CN102013483A - Preparation method for ferrous silicate lithium cathode material simultaneously doped with fluorine and zirconium - Google Patents
Preparation method for ferrous silicate lithium cathode material simultaneously doped with fluorine and zirconium Download PDFInfo
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- CN102013483A CN102013483A CN2010105078288A CN201010507828A CN102013483A CN 102013483 A CN102013483 A CN 102013483A CN 2010105078288 A CN2010105078288 A CN 2010105078288A CN 201010507828 A CN201010507828 A CN 201010507828A CN 102013483 A CN102013483 A CN 102013483A
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Abstract
The invention relates to a preparation method for a ferrous silicate lithium cathode material simultaneously doped with fluorine and zirconium, which is characterized by comprising the following steps of: weighing a lithium compound, a ferrous compound, a zirconium compound, a silicon compound and a fluorine compound as reactants in accordance with the molar ratio of lithium ion to ferrous ion to zirconium ion to silicon ion to fluorine ion being (1.90-2.05): (1-y): x: (1-z): k; weighing a carbon-containing compound or carbon powder based on 1-30 percent of total mass of the reactants; mixing the silicon compound with hot water, adding the lithium compound, then mixing all other reactants and the carbon-containing compound or the carbon powder, carrying out ball mill mixture process and vacuum drying to prepare dry powder; and placing the dry powder in an inert atmosphere or a weakly reducing atmosphere, and then preparing ferrous silicate lithium through the two-stage sintering process. The cycle performance of the prepared material is excellent in the 1C-rate current, and a good foundation can be built for industrialization.
Description
Technical field
The invention belongs to the technical field of lithium ion battery electrode material, relate to a kind of mix fluorine simultaneously and mix zirconium, can be used for lithium ion battery, the preparation method of the ferrous silicate lithium anode material of lithium 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 electric automobile.The principal element that influences lithium ion battery performance and price ratio is the performance of its positive electrode.Since 2000, the preparation patent that Armand etc. [patent US 6085015] have applied for ferrosilicon silicate of lithium, [Nyten A such as Nyt é n, et al., Electrochem.Commun., 2005,7 (2): 156-160.] reported the orthohormbic structure of ferrosilicon silicate of lithium, the research of ferrosilicon silicate of lithium has caused attention.Ferrous silicate lithium anode material has advantages such as raw material sources are extensive, asepsis environment-protecting, Stability Analysis of Structures.The deficiency of ferrosilicon silicate of lithium mainly is that electronic conductivity is low, and the lithium ion diffusion rate is slow, will discharge and recharge under very little electric current mostly, becomes one barrier of this material practicability.The ferrosilicon silicate of lithium main methods of modification comprises that carbon coats processing and doping vario-property etc. at present.Specifically can be divided into solid sintering technology, sol-gel process, hydrothermal synthesis method etc.
From solid sintering technology, Armand etc. [patent US 6085015] are in 800 ℃ of sintering FeO and Li
2SiO
3Mixture, 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.Power Sources, 2006,160 (2): 1381-1386.] are with FeC
2O
42H
2O and Li
2SiO
3Ball milling mixes, and has prepared Li at 800 ℃ of sintering
2FeSiO
4Xiang Kaixiong etc. [Xiang Kaixiong etc., functional material, 2008,9 (39): 1455-1457.] are with CH
3COOLi, FeC
2O
42H
2O, Si (OC
2H
5)
4Mixture solid-phase sintering with cement has prepared Li
2FeSiO
4/ C composite sample.Hu Guorong [Acta PhySico-Chimica Sinica, 2009,25 (5): 1004-1008] is with Li
2SiO
3, FeC
2O
42H
2O, nanometer SiO
2Prepare with microwave heating treatment with the mixture of glucose.
From sol-gel process; [Dominko R such as Dominko; Electrochem.Commun.; 2006,8 (2): 217-222.] ironic citrate and ferric 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 obtains preparing product.
