CN1275342C - Preparation method of spherical Li4Ti5O12 as lithium ion cell cathode material - Google Patents

Preparation method of spherical Li4Ti5O12 as lithium ion cell cathode material Download PDF

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CN1275342C
CN1275342C CNB2004100989443A CN200410098944A CN1275342C CN 1275342 C CN1275342 C CN 1275342C CN B2004100989443 A CNB2004100989443 A CN B2004100989443A CN 200410098944 A CN200410098944 A CN 200410098944A CN 1275342 C CN1275342 C CN 1275342C
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make
spherical
colloidal sol
gained
concentration
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CN1622368A (en
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高剑
姜长印
应皆荣
万春荣
何向明
李建军
王莉
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a preparation method for spherical Li4Ti5O12 which is the material of the negative electrode of a lithium ion battery. The present invention relates to a process for preparing the spherical Li4Ti5O12 which is the material of the negative electrode of a lithium ion battery. The method uses TiCl4 as a raw material to prepare a sol A via water hydrolysis. A solution B is prepared by hexamethylenetetramine and urea which are dissolved in water, and the solution B is added in the sol A so as to prepare a new sol. The present invention uses kerosene as a medium, the mixing sol is dropped in the kerosene, the kerosene is subsequently heated so as to convert the sol into a gel precipitation, and a spherical precursor is obtained via separation, washing, aging and drying. Lithium is added in the precursor and is heated so as to prepare the spherical Li4Ti5O12, and doping ions only need to be added into the sol A when doped. The preparation method has simple technical processes, the prepared Li4Ti5O12 is spherical, and the accumulation density is high. The process is easy for doping and carbon dosing so as to increase the electric conductivity of products, and the method has great application value.

Description

The spherical Li of lithium ion battery negative material 4Ti 5O 12The preparation method
Technical field
The present invention relates to the spherical Li of a kind of preparation lithium ion battery negative material 4Ti 5O 12Technology, belong to Chemical Engineering and field of new.
Background technology
The negative material of lithium ion battery adopts various embedding lithium material with carbon elements mostly at present, but still there are some shortcomings in material with carbon element as lithium ion battery negative material: first charge-discharge efficiency is low; Have an effect with electrolyte; There is tangible voltage delay phenomenon; Preparation method's more complicated of material with carbon element.Compare with the carbon negative pole in the lithium ion battery, though the alloy type negative material generally has higher specific capacity, the embedding repeatedly of lithium is taken off and is caused the change in volume of alloy type electrode in charge and discharge process bigger, and efflorescence was lost efficacy gradually, thereby cycle performance is relatively poor.Therefore, seek cheap easily preparation, good cycle, new negative material safe and reliable and that have a good electric chemical property are problems highly significant.Spinel type lithium titanate (Li 4Ti 5O 12) have remarkable advantages as lithium ion battery negative material: be a kind of unstressed insertion material, recurring structure does not change in charge and discharge process, good cycle; Good charge and discharge platform is arranged; Theoretical specific capacity is 175mAh/g, and actual specific capacity can reach 165mAh/g, and concentrates on land regions; Do not react with electrolyte; Low price, preparation easily.But, all do not solve poorly conductive and low density problem well from present achievement in research.
Summary of the invention
The objective of the invention is to propose the spherical Li of a kind of preparation 4Ti 5O 12New technology, improving the tap density of this material, and the doping by carbon dope and transition metal (for example Co, Mn, Cr, La, Y etc.), improve the conductivity of material.
Technical scheme of the present invention is as follows:
The spherical Li of preparation that the present invention is designed 4Ti 5O 12Technology, comprise following each step:
1) takes by weighing a certain amount of TiCl 4, under stirring condition, drip deionized water, make its hydrolysis, make the TiO that concentration is 2～5mol/L 2NH 2The O Sol A;
2) be to take by weighing certain amount of urea and hexamethylenetetramine at 1～5: 1 by mass ratio, add deionized water and make its dissolving, make the solution B that concentration is 200～400g/L;
3) in 0 ℃～10 ℃ temperature range and under the stirring condition, the B drips of solution is added in the A colloidal sol, make new colloidal sol;
4) with kerosene be dispersant, the span80 that adds 0.1%-5% therein is as surfactant; With the 3rd) colloidal sol that makes of step slowly is added dropwise in the dispersant under stirring condition, is warming up to 70～80 ℃ after being added dropwise to complete, and be incubated to stop heating and stirring after 10～20 minutes, and gel precipitation is come out;
5) centrifugation of step 4) gained gel is obtained xerogel, with concentration be 0.5～0.7% soil temperature 80 (tween80) aqueous solution 60～70 ℃ of washings once, more at normal temperatures with deionized water washed twice at least; Then with concentration be 1～10% ammoniacal liquor with gained xerogel ageing 24～48 hours, dry after the centrifugation, obtain spherical presoma;
6) be that 4: 5 ratio takes by weighing Li in lithium titanium mol ratio 2CO 3Or LiOH, mix with the spherical presoma of step 5) gained, make uniform powder;
7) powder with the step 6) gained promptly obtains spherical Li 700 ℃～900 ℃ following heat treatments after 10～20 hours 4Ti 5O 12Product.
