CN101734675A - Preparation method of Li2FeSiO4 cathode material used for controlling Fe3P - Google Patents
Preparation method of Li2FeSiO4 cathode material used for controlling Fe3P Download PDFInfo
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Abstract
The invention relates to a preparation method of Li2FeSiO4 cathode material used for controlling Fe3P. The technical scheme comprises the following steps: weighting lithium salt or hydrate of lithium salt, ferrous salt or hydrate of ferrous salt, silicon compound and phosphorous acid or aqueous solution of phosphorous acid according to a molar ratio of the reactants that Li<+>:Fe<2+>:Si:H3PO3=0.95-1.10:0.95-1.10:0.70-0.999:0.001-0.429, mixing the reactants, then adding carbon-containing compound which accounts for 1wt%-20wt% of anhydrous reactants and wet grinding medium which accounts for 0.10-10 times of anhydrous reactants by volume, mixing with a ball mill, heating with water bath, mixing with a ball mill again, heating and drying in vacuum, and then using the two-stage sintering process or temperature programmed two-stage sintering process to prepare Li2FeSiO4 with controllable Fe3P under inert atmosphere or weak reduction atmosphere. The material prepared by the method of the invention has better discharge performance, the discharge capacity is significantly increased in 2.9V zone and the cycle performance is good under 0.3C current.
Description
Technical field
The invention belongs to the technical field of lithium ion battery electrode material, relate to a kind of preparation method who can be used for the ferrous silicate lithium anode material of lithium ion battery, lithium cell, polymer Li-ion battery and ultracapacitor.
Technical background
Lithium ion battery is widely used in mobile communication, notebook computer, portable power tool, also is the first-selected power supply of electromobile.The principal element that influences lithium ion battery performance and price ratio is its positive electrode material.Since [patent US 6085015] such as Armand in 2000 have applied for [Nyten A such as the preparation patent of ferrosilicon silicate of lithium and Nyt é n, et al., Electrochem.Commun., 2005,7 (2): 156-160.] since the report ferrosilicon silicate of lithium orthohormbic structure, the research of ferrosilicon silicate of lithium has caused attention.Ferrous silicate lithium anode material have the preparation raw material sources extensively, advantage such as less, the Stability Analysis of Structures of asepsis environment-protecting, electron energy band width.Work as Li
2FeSiO
4When 1 electronics was provided, its theoretical capacity was 166mAh/g, and discharge platform is positioned at about the 3.1V district.Work as Li
2FeSiO
4When the 2nd electronics was provided, corresponding discharge voltage plateau was the 4.8V district.The deficiency of ferrosilicon silicate of lithium mainly is that its electronic conductivity is not high, and the lithium ion rate of diffusion is slower, will discharge and recharge under C/30 to C/16 multiplying power electric current mostly, and this becomes one barrier of this material practicability.At present the ferrosilicon silicate of lithium main methods of modification is comprised that carbon coats methods such as processing and doping vario-property.
The method for preparing ferrosilicon silicate of lithium comprises solid sintering technology, sol-gel method, hydrothermal synthesis method etc.
From solid sintering technology, Armand etc. [patent US 6085015] are at FeO and the Li of 800 ℃ of sintering through ball milling
2SiO
3Mixture has prepared Li
2FeSiO
4Nyten etc. [Nyten A, et al., Electrochem.Commun., 2005,7 (2): 156-160.] are with FeC
2O
42H
2O, Li
2SiO
3Mix with carbon gel ball milling, at CO/CO
2Atmosphere in prepare Li
2FeSiO
4Material.Zaghib etc. [Zaghib K et al., J.PowerSources, 2006,160 (2): 1381-1386.] are also with FeC
2O
42H
2O and Li
2SiO
3Ball milling has prepared Li at 800 ℃ of following sintering
2FeSiO
4Xiang Kaixiong etc. [Xiang Kaixiong etc., functional materials, 2008,9 (39): 1455-1457.] are with CH
3COOLi, FeC
2O
42H
2O, Si (OC
2H
5)
4Prepared Li with the ball milling mixture solid state sintering of cement
2FeSiO
4/ C composite sample.
