CN101982410B - Preparation method of rare earth compound doped lithium ferrous silicate cathode material - Google Patents
Preparation method of rare earth compound doped lithium ferrous silicate cathode material Download PDFInfo
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- CN101982410B CN101982410B CN2010105078292A CN201010507829A CN101982410B CN 101982410 B CN101982410 B CN 101982410B CN 2010105078292 A CN2010105078292 A CN 2010105078292A CN 201010507829 A CN201010507829 A CN 201010507829A CN 101982410 B CN101982410 B CN 101982410B
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Abstract
The invention relates to a preparation method of rare earth compound doped lithium ferrous silicate cathode material. The preparation process includes the following steps: reactants of lithium compound, ferrous compound, rare earth element compound and silicon compound are weighed according to the mol ratio that lithium ion: ferrous ion: rare earth element ion: silicon ion is equal to (1.90-2.05): (1-y): z: 1, and a certain amount of carbon containing compound is added. Silicon compound and hot water or ethanol water are mixed, lithium compound is added, stirring and mixing are carried out, the other reactants and carbon containing compound are added, and vacuum drying is carried out. The dried powder is used for preparing lithium ferrous silicate by adopting two-stage sintering method. Discharging capacity of the prepared material at 3.0V region is obviously improved, and cycle performance at 0.3C current is good, thus laying good foundation for industrialization.
Description
Technical field
The invention belongs to the technical field of lithium ion battery electrode material, relate to a kind of rare earth doped compound, can be used for the preparation method of the ferrous silicate lithium anode material of lithium ion battery, lithium cell 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 the performance of positive electrode material.Since 2000; The preparation patent that Armand etc. [patent US 6085015] have applied for ferrosilicon silicate of lithium, [Nyten A, et al. such as Nyt é n; Electrochem.Commun.; 2005,7 (2): 156-160.] reported the orthohormbic structure of ferrosilicon silicate of lithium, the research of ferrosilicon silicate of lithium draws 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 its electronic conductivity is low, and the lithium ion rate of diffusion is slow, can only under very little electric current, discharge and recharge mostly, and this becomes one barrier of this material practicability.Method to the ferrosilicon silicate of lithium modification comprises that carbon coats methods such as processing and doping vario-property at present.Specifically can be divided into solid sintering technology, sol-gel method, 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
3With carbon gel ball mill mixing, at CO/CO
2Atmosphere in prepared 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
3The ball mill mixing thing at 800 ℃ of following sintering, prepared Li
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)
4Ball mill mixing thing 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
2Mixture microwave heating treatment with glucose prepares.
From sol-gel method, [Dominko R, Electrochem.Commun. such as Dominko; 2006,8 (2): 217-222.] ironic citrate and iron nitrate are mixed, earlier preparation colloidal sol under protective atmosphere; Then; The mixture that adds Lithium Hydroxide MonoHydrate and silicon-dioxide prepares xerogel through hydrothermal treatment consists, and last sintering prepares product.
Because the Li of above method preparation
2FeSiO
4Discharge performance under little electric current is still relatively poor, attempts to adopt adulterating method further to improve the chemical property of ferrosilicon silicate of lithium in recent years.Li etc. [Li L.M.et al., J.Power Sources, 2009] have synthesized LiFe with wet method-high temperature solid-phase sintering bonded method
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 x value scope was 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.
It is generally acknowledged; REE comprises that lanthanon reaches and the scandium (Sc) and the yttrium (Y) of lanthanon similar performance; Be specially lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu); Scandium (Sc) and yttrium (Y), rare earth compound is the compound of these 17 kinds of elements.Wherein, the valence electron structure of scandium is 3d
14s
2, yttrium is 4d
15s
2, cerium is [Xe] 4f
15d
16s
2, gadolinium is [Xe] 4f
75d
16s
2, lutetium is [Xe] 4f
145d
16s
2, the electronic structure of all the other REEs can be used [Xe] 4f
x6s
2Expression (x is between 0～14).In rare earth metal, 6s electronics and 5d electronics form conduction band, and the 4f electronics is in localization, and track is in incomplete occupied state, and the REE from the lanthanum to the lutetium all loses 2 6s electronics easily, and 1 5d electronics or 4f electronics form trivalent positive ion (4f
x5s
25p
6).REE from metal become+3 valency ions after, electronic structure is [Xe] 4f
x, wherein x is between 0～14.There is " lanthanide contraction " phenomenon in the atomic radius of REE, and the few electronic shell of the ion ratio atom of REE makes the contractive effect of ionic radius more obvious than atomic radius; Therefore, compare with the ion of synperiodic earth alkali metal, the ionic electric charge of REE is high; Radius is slightly little; From hard and soft acid and base, the ion of REE belongs to hard acid, is easy to hard base such as O
2-, OH
-Ionic bond with halogen.The ion of REE does not but cause the obvious change of structural stability if in the structure of the ferrous silicate lithium anode material that mixes, can cause the defective of ferrosilicon silicate of lithium lattice and the miniature deformation of structure cell, has improved the chemical property of preparation sample.