Because the Li of above method preparation
2FeSiO
4Still relatively poor than the discharge performance under the low range, many in recent years researchers attempt to adopt doping method further to improve the chemical property of ferrosilicon silicate of lithium.The method that Li etc. [Li L.M.et al., J.Power Sources, 2009] adopt wet method-high temperature solid-phase sintering to combine has been synthesized LiFe
1-xNi
xSiO
4/ C (x=0,0.1,0.3) positive electrode.Yang Yongs etc. [patent CN200610005329.2] mix lithium salts, manganese salt, ferrous salt and positive esters of silicon acis in water-ethanol system, make the mixing presoma behind the heating, drying, sneak into sugar, and sintering has prepared Li under nitrogen atmosphere
2Mn
xFe
1-xSiO
4/ C composite material.They find to work as Li
2Mn
xFe
1-xSiO
4When x value scope was in 0 to 0.5 scope among the/C, the discharge capacity first of sample raise along with the increase of mixing the manganese amount.Gong just very adopts sol-gal process 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 hydrolysis-sintering process preparation to mix fluorine simultaneously and mix the ferrous silicate lithium anode material of zirconium, with the heavy-current discharge performance and the cycle performance that improve ferrous silicate lithium anode material, the technical scheme of employing is:
(1) reactant is according to lithium ion: ferrous ion: zirconium ion: silicon ion: the mol ratio of fluorine ion is (1.90～2.05): (1-y): x: (1-z): the compound of the compound of k weighing lithium, ferrous compound, zirconium, the compound of silicon, the compound of fluorine, according to 1%～30% weighing carbon compound or carbon dust of reactant quality summation; Wherein, x, y, z, k satisfy following relation simultaneously: 0.002≤y≤0.10,0.002≤z≤0.10,0.5y≤x≤y, z≤k≤3z;
The compound of silicon is mixed with the hot water of 50 ℃～98 ℃ of temperature, the compound that adds lithium, mix, sneak into other all reactants and carbon compound or carbon dust again, the consumption of described hot water is 0.10 times～10 times volumes of cumulative volume of the solid of reactant; Rotating speed ball milling with 100rpm～900rpm mixed 10 minutes～5 hours; The powder dry in the vacuum of 50 ℃～150 ℃ of temperature, pressure 10Pa～10132Pa, that preparation is dry places inert atmosphere or weakly reducing atmosphere with the powder of drying, adopts the double sintering legal system to be equipped with ferrosilicon silicate of lithium.
Described double sintering method is in inert atmosphere or weakly reducing atmosphere, the powder of drying is heated to arbitrary temperature of 200 ℃～500 ℃ of temperature ranges according to 0.5 ℃/min～30 ℃/rate of heat addition of min by room temperature, kept this temperature sintering 3 hours～12 hours, and then further be heated to arbitrary temperature of 550 ℃～850 ℃ of temperature ranges according to 0.5 ℃/min～30 ℃/rate of heat addition of min, keep this temperature sintering 3 hours～24 hours, and be prepared into ferrosilicon silicate of lithium.
The compound of described silicon is tetraethyl orthosilicate, quanmethyl silicate, silicic acid trimethyl, silicic acid dimethyl ester, silicon dioxide, silicic acid, metasilicic acid or four (1-Methylethyl) esters of silicon acis.
The compound of described lithium is lithium carbonate, lithia, lithium hydroxide, lithium chloride, lithium oxalate, lithium acetate, lithium nitrate, lithium sulfate or lithium dihydrogen phosphate.
Described ferrous compound is ferrous oxalate, ferrous acetate, frerrous chloride, ferrous sulfate, ferrous hydroxide, ferrous nitrate, ferrous citrate, ferrous carbonate or ferrous oxide.
The compound of described zirconium is zirconium dioxide, zirconium hydroxide, sodium zirconate, potassium fluorozirconate or zirconium sulfate.
The compound of described fluorine is lithium fluoride, sodium fluoride, potassium fluoride or ammonium fluoride.
Described carbon compound is polypropylene, polyacrylamide, polyvinyl alcohol, glucose, sucrose, flour, tapioca flour, dehydrated potato powder, corn flour, taro meal, rice meal or bran powder.
Described carbon dust is natural graphite powder, graphous graphite powder or acetylene black.
Described inert atmosphere and weakly reducing atmosphere are nitrogen, argon gas, carbon monoxide or carbon dioxide, or the gaseous mixture of gaseous mixture, carbon dioxide and the argon gas of gaseous mixture, carbon dioxide and the nitrogen of gaseous mixture, carbon monoxide and the argon gas of gaseous mixture, carbon monoxide and the nitrogen of gaseous mixture, carbon monoxide and the carbon dioxide of gaseous mixture, hydrogen and the argon gas of the hydrogen of arbitrary volume ratio and nitrogen, or the gaseous mixture of nitrogen and argon gas.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, and preparation technology is simple.The sample of preparation has discharge performance preferably, and the discharge capacity in the 3.0V district obviously increases, discharge platform prolongs, and cycle performance is good under 1C multiplying power electric current, for industrialization is laid a good foundation.
