CN101673822B - Preparation method of lithium iron phosphate cathode material simultaneously blended with silver and iodine - Google Patents
Preparation method of lithium iron phosphate cathode material simultaneously blended with silver and iodine Download PDFInfo
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- CN101673822B CN101673822B CN2009101125643A CN200910112564A CN101673822B CN 101673822 B CN101673822 B CN 101673822B CN 2009101125643 A CN2009101125643 A CN 2009101125643A CN 200910112564 A CN200910112564 A CN 200910112564A CN 101673822 B CN101673822 B CN 101673822B
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to a preparation method of a lithium iron phosphate cathode material which can be used for lithium ion batteries, lithium batteries, polymer lithium ion batteries and super capacitors. The adopted technical scheme is as follows: mixing lithium source compounds, ferrous source compounds, phosphate source compounds and silver blending agent, adding wet-milling medium and carbon-containing compounds or carbon powder, ball milling and mixing for 1-15 hours, vacuum drying at any temperature between 70 DEG C and 135 DEG C, then preparing a silver-doped precursor out of the dried powder samples by a two-section sintering method; and then mixing the silver-doped precursor, nickel blending agent and wet-milling medium, ball milling and mixing for 1-15 hours, vacuum drying at any temperature between 70 DEG C and 120 DEG C, then preparing the lithium iron phosphate simultaneously blended with silver and iodine from the dried powder samples by a low-temperature sintering method. The method has lower raw material cost, wide raw material source and simple preparation process, simultaneously, the discharge platform of the sample rises in voltage, is prolonged and has excellent cycle performance under the situation of large-current discharge.
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 lithium iron phosphate cathode material of lithium ion battery, lithium battery, polymer Li-ion battery and ultracapacitor.
Technical background
As energy resource system of new generation, lithium ion battery is widely used in electric automobile, satellite, space flight and military field.Numerous researchs show, LiFePO
4Possibly become one of positive electrode of the most promising lithium ion battery.Yet, because LiFePO
4The restriction of this body structure, the electronic conductivity of this material is low, ionic conductivity is poor, causes the poor-performing of high power charging-discharging, and non-modified does not reach requirement of actual application.In order to overcome the deficiency of LiFePO 4, carried out extensive studies both at home and abroad.
LiFePO
4The main methods such as solid sintering technology, sol-gel process, oxidation-reduction method, microwave process for synthesizing and hydro thermal method that adopt prepare.Wherein, solid sintering technology has the cheap clear superiority of Denging, possibly be to realize LiFePO
4The optimal preparation method of industrialization.The main solid phase doping method that adopts carries out modification to the chemical property of LiFePO 4.The dopant that is used for doping vario-property relates to many elements of the periodic table of elements, comprises nickel fiber, copper fiber, iron fiber, zinc fiber, acetylene black, crystalline flake graphite, boride, carbide, transistion metal compound, carbon dust, sucrose, glucose, polyvinyl alcohol, dextrin, starch, alkali metal, alkaline-earth metal, halogen, rare earth element etc.Wherein, mix silver or mix iodine LiFePO 4 prepared attention.
The preparation method who mixes silver-colored LiFePO 4 roughly is divided into three types.
The first kind of preparation method (patent CN1903708A, CN101112979A, CN1903707A, CN101327921A, CN101162776A) who mixes silver-colored LiFePO 4 be add silver powder in the preparation or with the argent of silver ion reduction as conductive agent, utilize the outstanding electric conductivity of argent to improve the conductivity of lithium ferrous silicate lithium.Yet this preparation method can only improve conductivity between lithium ferrous silicate lithium particle, can not improve the conductivity of lithium ferrous silicate lithium itself.For example; It is water-soluble that patent CN1903708A will contain the compound of lithium, iron, phosphorus, adds oxide, the hydroxide of Ag or Cu, nitrate, acylate or metallo-organic compound; Add superconduction carbon black, superfine graphite, sucrose, citric acid, starch, polyethylene powders or polyvinyl alcohol conductive agent again; With silver ion reduction is argent, through spray drying, and the LiFePO 4 that preparation Ag or Cu powder coat.Patent CN101112979A mixes source of iron, phosphorus source, lithium source, nucleus growth agent and deionized water, and vacuumize is under nitrogen protection, earlier through double sintering.Again intermediate product is mixed with conductive agent silver powder or copper powder, through sintering preparing product once more.Water-fast and water-soluble reagent is processed suspension-turbid liquid in the compound of patent CN1903707A with Li, Fe, P, adds the Ag powder or makes the LiFePO 4 that silver coats with reduction silver ions such as charcoal, sucrose, citric acids.