Summary of the invention
In order to improve the chemical property of ferrosilicon silicate of lithium; The present invention adopts hydrolysis-sintering process preparation ferrous silicate lithium anode material of doped rare earth element simultaneously; With the discharge performance and the cycle performance that improve the big electric current of ferrous silicate lithium anode material, the technical scheme that is adopted is:
Reactant is according to lithium ion: ferrous ion: the ion of REE: the mol ratio of silicon ion is (1.90～2.05): (1-y): z: the compound of the compound of 1 weighing lithium, ferrous compound, REE, the compound of silicon, according to 1%～30% weighing carbon compound of reactant quality summation; When x is the valency of rare earth element ion, relation below y and z satisfy simultaneously: 0.002≤y≤0.10 ,-0.05≤xz-y≤0.10;
The compound of silicon is added in the aqueous ethanolic solution of 50 ℃～80 ℃ of hot water or temperature of 50 ℃～90 ℃ of temperature; Described aqueous ethanolic solution is 1: 1～4: 1 the mixing solutions of volume ratio of ethanol and water; The compound that adds lithium; Mix, sneak into other all reactants and carbon compound, the consumption of described hot water or aqueous ethanolic solution is 1 times～20 times volumes of the total solid capacity of reactant; With the rotating speed ball mill mixing of 100rpm～900rpm 10 minutes～5 hours; Dry in the vacuum of 50 ℃～150 ℃ of temperature, pressure 10Pa～10132Pa, prepare dry powder; Dry powder 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; Dry powder is heated to arbitrary temperature of 200 ℃～500 ℃ of temperature ranges according to 0.5 ℃/min～30 ℃/heating rate 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 ℃/heating rate of min, kept this temperature sintering 3 hours～24 hours, the preparation ferrosilicon silicate of lithium.
The compound of described silicon is tetraethyl orthosilicate, quanmethyl silicate, silicic acid trimethyl, silicic acid dimethyl ester, silicon-dioxide, nano silicon, silicic acid or metasilicic acid.
The compound of described lithium is Quilonum Retard, Lithium Oxide 98min, Lithium Hydroxide MonoHydrate, lithium chloride, lithium oxalate, lithium acetate, lithium nitrate, Lithium Sulphate or monometallic.
Described ferrous compound is Ferrox, ferrous acetate, iron protochloride, ferrous sulfate, ferrous hydroxide, Iron nitrate, ferrous citrate, iron protocarbonate or iron protoxide.
The compound of described REE is oxide compound, nitrate salt, oxyhydroxide, carbonate or the muriate of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium.
Described carbon compound is Vestolen PP 7052, SEPIGEL 305, Z 150PH, glucose, sucrose, starch, flour, tapioca flour, potato powder, Semen Maydis powder, taro meal, rice meal or bran powder.
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, 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 carbon monoxide and argon gas.
Compare with other inventive method, raw materials cost of the present invention is lower, and raw material sources are extensive, and the preparation process is simple.The sample of preparation has discharge performance preferably, and the loading 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
Below in conjunction with embodiment the present invention is further specified.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: lanthanum ion: the mol ratio of silicon ion is 1.90: 0.998: 0.04: 1 weighing Quilonum Retard, Ferrox, lanthanum sesquioxide, tetraethyl orthosilicate, and according to 1% weighing Vestolen PP 7052 of reactant quality summation.
Tetraethyl orthosilicate is added in the hot water of 50 ℃ of 1 times of volume, temperature of total solid capacity that consumption is a reactant, add Quilonum Retard, mix, sneak into other all reactants and Vestolen PP 7052, with the rotating speed ball mill mixing of 100rpm 10 minutes; Dry in the vacuum of 50 ℃ of temperature, pressure 10Pa, prepare dry powder; Dry powder is placed nitrogen atmosphere; Heating rate according to 0.5 ℃/min is heated to 200 ℃ by room temperature, keeps this temperature sintering 3 hours, and then further is heated to 550 ℃ according to the heating rate of 0.5 ℃/min; Kept this temperature sintering 3 hours, the preparation ferrosilicon silicate of lithium.