Embodiment
The present invention is further described below in conjunction with embodiment.Embodiment further replenishes and explanation of the present invention, rather than the restriction to inventing.
Embodiment 1
Reactant is according to lithium ion: ferrous ion: zirconium ion: silicon ion: the mol ratio of fluorine ion is 1.95: 0.998: 0.001: 0.998: 0.002 weighing lithium carbonate, ferrous oxalate, zirconium dioxide, tetraethyl orthosilicate, lithium fluoride, and according to 1% weighing polypropylene of reactant quality summation.
The hot water of 50 ℃ of tetraethyl orthosilicate and temperature is mixed, add lithium carbonate, mix, sneak into other all reactants and polypropylene again, the consumption of hot water is 0.10 times of cumulative volume of the solid of all reactants.Rotating speed ball milling with 100rpm mixed 10 minutes; Dry in the vacuum of 50 ℃ of temperature, pressure 10Pa, the powder that preparation is dry, the powder of drying is placed nitrogen atmosphere, the rate of heat addition according to 0.5 ℃/min is heated to 200 ℃ by room temperature, kept this temperature sintering 3 hours, the rate of heat addition according to 0.5 ℃/min further is heated to 550 ℃ then, keeps this temperature sintering 3 hours, the preparation ferrosilicon silicate of lithium.
Embodiment 2
Reactant is according to lithium ion: ferrous ion: zirconium ion: silicon ion: the mol ratio of fluorine ion is 2.05: 0.90: 0.10: 0.90: 0.10 weighing lithium hydroxide, ferrous acetate, zirconium hydroxide, quanmethyl silicate, sodium fluoride, and according to 30% weighing polyacrylamide of reactant quality summation.
The hot water of 98 ℃ of quanmethyl silicate and temperature is mixed, add lithium hydroxide, mix, sneak into other all reactants and polyacrylamide again, the consumption of described hot water is 10 times of volumes of the total solid capacity of all reactants, rotating speed ball milling with 900rpm mixed 5 hours, and is dry in the vacuum of 150 ℃ of temperature, pressure 10132Pa, prepares dry powder.The powder of drying is placed argon gas atmosphere, the rate of heat addition according to 30 ℃/min is heated to 500 ℃ by room temperature, keeps this temperature sintering 12 hours, and the rate of heat addition according to 30 ℃/min further is heated to 850 ℃ then, kept this temperature sintering 24 hours, the preparation ferrosilicon silicate of lithium.
Embodiment 3
Reactant is according to lithium ion: ferrous ion: zirconium ion: silicon ion: the mol ratio of fluorine ion is 1.0: 0.95: 0.025: 0.90: 0.10 weighing lithium oxalate, ferrous hydroxide, potassium fluorozirconate, nano silicon, ammonium fluoride, and according to 15% weighing flour of reactant quality summation.
The hot water of 80 ℃ of nano silicon and temperature is mixed, add lithium oxalate, mix, sneak into other all reactants and flour again, the consumption of described hot water is 5 times of volumes of the total solid capacity of all reactants, rotating speed ball milling with 600rpm mixed 3 hours, and is dry in the vacuum of 100 ℃ of temperature, pressure 1010Pa, prepares dry powder.The powder of drying is placed carbon monoxide atmosphere, the rate of heat addition according to 10 ℃/min is heated to 400 ℃ by room temperature, keeps this temperature sintering 8 hours, and the rate of heat addition according to 15 ℃/min further is heated to 750 ℃ then, kept this temperature sintering 24 hours, the preparation ferrosilicon silicate of lithium.
Embodiment 4
Reactant is according to lithium ion: ferrous ion: zirconium ion: silicon ion: the mol ratio of fluorine ion is 1.00: 0.90: 0.10: 0.90: 0.30 weighing lithium acetate, ferrous carbonate, sodium zirconate, silicic acid, lithium fluoride, and according to 10% weighing rice meal of reactant quality summation.