The spherical Li that the present invention also provides a kind of lithium ion battery negative material to mix 4Ti 5O 12The preparation method is characterized in that this method carries out according to the following steps:
1) takes by weighing a certain amount of TiCl 4, under stirring condition, drip deionized water, make its hydrolysis, make the TiO that concentration is 2～5mol/L 2NH 2O colloidal sol takes by weighing M (CH for M/Ti=1%-10% more in molar ratio 3COO) 2, wherein M=Co, Mn, Cr, La or Y make in its colloidal sol that is dissolved in gained, are designated as Sol A;
2) be to take by weighing certain amount of urea and hexamethylenetetramine at 1～5: 1 by mass ratio, add deionized water and make its dissolving, make the solution B that concentration is 200～400g/L;
3) in 0 ℃～10 ℃ temperature range and under the stirring condition, the B drips of solution is added in the A colloidal sol, make new colloidal sol;
4) with kerosene be medium, the class of department 80 that adds 0.1%-5% therein is as surfactant; With the 3rd) colloidal sol that makes of step slowly is added dropwise in the medium under stirring condition, is warming up to 70～80 ℃ after being added dropwise to complete, and be incubated to stop heating and stirring after 10～20 minutes, and gel precipitation is come out;
5) centrifugation of step 4) gained gel is obtained xerogel, with concentration be 0.5～0.7% soil temperature 80 aqueous solution 60～70 ℃ of washings once, more at normal temperatures with deionized water washed twice at least; Then with concentration be 1～10% ammoniacal liquor with gained xerogel ageing 24～48 hours, dry after the centrifugation, obtain spherical presoma;
6) be that 4: 5 ratio takes by weighing Li in lithium titanium mol ratio 2CO 3Or LiOH, mix with the spherical presoma of step 5) gained, make uniform powder;
7) powder with the step 6) gained promptly obtains spherical Li 700 ℃～900 ℃ following heat treatments after 10～20 hours 4Ti 5O 12Product.
The present invention also provides a kind of spherical Li of lithium ion battery negative material carbon dope 4Ti 5O 12The preparation method is characterized in that this method carries out according to the following steps:
1) takes by weighing a certain amount of TiCl 4, under stirring condition, drip deionized water, make its hydrolysis, make the TiO that concentration is 2～5mol/L 2NH 2The O Sol A;
2) be to take by weighing certain amount of urea and hexamethylenetetramine at 1～5: 1 by mass ratio, add deionized water and make its dissolving, make the solution B that concentration is 200～400g/L;
3) in 0 ℃～10 ℃ temperature range and under the stirring condition, the B drips of solution is added in the A colloidal sol, make new colloidal sol, the mole according to institute's titaniferous in the colloidal sol calculates Li by stoichiometric proportion earlier 4Ti 5O 12Amount, will account for Li 4Ti 5O 12Mass percent be that 1%～10% graphite adds in the colloidal sol, the triton x-100 that adds 0.1%-5% simultaneously is as surfactant, stirs to make graphite be scattered in the colloidal sol equably;
4) with kerosene be medium, the class of department 80 that adds 0.1%-5% therein is as surfactant; With the 3rd) colloidal sol that makes of step slowly is added dropwise in the medium under stirring condition, is warming up to 70～80 ℃ after being added dropwise to complete, and be incubated to stop heating and stirring after 10～20 minutes, and gel precipitation is come out;
5) centrifugation of step 4) gained gel is obtained xerogel, with concentration be 0.5～0.7% soil temperature 80 aqueous solution 60～70 ℃ of washings once, more at normal temperatures with deionized water washed twice at least; Then with concentration be 1～10% ammoniacal liquor with gained xerogel ageing 24～48 hours, dry after the centrifugation, obtain spherical presoma;
6) be that 4: 5 ratio takes by weighing Li in lithium titanium mol ratio 2CO 3Or LiOH, mix with the spherical presoma of step 5) gained, make uniform powder;
7) with the powder of step 6) gained in the tube furnace of logical argon gas or nitrogen 700 ℃ promptly obtain carbon-doped spherical Li after-900 ℃ of following heat treatment 10-20 hours 4Ti 5O 12Product.