Embodiment 2
Reactant is according to lithium ion: ferrous ion: praseodymium ion: the mol ratio of silicon ion is 1.90: 0.90: 0.0125: 1 weighing Lithium Hydroxide MonoHydrate, iron protochloride, titanium dioxide praseodymium, silicic acid trimethyl, and according to 30% weighing glucose of reactant quality summation.
The silicic acid trimethyl is added in the hot water of 90 ℃ of temperature, the consumption of hot water was 20 times of volumes of reactant total solid capacity, adds Lithium Hydroxide MonoHydrate again, mixes, and sneaks into other all reactants and glucose, with the rotating speed ball mill mixing of 900rpm 5 hours; Dry in the vacuum of 150 ℃ of temperature, pressure 10132Pa, prepare dry powder; Dry powder is placed carbon monoxide atmosphere; Heating rate according to 30 ℃/min is heated to 500 ℃ by room temperature, keeps this temperature sintering 12 hours, and then further is heated to 550 ℃ according to the heating rate of 30 ℃/min; Kept this temperature sintering 24 hours, the preparation ferrosilicon silicate of lithium.
Embodiment 3
Reactant is according to lithium ion: ferrous ion: scandium ion: the mol ratio of silicon ion is 2.05: 0.90: 0.067: 1 weighing lithium chloride, ferrous sulfate, Scium trinitrate, nano silicon, and according to 15% weighing sucrose of reactant quality summation.
Nano silicon is added in the aqueous ethanolic solution of 80 ℃ of temperature; Described aqueous ethanolic solution is that the volume ratio of ethanol and water is 1: 1 a mixing solutions; Add lithium chloride; Mix, sneak into other all reactants and sucrose, the consumption of ethanol and water mixed solution is 10 times of volumes of reactant total solid capacity; With the rotating speed ball mill mixing of 500rpm 1 hour; Dry in the vacuum of 100 ℃ of temperature, pressure 1010Pa, prepare dry powder; Dry powder is placed carbon dioxide atmosphere; Heating rate according to 20 ℃/min is heated to 400 ℃ by room temperature, keeps this temperature sintering 10 hours, and then further is heated to 850 ℃ according to the heating rate of 22 ℃/min; Kept this temperature sintering 24 hours, the preparation ferrosilicon silicate of lithium.
Embodiment 4
Reactant is according to lithium ion: ferrous ion: cerium ion: the mol ratio of silicon ion is 2.00: 0.90: 0.012: 1 weighing Lithium Hydroxide MonoHydrate, iron protochloride, cerous hydroxide, silicic acid, and according to 15% weighing flour of reactant quality summation.
Silicic acid is added in the aqueous ethanolic solution of 80 ℃ of temperature; Described aqueous ethanolic solution is that the volume ratio of ethanol and water is 3: 1 a mixing solutions; Add Lithium Hydroxide MonoHydrate; Mix, sneak into other all reactants and flour, the consumption of the mixing solutions of described ethanol and water is 10 times of volumes of the total solid capacity of reactant; With the rotating speed ball mill mixing of 700rpm 3 hours; Dry in the vacuum of 120 ℃ of temperature, pressure 100Pa, prepare dry powder; Dry powder is placed the atmosphere of the gas mixture of 1: 10 hydrogen of volume ratio and nitrogen; Heating rate according to 25 ℃/min is heated to 500 ℃ by room temperature; Kept this temperature sintering 10 hours; And then further be heated to 850 ℃ according to the heating rate of 30 ℃/min, kept this temperature sintering 20 hours, the preparation ferrosilicon silicate of lithium.
Embodiment 5
Reactant is according to lithium ion: ferrous ion: scandium ion: the mol ratio of silicon ion is 2.05: 0.95: 0.05: 1 weighing lithium acetate, ferrous citrate, scandium oxide, metasilicic acid, and according to 30% weighing taro meal of reactant quality summation.