The second kind of preparation method (patent CN1291508C, CN1982207A, CN1982208A, CN101070148A) who mixes silver-colored LiFePO 4 mixes silver ion with predecessor or LiFePO 4; Pass through sintering processes; Attempt silver ion is embedded in the construction unit of LiFePO 4, thereby improve the chemical property of lithium ferrous silicate lithium.Patent CN101070148A is with iron, lithium and phosphatic compound, and sintering prepares LiFePO 4 at a lower temperature earlier.Then, again with LiFePO 4 and Ag
2O is mixed, and silver-colored LiFePO 4 is mixed in the sintering preparation under higher temperature.Patent CN1291508C mixes compound, phosphate, silver salt and the organic acid of lithium salts, iron earlier through sol-gel process, adds high molecular polymer again and prepares predecessor, and silver-colored ferrous phosphate lithium/carbon composite material is mixed in the sintering preparation.Patent CN101315981A mixes phosphorus source, source of iron, lithium source solution and reducing agent, under cryogenic high pressure, prepares lithium iron phosphate precursor earlier.Then, add silver and other dopant ion again, mix back sintering preparing product.Patent CN1797823A has prepared the silver-colored lithium iron phosphate positive material of mixing of oxygen-containing vacancy.
The third preparation method (CN101212049A) who mixes silver-colored LiFePO 4 is the Li that has Nasicon type tunnel structure with solid phase reaction, hydro-thermal reaction and Prepared by Sol Gel Method
3+yFe
2-xAg
x(PO
4)
3, and then with the preparation powder and carbon ball mill mixing prepare Li
3+yFe
2-xAg
x(PO
4)
3/ C.
Because iodide ion has stronger reproducibility, the LiFePO 4 of lower valency iron of chemical property iodide contain to(for) improvement possibly produce special effect.Mixing the iodine LiFePO 4 also draws attention.Patent CN101202361A is with LiFePO
4With contain lithium anode material Li
mI
nO
x(wherein, m=1～4, n=1～5, x=2～12) mixes, and to improve the tap density of positive electrode, improves processing characteristics.Wherein, Li
mI
nO
xCan use LiBO earlier
2, Li
2CO
3, LiCoO
2, LiNi
0.2Co
0.8O
2Or ZnO coats, again and LiFePO
4Mix.Patent CN101262059A mixes source of iron, phosphorus source and lithium iodide, adds reducing agents such as ascorbic acid, adipic acid, and sintering prepares LiFePO
4Patent CN100343332C mixes the high conduction coalescence benzene of ferrous source, phosphorus source, lithium iodide, themselves preparation, and sintering prepares LiFePO 4/coalescence benzene (PAS) composite material.
Because single ion doping of planting is not obvious to the effect of the multiplying power discharging property that improves LiFePO 4, patent CN101339994A is through to LiFePO
4At least two parent positions of lithium position, iron position, phosphate potential and oxygen position method of mixing simultaneously carry out modification.Their lithium position dopant is selected the compound of lanthanide series rare-earth elements; Iron position dopant is selected Mn, Co, Ni and lanthanide series rare-earth elements compound; P site doped dose of compound or the simple substance of selecting B, W, S and Si element, oxygen group elements and oxygen place doped dose are selected for use in itrogenous organic substance, sulfur-containing compound, sulphur simple substance, chlorine-containing compound and the fluorochemical at least a.The preparation process adopts the solid sintering technology with a dopant and a batch mixing of parent stock, the solid phase method preparation method that perhaps oxygen place doped dose of pre-burning material that mixes with other positions of parent is mixed.When adopting oxygen place doped dose during with solid sintering technology that the pre-burning material of other parent position dopants mixes; Because the sintering temperature of this patent is in 550 ℃～850 ℃ temperature ranges; And it is at high temperature scarcely stable to be used for oxygen place doped dopant, is used for oxygen place doped dopant and is difficult to control in the stoichiometric proportion of preparing product.