From sol-gel method; [Dominko R such as Dominko; Electrochem.Commun.; 2006,8 (2): 217-222.] ironic citrate and iron nitrate are mixed, under protective atmosphere, prepare colloidal sol earlier; then; the mixture that adds lithium hydroxide and silicon-dioxide again prepares xerogel through hydrothermal treatment consists, and last sintering prepares product.
Because the Li of above method preparation
2FeSiO
4Still relatively poor, attempt to adopt adulterating method further to improve the chemical property of ferrosilicon silicate of lithium in recent years than the discharge performance under the low range.Li etc. [Li L.M.et al., J.Power Sources, 2009] adopt wet method-high temperature solid-phase sintering bonded method to synthesize LiFe
1-xNi
xSiO
4/ C (x=0,0.1,0.3) positive electrode material.Yang Yongs etc. [patent CN200610005329.2] mix lithium salts, manganese salt, ferrous salt and positive silicon ester in water-ethanol system, the oven dry of heating back makes the mixing presoma, sneak into sugar after, sintering processes has prepared Li under nitrogen atmosphere
2Mn
xFe
1-xSiO
4/ C matrix material.They find to work as Li
2Mn
xFe
1-xSiO
4When the x value dropped in 0 to 0.5 scope among the/C, the loading capacity first of sample raise along with the increase of mixing the manganese amount.Gong just very adopts sol-gel method and hydro-thermal assisting sol gel method to prepare Li
2Mn
xFe
1-xSiO
4/ C sample [Chinese doctorate paper full-text database, 2007].
Summary of the invention
In order to improve the chemical property of ferrosilicon silicate of lithium, the present invention adopts the phosphorous acid preparation to contain the ferrosilicon silicate of lithium of controlled iron phosphide, and the technical scheme that is adopted is:
(1) according to lithium ion in the reactant: ferrous ion: Siliciumatom: the mol ratio of phosphorous acid=0.95～1.10: 0.95～1.10: 0.70～0.999:: 0.001～0.429 weighing lithium salts or lithium salts hydrate, ferrous salt or ferrous salt hydrate, silicon compound, phosphorous acid or phosphorous acid aqueous solution.Mix above reactant and obtain initial reaction mixture.
(2) according to 1%～20% weighing carbon compound of the total weight of the anhydrous state compound of initial reaction mixture in (1), measure wet grinding media according to 0.10 times～10 times volumes of the total volume of the anhydrous state compound of initial reaction mixture in (1) again; The carbon compound of weighing, the wet grinding media of measuring are mixed with initial reaction mixture in (1), use the rotating speed ball milling of 100rpm～1000rpm to mix 10 minutes～4 hours; Then in 40 ℃～90 ℃ water-bath, heated 1 hour～10 hours; Rotating speed ball milling with 100rpm clock～1000rpm mixed 3 hours～12 hours again; Dry in the vacuum of 10Pa～10132Pa pressure under 50 ℃～120 ℃, obtain the exsiccant powder at last.
(3) exsiccant powder in (2) is placed inert atmosphere or weakly reducing atmosphere, adopt the preparation of double sintering method or temperature programming double sintering method to contain the ferrosilicon silicate of lithium of controlled iron phosphide.
Described double sintering method is under arbitrary temperature of 200 ℃～500 ℃ of temperature ranges, with exsiccant powder presintering 3 hours～12 hours, is cooled to room temperature and makes the pre-imitation frosted glass of parent.0.10 times～10 times wet grinding media that volume is measured of the total volume of the anhydrous state compound of adding initial reaction mixture in the pre-imitation frosted glass of parent, with the rotating speed ball milling of 100rpm～1000rpm 3 hours～12 hours, dry in the vacuum of 10Pa～10132Pa pressure at 50 ℃～120 ℃.The exsiccant powder places inert atmosphere or weakly reducing atmosphere, and arbitrary sintering temperature of 550 ℃～850 ℃ of temperature ranges 3 hours～24 hours, preparation contained the ferrosilicon silicate of lithium of controlled iron phosphide.