Metasilicic acid is added in the hot water of 90 ℃ of temperature, add lithium acetate, mix, sneak into other all reactants and taro meal, the consumption of described hot water is 1 times of volume of reactant total solid capacity; With the rotating speed ball mill mixing of 900rpm 10 minutes; Dry in the vacuum of 50 ℃ of temperature, pressure 10132Pa, prepare dry powder; Dry powder is placed the atmosphere of carbon monoxide and 1: 10 gas mixture of carbonic acid gas volume ratio; Heating rate according to 0.5 ℃/min is heated to 280 ℃ by room temperature; Kept this temperature sintering 3 hours; And then further be heated to 830 ℃ according to the heating rate of 30 ℃/min, kept this temperature sintering 24 hours, the preparation ferrosilicon silicate of lithium.
Claims (8)
1. the preparation method of the ferrous silicate lithium anode material of a rare earth doped compound is characterized in that the preparation process is made up of following steps:
Reactant is according to lithium ion: ferrous ion: the ion of REE: the mol ratio of silicon ion is (1.90～2.05): (1-y): z: the compound of the compound of 1 weighing lithium, ferrous compound, REE, the compound of silicon, according to 1%～30% weighing carbon compound of reactant quality summation;
X representes the valency of rare earth element ion, relation below y and z satisfy simultaneously: 0.002≤y≤0.10 ,-0.05≤xz-y≤0.10;
The compound of silicon is added in the aqueous ethanolic solution of 50 ℃-80 ℃ of hot water or temperature of 50 ℃～90 ℃ of temperature; Described aqueous ethanolic solution is the volume ratio 1 of ethanol and water: 1-4: 1 mixing solutions; The compound that adds lithium; Mix, sneak into other all reactants and carbon compound, the consumption of described hot water or aqueous ethanolic solution is 1 times～20 times volumes of the total solid capacity of reactant; With the rotating speed ball mill mixing of 100rpm～900rpm 10 minutes～5 hours; Dry in the vacuum of 50 ℃～150 ℃ of temperature, pressure 10Pa～10132Pa, prepare dry powder; Dry powder 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; Dry powder is heated to arbitrary temperature of 200 ℃～500 ℃ of temperature ranges according to 0.5 ℃/min～30 ℃/heating rate 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 ℃/heating rate of min, kept this temperature sintering 3 hours～24 hours, the preparation ferrosilicon silicate of lithium.
2. the preparation method of the ferrous silicate lithium anode material of a kind of rare earth doped compound 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 or metasilicic acid.
3. the preparation method of the ferrous silicate lithium anode material of a kind of rare earth doped compound according to claim 2 is characterized in that described silicon-dioxide is nano silicon.
4. the preparation method of the ferrous silicate lithium anode material of a kind of rare earth doped compound according to claim 1, the compound that it is characterized in that described lithium is Quilonum Retard, Lithium Oxide 98min, Lithium Hydroxide MonoHydrate, lithium chloride, lithium oxalate, lithium acetate, lithium nitrate, Lithium Sulphate or monometallic.
5. the preparation method of the ferrous silicate lithium anode material of a kind of rare earth doped compound according to claim 1 is characterized in that described ferrous compound is Ferrox, ferrous acetate, iron protochloride, ferrous sulfate, ferrous hydroxide, Iron nitrate, ferrous citrate, iron protocarbonate or iron protoxide.
6. the preparation method of the ferrous silicate lithium anode material of a kind of rare earth doped compound according to claim 1, the compound that it is characterized in that described REE is oxide compound, nitrate salt, oxyhydroxide, carbonate or the muriate of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium.
7. the preparation method of the ferrous silicate lithium anode material of a kind of rare earth doped compound according to claim 1 is characterized in that described carbon compound is Vestolen PP 7052, SEPIGEL 305, Z 150PH, glucose, sucrose, starch, flour, tapioca flour, potato powder, Semen Maydis powder, taro meal, rice meal or bran powder.
8. the preparation method of the ferrous silicate lithium anode material of a kind of rare earth doped compound 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, 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 carbon monoxide and argon gas.
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| CN102723488B (en) * | 2012-06-22 | 2015-05-13 | 三峡大学 | Vanadium-doped lithium iron silicate anode material and preparation method thereof |
| CN102969503B (en) * | 2012-12-04 | 2015-08-12 | 奇瑞汽车股份有限公司 | Composite material of composition silicate and carbon and preparation method thereof, lithium ion battery containing this material |
| 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 |
| 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 |
| CN113830774A (en) * | 2021-10-18 | 2021-12-24 | 浙江长兴中俄新能源材料技术研究院有限公司 | Method for preparing carbon composite lithium ferrous silicate by ilmenite based on sol-gel method |
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