In order to improve the performance of LiFePO 4, the present invention mixes lithium source, ferrous source, source of phosphoric acid, silver-colored dopant, adds wet grinding media and carbonaceous material, mixes, and mixes silver-colored predecessor through the preparation earlier of double sintering method.Then, will mix silver-colored predecessor again, mix idodine and wet grinding media mixes once more, and handle through low-temperature sintering, the silver iodide that are utilized in the high conduction that is evenly distributed in the LiFePO 4 improve the chemical property of ferrous phosphate doping lithium/carbon composite sample.Because the silver iodide of high conduction performance embed in the structure of LiFePO 4 uniformly, can obviously improve the heavy-current discharge performance of LiFePO 4 sample.
Summary of the invention
The purpose of this invention is to provide a kind of silver and preparation method who mixes the lithium iron phosphate cathode material of iodine of mixing simultaneously.For realizing above-mentioned purpose, the technical scheme that the present invention adopted is:
1) silver-colored predecessor is mixed in preparation
With initial compounds Li source compound, ferrous source compound, the source of phosphoric acid compound of weighing with mix silver-colored agent and mix; Add wet grinding media I and carbonaceous material in the wet grinding media; Ball mill mixing is 1 hour～15 hours under 100 rev/mins～1000 rev/mins rotating speed, and is dry in arbitrary vacuum under pressure of 10Pa～10132Pa pressure limit in arbitrary temperature of 70 ℃～135 ℃ of temperature ranges.Dry powder sample adopts the preparation of double sintering method to mix silver-colored predecessor.
Described carbonaceous material is polyvinyl alcohol, glucose, sucrose, polyethyl acrylate, flour, tapioca flour, pachyrhizus, dehydrated potato powder, taro powder, bran powder, acetylene black or graphite powder.
2) silver and the LiFePO 4 of mixing iodine are mixed in preparation
To mix silver-colored predecessor, mix wet grinding media II in idodine and wet grinding media ball mill mixing 1 hour～15 hours under 100 rev/mins～1000 rev/mins rotating speed, dry in arbitrary temperature of 70 ℃～120 ℃ of temperature ranges in arbitrary vacuum under pressure of 10Pa～10132Pa pressure limit.Dry powder sample adopts the low-temperature sintering legal system to mix silver and the LiFePO 4 of mixing iodine fully simultaneously.
The mol ratio of initial action compound of the present invention is according to Li source compound, ferrous source compound, source of phosphoric acid compound, mixes silver-colored agent and mix the lithium ion in the idodine: ferrous ion: phosphate anion: silver ion: the mol ratio of iodide ion is x: y: z: k: m weighing compound of reaction Li source compound, ferrous source compound, source of phosphoric acid compound, mix silver-colored agent, mix idodine.Wherein, the scope of the numerical value of the x of reactant molar ratio, y, z, k, m is: 0.95≤x≤1.10,0.90≤y≤1.05,0.90≤z≤1.15,0.0010≤k≤0.15,0.0010≤m≤0.15.
The consumption of carbonaceous material of the present invention is that 1%～20% of the LiFePO 4 product weight calculated according to compound of reaction weight carries out weighing.
Wet grinding media of the present invention is to measure according to 0.1～20 times of volume of initial action compound cumulative volume, and wet grinding media is divided into wet grinding media I and wet grinding media II according to volume ratio in 10: 1～100 scope.
Double sintering method of the present invention is that the powder sample with drying places inert atmosphere or weakly reducing atmosphere; Be heated to arbitrary temperature of 300 ℃～600 ℃ of temperature ranges by room temperature according to 1 ℃/min～30 ℃/heating rate of min; Kept the temperature sintering 3 hours～18 hours; Be heated to arbitrary temperature of 650 ℃～900 ℃ of temperature ranges according to the heating rate of 1 ℃/min～30 ℃/min by last sintering temperature then, kept the temperature sintering 3 hours～18 hours.Being cooled to room temperature makes and mixes silver-colored predecessor.
Low-temperature sintering method of the present invention is that the powder sample with drying places inert atmosphere or weakly reducing atmosphere; Be heated to arbitrary temperature of 150 ℃～370 ℃ of temperature ranges by room temperature according to 1 ℃/min～30 ℃/heating rate of min; Kept the temperature sintering 2 hours～18 hours, and be cooled to room temperature and make the LiFePO 4 of mixing silver simultaneously and mixing iodine.