Described temperature programming double sintering method is the heating rate according to 0.5 ℃/min～30 ℃/min, the exsiccant powder is heated to arbitrary temperature of 200 ℃～550 ℃ of temperature ranges by room temperature, insulation presintering 3 hours～12 hours is cooled to room temperature and makes the pre-imitation frosted glass of parent.0.10 times～10 times wet grinding media that volume is measured of the total volume of the anhydrous state compound of adding initial reaction mixture in the pre-imitation frosted glass of parent, with the rotating speed ball milling of 100rpm～1000rpm 3 hours～12 hours, dry in the vacuum of 10Pa～10132Pa pressure under 50 ℃～120 ℃.The exsiccant powder places inert atmosphere or weakly reducing atmosphere, be heated to arbitrary temperature of 600 ℃～850 ℃ of temperature ranges by room temperature according to 0.5 ℃/min～30 ℃/heating rate of min, heat preservation sintering 3 hours～24 hours, preparation contains the ferrosilicon silicate of lithium of controlled iron phosphide.
Described silicon compound is positive tetraethyl orthosilicate, positive quanmethyl silicate, silicon-dioxide, nano silicon, silicic acid, metasilicic acid, four (1-methylethyl) silicon ester, tetrabutyl ethylene glycol silicon ester, hexamethyldisilazane, heptamethyldisilazane, triethyl-silicane or chlorotriethyl silane.
Described lithium salts or lithium salts hydrate are Li
2CO
3XH
2O, LiOHxH
2O, LiClxH
2O, Li
2C
2O
4XH
2O, Li
2O, LiCOOCH
3XH
2O, LiNO
3XH
2O, Li
2SO
4XH
2O or LiH
2PO
4XH
2O, wherein, 0≤x≤2.
Described ferrous salt or ferrous hydrate are FeC
2O
4YH
2O, Fe (COOCH
3)
2YH
2O, FeCl
2YH
2O, FeSO
4YH
2O, Fe (OH)
2YH
2O, FeCO
3Or FeO, wherein, 0≤y≤7.
Described phosphorous acid aqueous solution is the solution of phosphorous acid and water arbitrary proportion.
Described carbon compound is polypropylene, polyacrylamide, polyvinyl alcohol, glucose, sucrose, flour, tapioca flour, potato powder, Semen Maydis powder, taro meal, rice meal, carbon dust, bran powder, Graphite Powder 99 or acetylene black.
Described inert atmosphere and weakly reducing atmosphere are nitrogen, argon gas, carbon monoxide or carbonic acid gas, or the gas mixture of the gas mixture of gas mixture, carbonic acid gas and the argon gas of gas mixture, carbonic acid gas and the nitrogen of gas mixture, carbon monoxide and the argon gas of gas mixture, carbon monoxide and the nitrogen of gas mixture, carbon monoxide and the carbonic acid gas of gas mixture, hydrogen and the argon gas of the hydrogen of arbitrary volume ratio and nitrogen or nitrogen and argon gas.
Described wet grinding media is deionized water, distilled water, methyl alcohol, ethanol, formaldehyde, acetaldehyde or propyl alcohol, or volume ratio the deionized water of 1: 0.10～100 scopes respectively with the mixed solution of distilled water, methyl alcohol, ethanol, acetone, formaldehyde, acetaldehyde or propyl alcohol.
Compare with other inventive method, raw materials cost of the present invention is lower, and raw material sources are extensive, and preparation process is simple.This electrode materials has discharge performance preferably, and the discharge platform voltage of the sample of preparation raises, discharge platform prolongs, and cycle performance is good, for industrialization is laid a good foundation.
Embodiment
Below in conjunction with embodiment the present invention is further detailed.Embodiment further replenishes and explanation of the present invention, rather than the restriction to inventing.