The compound of silicon is mixed with the hot water of 88 ℃ of temperature, add lithium acetate, mix, sneak into other all reactants and acetylene black again, the consumption of described hot water is 3 times of volumes of the total solid capacity of all reactants, rotating speed ball milling with 700rpm mixed 2 hours, 80 ℃ of temperature, dry in the vacuum of pressure 10132Pa, prepare dry powder, it is the atmosphere of 1: 10 gaseous mixture that the powder of drying is placed carbon monoxide and nitrogen volume ratio, the rate of heat addition according to 0.5 ℃/min is heated to 450 ℃ by room temperature, kept this temperature sintering 12 hours, the rate of heat addition according to 25 ℃/min further is heated to 650 ℃ then, keeps this temperature sintering 18 hours, the preparation ferrosilicon silicate of lithium.
Embodiment 5
Reactant is according to lithium ion: ferrous ion: zirconium ion: silicon ion: the mol ratio of fluorine ion is 2.05: 0.99: 0.005: 0.99: 0.03 weighing lithium nitrate, ferrous oxide, zirconium dioxide, metasilicic acid, ammonium fluoride, and according to 20% weighing tapioca flour of reactant quality summation.
The hot water of 78 ℃ of metasilicic acid and temperature is mixed, add lithium nitrate, mix, sneak into other all reactants and starch again, the consumption of described hot water is 5 times of volumes of the total solid capacity of all reactants.Rotating speed ball milling with 600rpm mixed 1 hour; Dry in the vacuum of 120 ℃ of temperature, pressure 10Pa, prepare dry powder.It is the atmosphere of 10: 1 gaseous mixture that the powder of drying is placed hydrogen and nitrogen volume ratio, the rate of heat addition according to 0.5 ℃/min is heated to 500 ℃ by room temperature, kept this temperature sintering 12 hours, the rate of heat addition according to 20 ℃/min further is heated to 850 ℃ then, kept this temperature sintering 24 hours, the preparation ferrosilicon silicate of lithium.
Claims (7)
1. mix fluorine and the preparation method that mixes the ferrous silicate lithium anode material of zirconium simultaneously for one kind, it is characterized in that preparation process is made up of following steps:
Reactant is according to lithium ion: ferrous ion: zirconium ion: silicon ion: the mol ratio of fluorine ion is (1.90～2.05): (1-y): x: (1-z): the compound of the compound of k weighing lithium, ferrous compound, zirconium, the compound of silicon, the compound of fluorine, according to 1%～30% weighing carbon compound or carbon dust of reactant quality summation; Wherein, x, y, z, k satisfy following relation simultaneously: 0.002≤y≤0.10,0.002≤z≤0.10,0.5y≤x≤y, z≤k≤3z; Described carbon compound is polypropylene, polyacrylamide, polyvinyl alcohol, glucose, sucrose, flour, tapioca flour, dehydrated potato powder, corn flour, taro meal, rice meal or bran powder;
The compound of silicon is mixed with the hot water of 50 ℃～98 ℃ of temperature, add the compound of lithium, mix, sneak into other all reactants and carbon compound or carbon dust again, the consumption of described hot water is 0.10 times～10 times volumes of the total solid capacity of reactant; Rotating speed ball milling with 100rpm～900rpm mixed 10 minutes～5 hours; Dry in the vacuum of 50 ℃～150 ℃ of temperature, pressure 10Pa～10132Pa, prepare dry powder, the powder of drying is placed inert atmosphere or weakly reducing atmosphere, adopt the double sintering legal system to be equipped with ferrosilicon silicate of lithium;
Described double sintering method is in inert atmosphere or weakly reducing atmosphere, the powder of drying is heated to arbitrary temperature of 200 ℃～500 ℃ of temperature ranges according to 0.5 ℃/min～30 ℃/rate of heat addition of min by room temperature, kept this temperature sintering 3 hours～12 hours, and then further be heated to arbitrary temperature of 550 ℃～850 ℃ of temperature ranges according to 0.5 ℃/min～30 ℃/rate of heat addition of min, keep this temperature sintering 3 hours～24 hours, and be prepared into ferrosilicon silicate of lithium.
2. a kind of preparation method who mixes fluorine simultaneously and mix the ferrous silicate lithium anode material of zirconium according to claim 1, the compound that it is characterized in that described silicon is tetraethyl orthosilicate, quanmethyl silicate, silicic acid trimethyl, silicic acid dimethyl ester, silicon dioxide, silicic acid, metasilicic acid or four (1-Methylethyl) esters of silicon acis.