The idodine of mixing of the present invention is lithium iodide, sodium iodide, calcium iodide, strontium iodide, barium iodide, iodate germanium, silver iodide, KI or hydrogen iodide.
It is of the present invention that to mix silver-colored agent be silver chlorate, silver sulfate, silver hydroxide, basic carbonate silver, silver carbonate or silver nitrate.
Li source compound of the present invention is lithium carbonate, lithium oxalate, lithium citrate, lithium acetate, lithium chloride, lithia or lithium hydroxide.
Ferrous source compound of the present invention is ferrous oxalate, ferrous acetate, frerrous chloride, ferrous carbonate, ferrous hydroxide or ferrous oxide.
Source of phosphoric acid compound of the present invention is phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium hydrogen phosphate or potassium dihydrogen phosphate.
Inert atmosphere of the present invention or weakly reducing atmosphere are nitrogen, argon gas, carbon monoxide or volume ratio at the gaseous mixture of gaseous mixture, argon gas and the hydrogen of the nitrogen of 10: 1～100 scopes and hydrogen or the gaseous mixture of nitrogen and argon gas.
Wet grinding media of the present invention is methyl alcohol, ethanol, propyl alcohol, acetone, formaldehyde, distilled water, deionized water or formic acid.
Compare with other inventive method; Cost of material of the present invention is lower, and raw material sources are extensive, and the preparation process is simple; Silver ion that mixes simultaneously and iodide ion can play synergy in charge and discharge process; The discharge voltage plateau of the sample of preparation raises, discharge platform prolongs, and cycle performance is good under the situation of heavy-current discharge, for industrialization is laid a good foundation.
Embodiment
Below in conjunction with embodiment the present invention is further explained.Embodiment further replenishes and explanation of the present invention, rather than the restriction to inventing.
Embodiment 1
According to lithium ion: ferrous ion: phosphate anion: silver ion: the mol ratio of iodide ion is 0.95: 0.90: 0.90: 0.0010: 0.0010 weighing compound of reaction lithium carbonate (Li
2CO
3) 35 the gram, ferrous oxalate (FeC
2O
42H
2O) 161 grams, phosphoric acid (H
3PO
4) 88.2 grams, silver chlorate (AgCl) 0.14 gram, lithium iodide (LiI3H
2O) 0.19 gram.Weighing 1.4 gram polyvinyl alcohol.Measure 28.5mL methyl alcohol, and be divided into two parts of 4.75mL and 23.75mL.
Lithium carbonate, ferrous oxalate, phosphoric acid, the silver chlorate of weighing are mixed, add 1.4 gram polyvinyl alcohol and 4.75mL methyl alcohol, ball mill mixing is 1 hour under 100 rev/mins rotating speed, and is dry in the 10Pa vacuum under pressure under 70 ℃.Dry powder sample places nitrogen atmosphere; Programming rate according to 1 ℃/min is heated to 300 ℃ by room temperature, keeps the temperature sintering 3 hours, and the programming rate according to 1 ℃/min is heated to 650 ℃ by 300 ℃ then; Kept the temperature sintering 18 hours, and be cooled to room temperature and make and mix silver-colored predecessor.
Lithium iodide and the 23.75mL methyl alcohol that to mix silver-colored predecessor, weighing ball mill mixing 15 hours under 100 rev/mins rotating speed, dry at 120 ℃ in the 10132Pa vacuum under pressure.Dry powder sample places under the nitrogen atmosphere, is heated to 150 ℃ according to the heating rate of 1 ℃/min by room temperature, keeps the temperature sintering 2 hours, is cooled to room temperature and makes and mix silver and the LiFePO 4 of mixing iodine simultaneously.
Embodiment 2
According to lithium ion: ferrous ion: phosphate anion: silver ion: the mol ratio of iodide ion is 1.10: 1.05: 1.15: 0.15: 0.15 weighing compound of reaction lithium hydroxide (LiOH H
2O) 46 grams, ferrous oxide (FeO) 75.4 grams, ammonium dihydrogen phosphate (NH
4H
2PO
4) 132 the gram, Ag
2O 17.4 grams, KI (KI) 24.9 grams.Weighing 43 gram bran powders.Measure 8662mL formic acid, and be divided into two parts of 787mL and 7875mL.