Embodiment 1
According to lithium ion in the reactant: ferrous ion: Siliciumatom: the mol ratio of phosphorous acid=0.95: 0.95: 0.999: 0.001 takes by weighing Carbon Dioxide lithium (Li
2CO
3) 35.1 the gram, Ferrox (FeC
2O
42H
2O) 170.5 grams, positive tetraethyl orthosilicate (C
8H
12O
8Si) 264 grams, phosphorous acid (H
3PO
3) 0.082 gram.Add polypropylene 4.35 grams, add deionized water 5600ml again, use the rotating speed ball milling of 100rpm to mix 10 minutes, heating is 10 hours in 40 ℃ of water-baths, and the rotating speed ball milling with 100rpm mixed 3 hours again, drying in the vacuum of 50 ℃ of temperature, pressure 10Pa.The exsiccant powder places nitrogen atmosphere, 200 ℃ of following presintering 3 hours, makes the pre-imitation frosted glass of parent.The mixed solution 55ml (mixed volume was than 1: 0.10) of deionized water that in the pre-imitation frosted glass of parent, adds and methyl alcohol, the rotating speed ball milling of usefulness 100rpm 3 hours, dry in the vacuum of 50 ℃ of temperature, pressure 200Pa.The exsiccant powder places nitrogen atmosphere, and 550 ℃ of sintering 3 hours, preparation contained the ferrosilicon silicate of lithium of controlled iron phosphide.The loading capacity of this electrode materials is higher than 110mAh/g, and the loading capacity in the 2.9V district obviously increases, discharge platform prolongs, and cycle performance is good under 0.3C multiplying power electric current, for industrialization is laid a good foundation.
Embodiment 2
According to lithium ion in the reactant: ferrous ion: Siliciumatom: the mol ratio of phosphorous acid=1.10: 1.10: 0.70: 0.30 takes by weighing lithium hydroxide (LiOHH
2O) 46.2 grams, ferrous sulfate (FeSO
47H
2O) 305.8 grams, metasilicic acid (H
2SiO
3) 54.7 grams, 0.1% phosphorous acid (H
3PO
3) 246000 grams.Add polyvinyl alcohol 54.5 grams, add deionized water and alcoholic acid mixed solution 4080ml (mixed volume was than 1: 100) again, rotating speed ball milling with 1000rpm mixed 4 hours, heating is 3 hours in 90 ℃ of water-baths, rotating speed ball milling with 800rpm mixed 12 hours again, and is dry in the vacuum of 120 ℃ of temperature, pressure 10132Pa.The exsiccant powder places carbon monoxide atmosphere, 500 ℃ of presintering 12 hours, is cooled to room temperature and makes the pre-imitation frosted glass of parent.In the pre-imitation frosted glass of parent, add deionized water and alcoholic acid mixed solution 4206ml (mixed volume was than 1: 0.50), the rotating speed ball milling of usefulness 900rpm 12 hours, dry in the vacuum of 120 ℃ of temperature, pressure 10132Pa.The exsiccant powder places carbon monoxide atmosphere, and 850 ℃ of sintering processes 24 hours, preparation contained the ferrosilicon silicate of lithium of controlled iron phosphide.The loading capacity of this electrode materials is higher than 100mAh/g, and the sample of preparation obviously increases in the loading capacity in 2.9V district, discharge platform prolongs, and cycle performance is good under 0.3C multiplying power electric current, for industrialization is laid a good foundation.
Embodiment 3
According to lithium ion in the reactant: ferrous ion: Siliciumatom: the mol ratio of phosphorous acid=0.95: 1.10: 0.80: 0.20 takes by weighing two hydration Lithium Acetate (CH
3COOLi2H
2O) 96.9 grams, Iron dichloride tetrahydrate (FeCl
24H
2O) 218.8 grams, nano silicon (SiO
2) 48.1 the gram, 90% phosphorous acid (H
3PO
3) 18.2 grams.Add glucose 26.6 grams, add the mixed solution 3769mL (mixed volume was than 1: 10) of deionized water and acetone again, use the rotating speed ball milling of 200rpm to mix 4 hours, heating is 4 hours in 60 ℃ of water-baths.Rotating speed ball milling with 500rpm mixed 10 hours again, and is dry in the vacuum of 100 ℃ of temperature, pressure 100Pa.The exsiccant powder places the atmosphere of the gas mixture (volume ratio was at 1: 100) of hydrogen and nitrogen, 400 ℃ of presintering 10 hours, is cooled to room temperature and makes the pre-imitation frosted glass of parent.The mixed solution 2090ml (mixed volume was than 1: 1) that in the pre-imitation frosted glass of parent, adds deionized water and acetone, the rotating speed ball milling of usefulness 500rpm 10 hours, dry under the vacuum of 100 ℃ of temperature, pressure 700Pa.The exsiccant powder places the atmosphere of the gas mixture (volume ratio was at 1: 20) of hydrogen and nitrogen, and 750 ℃ of sintering 24 hours, preparation contained the ferrosilicon silicate of lithium of controlled iron phosphide.The loading capacity of this electrode materials is higher than 100mAh/g, and the sample of preparation obviously increases in the loading capacity in 2.9V district, discharge platform prolongs, and cycle performance is good under 0.3C multiplying power electric current, for industrialization is laid a good foundation.
