * | 2017-01-26 | 2017-06-13 | 彭宪利 | A kind of negative electrode material for nonaqueous electrode secondary battery and its preparation method and application |
| CN110610813A (en) * | 2018-06-15 | 2019-12-24 | 天津大学 | Application of nickel silicate hydroxide/carbon nano tube flexible composite film material in super capacitor |
| CN110610819A (en) * | 2018-06-15 | 2019-12-24 | 天津大学 | Ferrosilicate hydroxide/carbon nanotube flexible composite film material and preparation method and application thereof |
| CN110610815A (en) * | 2018-06-15 | 2019-12-24 | 天津大学 | Cobalt silicate hydroxide/carbon nano tube flexible composite film material and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104009226A (en) * | 2014-05-13 | 2014-08-27 | 昆明理工大学 | Method for synthesis of lithium iron silicate/graphene composite positive electrode material |
| CN104538623A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Preparation method for sphere-like lithium nickel manganese oxide positive electrode material |
| CN105406037A (en) * | 2015-11-02 | 2016-03-16 | 国家纳米科学中心 | Porous lithium iron silicate and preparation method and application thereof |
| CN105428624A (en) * | 2015-12-08 | 2016-03-23 | 山东精工电子科技有限公司 | Method for preparing lithium ferrous silicate/carbon composite cathode material by alcohol-assisted hydrothermal method |
| CN106229512A (en) * | 2016-08-12 | 2016-12-14 | 中南大学 | A kind of battery preparation method of 3-D ordered multiporous silicate/C composite |
| CN106848282A (en) * | 2017-01-26 | 2017-06-13 | 彭宪利 | A kind of negative electrode material for nonaqueous electrode secondary battery and its preparation method and application |
| CN106848282B (en) * | 2017-01-26 | 2022-05-17 | 彭宪利 | Negative electrode material for non-aqueous electrolyte secondary battery and preparation method and application thereof |
| CN110610813A (en) * | 2018-06-15 | 2019-12-24 | 天津大学 | Application of nickel silicate hydroxide/carbon nano tube flexible composite film material in super capacitor |
| CN110610819A (en) * | 2018-06-15 | 2019-12-24 | 天津大学 | Ferrosilicate hydroxide/carbon nanotube flexible composite film material and preparation method and application thereof |
| CN110610815A (en) * | 2018-06-15 | 2019-12-24 | 天津大学 | Cobalt silicate hydroxide/carbon nano tube flexible composite film material and preparation method and application thereof |
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