Lithium hydroxide, ferrous oxide, ammonium dihydrogen phosphate, Ag with weighing
2O mixes, and adds 43 gram bran powder and 787mL formic acid, and ball mill mixing is 1 hour under 100 rev/mins rotating speed, and is dry in the 10Pa vacuum under pressure at 70 ℃.Dry powder sample places nitrogen and 10: 1 gaseous mixture of argon gas volume ratio; Programming rate according to 1 ℃/min is heated to 600 ℃ by room temperature; Kept the temperature sintering 18 hours; Heating rate according to 1 ℃/min is heated to 650 ℃ by 600 ℃ then, keeps the temperature sintering 3 hours, is cooled to room temperature and makes and mix silver-colored predecessor.
KI and the 7875mL formic acid that to mix silver-colored predecessor, weighing ball mill mixing 15 hours under 1000 rev/mins rotating speed, dry at 120 ℃ in the 10132Pa vacuum under pressure.Dry powder sample places nitrogen and 10: 100 gaseous mixture of argon gas volume ratio, is heated to 200 ℃ according to the heating rate of 1 ℃/min by room temperature, keeps the temperature sintering 18 hours, is cooled to room temperature and makes the LiFePO 4 of mixing silver simultaneously and mixing iodine.
Embodiment 3
According to lithium ion: ferrous ion: phosphate anion: silver ion: the mol ratio of iodide ion is 0.95: 1.05: 0.90: 0.0010: 0.15 weighing compound of reaction lithium acetate (LiCOOCH
32H
2O) 96 grams, frerrous chloride (FeCl
2) 133 the gram, ammonium hydrogen phosphate ((NH
4)
2HPO
4) 119 grams, basic carbonate silver (Ag
3(OH) CO
3) 0.14 the gram, iodate germanium (GeI
4) 21.7 grams.Weighing 1.7 gram flour.Measure the 3451mL propyl alcohol, and be divided into two parts of 575mL and 2876L.
Lithium acetate, frerrous chloride, ammonium hydrogen phosphate, the basic carbonate silver of weighing are mixed, add flour and 575mL propyl alcohol, ball mill mixing is 5 hours under 300 rev/mins rotating speed, and is dry in the 100Pa vacuum under pressure at 100 ℃.The powder sample of drying is placed nitrogen and the gaseous mixture of hydrogen volume than 10: 1; Heating rate according to 30 ℃/min is heated to 300 ℃ by room temperature; Kept the temperature sintering 3 hours, the heating rate according to 10 ℃/min is heated to 900 ℃ by 300 ℃ then, keeps the temperature sintering 15 hours.Being cooled to room temperature makes and mixes silver-colored predecessor.
Iodate germanium and the 2876mL propyl alcohol that to mix silver-colored predecessor, weighing ball mill mixing 10 hours under 600 rev/mins rotating speed, dry at 100 ℃ in the 600Pa vacuum under pressure.The powder sample of drying is placed under the nitrogen atmosphere, be heated to 370 ℃ by room temperature, kept the temperature sintering 18 hours, be cooled to room temperature and make and mix silver and the LiFePO 4 of mixing iodine simultaneously according to the heating rate of 5 ℃/min.
Embodiment 4
According to lithium ion: ferrous ion: phosphate anion: silver ion: the mol ratio of iodide ion is 1.00: 1.00: 1.05: 0.10: 0.050 weighing compound of reaction lithium citrate (Li
3C
6H
5O
74H
2O) 94 grams, ferrous carbonate (FeCO
3) 116 the gram, ammonium phosphate ((NH
4)
3PO
43H
2O) 213 grams, silver carbonate (Ag
2CO
3) 13.8 grams, sodium iodide (NaI) 7.5 gram.Weighing 18.1 gram sucrose are measured 1807mL acetone, and are divided into two parts of 602mL and 1205mL.
Lithium citrate, ferrous carbonate, ammonium phosphate, the silver carbonate of weighing are mixed, add 18.1 gram sucrose and 602mL acetone, ball mill mixing is 5 hours under 500 rev/mins rotating speed, and is dry in the 280Pa vacuum under pressure at 110 ℃.The powder sample of drying is placed argon gas and the gaseous mixture of hydrogen volume than 10: 1; Heating rate according to 15 ℃/min is heated to 500 ℃ by room temperature; Keep the temperature sintering 10 hours, and be heated to 800 ℃ according to 5 ℃/min heating rate by 500 ℃ then, kept the temperature sintering 8 hours.Being cooled to room temperature makes and mixes silver-colored predecessor.