Embodiment 4
According to lithium ion in the reactant: ferrous ion: Siliciumatom: the mol ratio of phosphorous acid=1.10: 0.95: 0.9: 0.143 takes by weighing anhydrous nitric acid lithium (LiNO
3) 75.8 the gram, five ferrous sulfate hydrate (FeSO
45H
2O) 229.9 grams, heptamethyldisilazane (CH
3) SiN (CH
3) Si (CH
3)
3) 158 the gram, 60% phosphorous acid (H
3PO
3) 19.5 grams.Add taro meal 58 grams, add the mixed solution 640ml (volume ratio was at 1: 1) of deionized water and formaldehyde again, use the rotating speed ball milling of 800rpm to mix 1 hour.Then, in 60 ℃ of water-baths, heated 2 hours.Rotating speed ball milling with 100rpm mixed 5 hours again, and is dry in the vacuum of 50 ℃ of temperature, pressure 10Pa.The exsiccant powder places carbon dioxide atmosphere, is heated to 200 ℃ according to the heating rate of 0.5 ℃/min by room temperature, and insulation presintering 3 hours is cooled to room temperature and makes the pre-imitation frosted glass of parent.In the pre-imitation frosted glass of parent, add acetaldehyde 3200ml, the rotating speed ball milling of usefulness 300rpm 3 hours, dry in the vacuum of 50 ℃ of temperature, pressure 1000Pa.The exsiccant powder is placed in the carbon monoxide atmosphere, is heated to 650 ℃ according to the heating rate of 10 ℃/min by room temperature, heat preservation sintering 10 hours, and preparation contains the ferrosilicon silicate of lithium of controlled iron phosphide.The loading capacity of this electrode materials is higher than 90mAh/g, and the sample of preparation obviously increases in the loading capacity in 2.9V district, discharge platform prolongs, and cycle performance is good under 0.3C multiplying power electric current, for industrialization is laid a good foundation.
Embodiment 5
According to lithium ion in the reactant: ferrous ion: Siliciumatom: the mol ratio of phosphorous acid=1.0: 1.0: 0.90: 0.143 takes by weighing anhydrous lithium acetate (CH
3COOLi) 66 grams, the ferrous (FeCO of Carbon Dioxide
3) 115.9 the gram, chlorotriethyl silane (C
6H
15ClSi) phosphorous acid (H of 135.6 grams, weight concentration 80%
3PO
3) 14.7 grams.Add Graphite Powder 99 69 grams, the mixed solution 564ml (mixed volume was than 1: 0.1) that adds deionized water and propyl alcohol again, mixed 10 minutes with 500rpm rotating speed ball milling, heating is 1 hour in 90 ℃ of water-baths, rotating speed ball milling with 800rpm mixed 3 hours again, and is dry in the vacuum of 50 ℃ of temperature, pressure 10Pa.The exsiccant powder places nitrogen atmosphere, is heated to 550 ℃ according to the heating rate of 0.5 ℃/min by room temperature, and insulation presintering 12 hours is cooled to room temperature and makes the pre-imitation frosted glass of parent.In the pre-imitation frosted glass of parent, add ethanol 1692ml, the rotating speed ball milling of usefulness 1000rpm 3 hours, dry in the vacuum of 120 ℃ of temperature, pressure 10132Pa.The exsiccant powder places argon gas atmosphere, is heated to 750 ℃ according to the heating rate of 30 ℃/min by room temperature, heat preservation sintering 24 hours, and preparation contains the ferrosilicon silicate of lithium of controlled iron phosphide.The loading capacity of this electrode materials is higher than 130mAh/g, and the sample of preparation obviously increases in the loading capacity in 2.9V district, discharge platform prolongs, and cycle performance is good under 0.3C multiplying power electric current, for industrialization is laid a good foundation.