3. a kind of preparation method who mixes fluorine simultaneously and mix the ferrous silicate lithium anode material of zirconium according to claim 1, the compound that it is characterized in that described lithium is lithium carbonate, lithia, lithium hydroxide, lithium chloride, lithium oxalate, lithium acetate, lithium nitrate, lithium sulfate or lithium dihydrogen phosphate.
4. a kind of preparation method who mixes fluorine simultaneously and mix the ferrous silicate lithium anode material of zirconium according to claim 1 is characterized in that described ferrous compound is ferrous oxalate, ferrous acetate, frerrous chloride, ferrous sulfate, ferrous hydroxide, ferrous nitrate, ferrous citrate, ferrous carbonate or ferrous oxide.
5. a kind of preparation method who mixes fluorine simultaneously and mix the ferrous silicate lithium anode material of zirconium according to claim 1, the compound that it is characterized in that described zirconium is zirconium dioxide, zirconium hydroxide, sodium zirconate, potassium fluorozirconate or zirconium sulfate; The compound of described fluorine is lithium fluoride, sodium fluoride, potassium fluoride or ammonium fluoride.
6. a kind of preparation method who mixes fluorine simultaneously and mix the ferrous silicate lithium anode material of zirconium according to claim 1 is characterized in that described carbon dust is natural graphite powder, graphous graphite powder or acetylene black.
7. a kind of preparation method who mixes fluorine simultaneously and mix the ferrous silicate lithium anode material of zirconium according to claim 1, it is characterized in that described inert atmosphere and weakly reducing atmosphere are nitrogen, argon gas, carbon monoxide or carbon dioxide, or the gaseous mixture of gaseous mixture, carbon dioxide and the argon gas of gaseous mixture, carbon dioxide and the nitrogen of gaseous mixture, carbon monoxide and the argon gas of gaseous mixture, carbon monoxide and the nitrogen of gaseous mixture, carbon monoxide and the carbon dioxide of gaseous mixture, hydrogen and the argon gas of the hydrogen of arbitrary volume ratio and nitrogen, or the gaseous mixture of nitrogen and argon gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104103836A (en) * | 2014-07-02 | 2014-10-15 | 三峡大学 | Sodium and manganese codoped modified lithium ferrosilite anode material and preparation method thereof |
| CN108063227A (en) * | 2017-12-11 | 2018-05-22 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of lithium ion battery fluorine, doped yttrium ferrosilicon silicate of lithium composite material |
| CN109638274A (en) * | 2018-12-14 | 2019-04-16 | 中科廊坊过程工程研究院 | A kind of molybdenum ytterbium is co-doped with silicic acid ferrisodium combination electrode material and preparation method thereof |
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| CN1692510A (en) * | 2002-12-19 | 2005-11-02 | 威伦斯技术公司 | Electrode active material and method of making the same |
| CN101734674A (en) * | 2009-11-24 | 2010-06-16 | 福建师范大学 | Preparation method of ferrous silicate lithium doped anode material |
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2010
- 2010-10-15 CN CN2010105078288A patent/CN102013483A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1692510A (en) * | 2002-12-19 | 2005-11-02 | 威伦斯技术公司 | Electrode active material and method of making the same |
| CN101734674A (en) * | 2009-11-24 | 2010-06-16 | 福建师范大学 | Preparation method of ferrous silicate lithium doped anode material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104103836A (en) * | 2014-07-02 | 2014-10-15 | 三峡大学 | Sodium and manganese codoped modified lithium ferrosilite anode material and preparation method thereof |
| CN108063227A (en) * | 2017-12-11 | 2018-05-22 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of lithium ion battery fluorine, doped yttrium ferrosilicon silicate of lithium composite material |
| CN109638274A (en) * | 2018-12-14 | 2019-04-16 | 中科廊坊过程工程研究院 | A kind of molybdenum ytterbium is co-doped with silicic acid ferrisodium combination electrode material and preparation method thereof |
| CN109638274B (en) * | 2018-12-14 | 2022-03-11 | 廊坊绿色工业技术服务中心 | Molybdenum-ytterbium co-doped sodium iron silicate composite electrode material and preparation method thereof |
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