Sodium iodide and the 1205mL acetone that to mix silver-colored predecessor, weighing ball mill mixing 10 hours under 700 rev/mins rotating speed, at 90 ℃ in dry between the 10132Pa vacuum under pressure.It is 10: 2 gaseous mixture that dry powder sample places argon gas and hydrogen volume ratio, is heated to 300 ℃ according to the heating rate of 5 ℃/min by room temperature, keeps the temperature sintering 10 hours, is cooled to room temperature and makes and mix silver and the LiFePO 4 of mixing iodine simultaneously.
Embodiment 5
According to lithium ion: ferrous ion: phosphate anion: silver ion: the mol ratio of iodide ion is 0.95: 1.00: 1.00: 0.15: 0.0010 weighing compound of reaction lithium oxalate (Li
2C
2O
4) 48 the gram, frerrous chloride (FeCl
2) 127 the gram, potassium dihydrogen phosphate (KH
2PO
4) 136 the gram, silver nitrate (AgNO
3) 25.5 the gram, silver iodide (AlI
3) 0.14 gram.Weighing 10.6 gram acetylene blacks are measured 425mL formaldehyde, and are divided into two parts of 170mL and 255mL.
Lithium oxalate, frerrous chloride, potassium dihydrogen phosphate, the silver nitrate of weighing are mixed, add 10.6 gram acetylene black and 170mL formaldehyde, ball mill mixing is 15 hours under 800 rev/mins rotating speed, and is dry in the 10Pa vacuum under pressure at 135 ℃.The powder sample of drying is placed under the carbon monoxide atmosphere, be heated to 600 ℃ according to the heating rate of 2 ℃/min by room temperature, kept the temperature sintering 3 hours, the heating rate according to 5 ℃/min is heated to 900 ℃ by 600 ℃ then, keeps the temperature sintering 18 hours.Being cooled to room temperature makes and mixes silver-colored predecessor.
To mix the silver iodide and the 255mL formaldehyde of silver-colored predecessor, weighing, ball mill mixing is 15 hours under 900 rev/mins rotating speed, at 90 ℃ in dry between the 10132Pa vacuum under pressure.The powder sample of drying is placed under the carbon monoxide atmosphere, be heated to 370 ℃ by room temperature, kept the temperature sintering 10 hours, be cooled to room temperature and make and mix silver and the LiFePO 4 of mixing iodine simultaneously according to the heating rate of 8 ℃/min.
Claims (8)
1. mix silver and the preparation method who mixes the lithium iron phosphate cathode material of iodine simultaneously, it is characterized in that:
1) silver-colored predecessor is mixed in preparation
With initial compounds Li source compound, ferrous source compound, the source of phosphoric acid compound of weighing with mix silver-colored agent and mix; Add wet grinding media I and carbonaceous material in the wet grinding media; Ball mill mixing is 1 hour～15 hours under 100 rev/mins～1000 rev/mins rotating speed; Arbitrary temperature 70 ℃～135 ℃ of temperature ranges is dry in arbitrary vacuum under pressure of 10Pa～10132Pa pressure limit, adopts the preparation of double sintering method to mix silver-colored predecessor then;
Described carbonaceous material is meant polyvinyl alcohol, glucose, sucrose, polyethyl acrylate, flour, tapioca flour, pachyrhizus, dehydrated potato powder, taro powder, bran powder, acetylene black or graphite powder;
Described double sintering method is that the powder sample with drying places inert atmosphere or weakly reducing atmosphere; Be heated to arbitrary temperature of 300 ℃～600 ℃ of temperature ranges by room temperature according to 1 ℃/min～30 ℃/heating rate of min; Kept the temperature sintering 3 hours～18 hours; Be heated to arbitrary temperature of 650 ℃～900 ℃ of temperature ranges according to the heating rate of 1 ℃/min～30 ℃/min by last sintering temperature then, kept the temperature sintering 3 hours～18 hours, be cooled to room temperature and make and mix silver-colored predecessor;
2) silver and the LiFePO 4 of mixing iodine are mixed in preparation
To mix silver-colored predecessor, mix wet grinding media II in idodine and wet grinding media ball mill mixing 1 hour～15 hours under 100 rev/mins～1000 rev/mins rotating speed; Arbitrary temperature 70 ℃～120 ℃ of temperature ranges is dry in arbitrary vacuum under pressure of 10Pa～10132Pa pressure limit, and dry powder sample adopts the low-temperature sintering legal system to mix silver and the LiFePO 4 of mixing iodine fully simultaneously;
Described low-temperature sintering method is that the powder sample with drying places under inert atmosphere or the weakly reducing atmosphere; Be heated to arbitrary temperature of 150 ℃～370 ℃ of temperature ranges by room temperature according to 1 ℃/min～30 ℃/heating rate of min; Kept the temperature sintering 2 hours～18 hours, and be cooled to room temperature and make the LiFePO 4 of mixing silver simultaneously and mixing iodine.