Claims (10)
1. preparation method who controls the ferrous silicate lithium anode material of iron phosphide is characterized in that preparation process is made up of following steps:
(1) according to lithium ion in the reactant: ferrous ion: Siliciumatom: the mol ratio of phosphorous acid=0.95～1.10: 0.95～1.10: 0.70～0.999: 0.001～0.429 weighing lithium salts or lithium salts hydrate, ferrous salt or ferrous salt hydrate, silicon compound, phosphorous acid or phosphorous acid aqueous solution; Mix above reactant and obtain initial reaction mixture;
(2) according to 1%～20% weighing carbon compound of the total weight of the anhydrous state compound of initial reaction mixture in (1), measure wet grinding media according to 0.10 times～10 times volumes of the total volume of the anhydrous state compound of initial reaction mixture in (1) again; The carbon compound of weighing, the wet grinding media of measuring are mixed with initial reaction mixture in (1), use the rotating speed ball milling of 100rpm～1000rpm to mix 10 minutes～4 hours; Then in 40 ℃～90 ℃ water-bath, heated 1 hour～10 hours; Rotating speed ball milling with 100rpm～1000rpm mixed 3 hours～12 hours again; Dry in the vacuum of 10Pa～10132Pa pressure under 50 ℃～120 ℃, obtain the exsiccant powder at last;
(3) exsiccant powder in (2) is placed inert atmosphere or weakly reducing atmosphere, adopt the preparation of double sintering method or temperature programming double sintering method to contain the ferrosilicon silicate of lithium of controlled iron phosphide.
2. a kind of preparation method who controls the ferrous silicate lithium anode material of iron phosphide according to claim 1, it is characterized in that described double sintering method is under arbitrary temperature of 200 ℃～500 ℃ of temperature ranges, presintering 3 hours～12 hours is cooled to room temperature and makes the pre-imitation frosted glass of parent; 0.10 times～10 times wet grinding media that volume is measured of the total volume of the anhydrous state compound of adding initial reaction mixture in the pre-imitation frosted glass of parent, with the rotating speed ball milling of 100rpm～1000rpm 3 hours～12 hours, dry in the vacuum of 10Pa～10132Pa pressure under 50 ℃～120 ℃; The exsiccant powder places inert atmosphere or weakly reducing atmosphere, and arbitrary sintering temperature of 550 ℃～850 ℃ of temperature ranges 3 hours～24 hours, preparation contained the ferrosilicon silicate of lithium of controlled iron phosphide.
3. a kind of preparation method who controls the ferrous silicate lithium anode material of iron phosphide according to claim 1, it is characterized in that described temperature programming double sintering method is the exsiccant powder to be heated to arbitrary temperature of 200 ℃～550 ℃ of temperature ranges by room temperature according to 0.5 ℃/min～30 ℃/heating rate of min, insulation presintering 3 hours～12 hours is cooled to room temperature and makes the pre-imitation frosted glass of parent; 0.10 times～10 times wet grinding media that volume is measured of the total volume of the anhydrous state compound of adding initial reaction mixture in the pre-imitation frosted glass of parent, with the rotating speed ball milling of 100rpm～1000rpm 3 hours～12 hours, dry in the vacuum of 10Pa～10132Pa pressure under 50 ℃～120 ℃; The exsiccant powder places inert atmosphere or weakly reducing atmosphere, be heated to arbitrary temperature of 600 ℃～850 ℃ of temperature ranges by room temperature according to 0.5 ℃/min～30 ℃/heating rate of min, heat preservation sintering 3 hours～24 hours, preparation contains the ferrosilicon silicate of lithium of controlled iron phosphide.
4. a kind of preparation method who controls the ferrous silicate lithium anode material of iron phosphide according to claim 1, the compound that it is characterized in that described silicon is positive tetraethyl orthosilicate, positive quanmethyl silicate, silicon-dioxide, nano silicon, silicic acid, metasilicic acid, four (1-methylethyl) silicon ester, tetrabutyl ethylene glycol silicon ester, hexamethyldisilazane, heptamethyldisilazane, triethyl-silicane or chlorotriethyl silane.
5. a kind of preparation method who controls the ferrous silicate lithium anode material of iron phosphide according to claim 1 is characterized in that described lithium salts or lithium salts hydrate are Li
2CO
3XH
2O, LiOHxH
2O, LiClxH
2O, Li
2C
2O
4XH
2O, LiCOOCH
3XH
2O, LiNO
3XH
2O, Li
2SO
4XH
2O or LiH
2PO
4XH
2O, wherein, 0≤x≤2.
6. a kind of preparation method who controls the ferrous silicate lithium anode material of iron phosphide according to claim 1 is characterized in that described ferrous salt or ferrous hydrate are FeC
2O
4YH
2O, Fe (COOCH
3)
2YH
2O, FeCl
2YH
2O, FeSO
4YH
2O, Fe (OH)
2YH
2O, FeCO
3Or FeO, wherein, 0≤y≤7.
7. a kind of preparation method who controls the ferrous silicate lithium anode material of iron phosphide according to claim 1 is characterized in that described phosphorous acid aqueous solution is the solution of the arbitrary proportion of phosphorous acid and water.
8. a kind of preparation method who controls the ferrous silicate lithium anode material of iron phosphide according to claim 1 is characterized in that described carbon compound is polypropylene, polyacrylamide, polyvinyl alcohol, glucose, sucrose, flour, tapioca flour, potato powder, Semen Maydis powder, taro meal, rice meal, carbon dust, bran powder, Graphite Powder 99 or acetylene black.
9. a kind of preparation method who controls the ferrous silicate lithium anode material of iron phosphide according to claim 1, it is characterized in that described inert atmosphere and weakly reducing atmosphere are nitrogen, argon gas, carbon monoxide or carbonic acid gas, or the gas mixture of the gas mixture of gas mixture, carbonic acid gas and the argon gas of gas mixture, carbonic acid gas and the nitrogen of gas mixture, carbon monoxide and the argon gas of gas mixture, carbon monoxide and the nitrogen of gas mixture, carbon monoxide and the carbonic acid gas of gas mixture, hydrogen and the argon gas of the hydrogen of arbitrary volume ratio and nitrogen or nitrogen and argon gas.
10. a kind of preparation method who controls the ferrous silicate lithium anode material of iron phosphide according to claim 1, it is characterized in that described wet grinding media is deionized water, distilled water, methyl alcohol, ethanol, formaldehyde, acetaldehyde or propyl alcohol, or volume ratio is at the deionized water of 1: 0.10～100 scopes and the mixed solution of distilled water, methyl alcohol, ethanol, acetone, formaldehyde, acetaldehyde or propyl alcohol.
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| US9406927B1 (en) * | 2016-02-04 | 2016-08-02 | StoreDot Ltd. | Method of preparing an anode for a Li-ion battery |
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Family Cites Families (3)
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|---|---|---|---|---|
| US6085015A (en) * | 1997-03-25 | 2000-07-04 | Hydro-Quebec | Lithium insertion electrode materials based on orthosilicate derivatives |
| CN101546828B (en) * | 2008-12-27 | 2010-11-03 | 深圳市德方纳米科技有限公司 | Nanometer ferrous silicate lithium material and preparation method thereof |
| CN101540394B (en) * | 2009-04-09 | 2010-12-29 | 西安建筑科技大学 | Method for preparing lithium ferrosilicon silicate of lithium-ion battery cathode material |
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2009
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