2. silver and the preparation method who mixes the lithium iron phosphate cathode material of iodine of mixing simultaneously according to claim 1; The mol ratio that it is characterized in that described initial action compound is according to Li source compound, ferrous source compound, source of phosphoric acid compound, mixes silver-colored agent and mix the lithium ion in the idodine: ferrous ion: phosphate anion: silver ion: the mol ratio of iodide ion is x: y: z: k: m weighing compound of reaction Li source compound, ferrous source compound, source of phosphoric acid compound, mix silver-colored agent, mix idodine; Wherein, The scope of the numerical value of the x of reactant molar ratio, y, z, k, m is: 0.95≤x≤1.10; 0.90≤y≤1.05; 0.90≤z≤1.15,0.0010≤k≤0.15,0.0010≤m≤0.15.
3. silver and the preparation method who mixes the lithium iron phosphate cathode material of iodine of mixing simultaneously according to claim 1; The consumption that it is characterized in that described carbonaceous material is that 1%～20% of the LiFePO 4 product weight calculated according to initial action compound weight carries out weighing.
4. silver and the preparation method who mixes the lithium iron phosphate cathode material of iodine of mixing simultaneously according to claim 1; It is characterized in that described wet grinding media is methyl alcohol, ethanol, propyl alcohol, acetone, formaldehyde, distilled water, deionized water or formic acid; Its consumption is 0.1～20 times of volume of initial action compound cumulative volume, simultaneously wet grinding media is divided into wet grinding media I and wet grinding media II according to volume ratio in 10: 1～100 scope.
5. silver and the preparation method who mixes the lithium iron phosphate cathode material of iodine of mixing simultaneously according to claim 1 is characterized in that the described idodine of mixing is lithium iodide, sodium iodide, calcium iodide, strontium iodide, barium iodide, iodate germanium, silver iodide, KI or hydrogen iodide; It is described that to mix silver-colored agent be silver chlorate, silver sulfate, silver hydroxide, basic carbonate silver, silver carbonate, silver nitrate or silver oxide.
6. silver and the preparation method who mixes the lithium iron phosphate cathode material of iodine of mixing simultaneously according to claim 1 is characterized in that described Li source compound is lithium carbonate, lithium oxalate, lithium citrate, lithium acetate, lithium chloride, lithia or lithium hydroxide; Described ferrous source compound is ferrous oxalate, ferrous acetate, frerrous chloride, ferrous carbonate, ferrous hydroxide or ferrous oxide.
7. silver and the preparation method who mixes the lithium iron phosphate cathode material of iodine of mixing simultaneously according to claim 1 is characterized in that described source of phosphoric acid compound is phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium phosphate,monobasic or potassium dihydrogen phosphate.
8. silver and the preparation method that mixes the lithium iron phosphate cathode material of iodine of mixing simultaneously according to claim 1 is characterized in that described inert atmosphere or weakly reducing atmosphere are nitrogen, argon gas, carbon monoxide or volume ratio at the gaseous mixture of gaseous mixture, argon gas and the hydrogen of the nitrogen of 10: 1～100 scopes and hydrogen or the gaseous mixture of nitrogen and argon gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101125643A CN101673822B (en) | 2009-09-24 | 2009-09-24 | Preparation method of lithium iron phosphate cathode material simultaneously blended with silver and iodine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101125643A CN101673822B (en) | 2009-09-24 | 2009-09-24 | Preparation method of lithium iron phosphate cathode material simultaneously blended with silver and iodine |
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| Publication Number | Publication Date |
|---|---|
| CN101673822A CN101673822A (en) | 2010-03-17 |
| CN101673822B true CN101673822B (en) | 2012-02-29 |
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