The present invention compared with prior art, have the following advantages and the high-lighting effect: technological process of the present invention is simple; Adopted a kind of new method to prepare Li 4Ti 5O 12Material; The Li for preparing 4Ti 5O 12Product is spherical in shape, the bulk density height; This technology is easy to realize mixing and carbon dope, to improve the conductivity of product, has very big using value.
Embodiment
Introduce embodiments of the invention below:
Embodiment 1:
Take by weighing 10gTiCl 4Insert in the beaker, add about 20ml deionized water, the TiO that hydrolysis must about 2.9mol/L 2NH 2The O Sol A.Take by weighing hexamethylenetetramine (methenamine) more respectively and each 4.5g of urea inserts in another beaker, add the solution B of about 20ml deionized water dissolving.Under temperature is 10 ℃ and stirring condition, the B drips of solution is added in the A colloidal sol, make new colloidal sol.With kerosene is medium, add 1% class of department 80 more therein as surfactant, the colloidal sol that newly makes slowly is added dropwise in the medium under stirring condition, be warming up to 70 ℃ after being added dropwise to complete, be incubated and stop heating after 10 minutes and stir, gel precipitation is come out.Centrifugation obtains xerogel, with concentration be 0.7% soil temperature 80 aqueous solution 70 ℃ of washings once, at room temperature use the deionized water washed twice again, be 5% ammoniacal liquor ageing 24 hours with concentration again, dry after the centrifugation, promptly obtain spherical presoma.Li: Ti=4 in molar ratio: 5 ratio takes by weighing Li 2CO 3, even with the spherical presoma ground and mixed that obtains, promptly obtain spherical Li after 16 hours 800 ℃ of following heat treatments 4Ti 5O 12Product.The tap density that records this sample is 1.55g/cm 3Take by weighing this sample of 71.8mg, with sample powder, acetylene black and the PTFE mixed with 8: 1: 1, be pressed into electrode slice, as anodal, make negative pole with the pure metal lithium sheet after vacuumize, recording this sample is 0.16mA/cm in current density 2Specific discharge capacity when discharging and recharging is 168mAh/g.
Embodiment 2:
Take by weighing 15gTiCl 4Insert in the beaker, add about 20ml deionized water, the TiO that hydrolysis must about 4.5mol/L 2NH 2The O Sol A.Take by weighing hexamethylenetetramine (methenamine) 4.5g more respectively and each 9g of urea inserts in another beaker, add the solution B of about 20ml deionized water dissolving.Under temperature is 5 ℃ and stirring condition, the B drips of solution is added in the A colloidal sol, make new colloidal sol.With kerosene is medium, add 0.5% class of department 80 more therein as surfactant, the colloidal sol that newly makes slowly is added dropwise in the medium under stirring condition, is warming up to 75 ℃ after being added dropwise to complete, be incubated and stop heating after 10 minutes and stir gel precipitation is come out.Centrifugation obtains xerogel, with concentration be 0.5% soil temperature 80 aqueous solution 65 ℃ of washings once, at room temperature use the deionized water washed twice again, be 1% ammoniacal liquor ageing 24 hours with concentration again, dry after the centrifugation, promptly obtain spherical presoma.Li: Ti=4 in molar ratio: 5 ratio takes by weighing Li 2CO 3, even with the spherical presoma ground and mixed that obtains, promptly obtain spherical Li after 20 hours 850 ℃ of following heat treatments 4Ti 5O 12Product.The tap density that records this sample is 1.50g/cm 3Take by weighing this sample of 71.8mg, with sample powder, acetylene black and the PTFE mixed with 8: 1: 1, be pressed into electrode slice, as anodal, make negative pole with the pure metal lithium sheet after vacuumize, recording this sample is 0.16mA/cm in current density 2Specific discharge capacity when discharging and recharging is 167mAh/g.
Embodiment 3:
Take by weighing 15gTiCl 4Insert in the beaker, add about 20ml deionized water, the TiO that hydrolysis must about 5mol/L 2NH 2The O Sol A.Take by weighing hexamethylenetetramine (methenamine) 4.5g more respectively and each 22.5g of urea inserts in another beaker, add the solution B of about 40ml deionized water dissolving.Under temperature is 10 ℃ and stirring condition, the B drips of solution is added in the A colloidal sol, make new colloidal sol.With kerosene is medium, add 5% class of department 80 more therein as surfactant, the colloidal sol that newly makes slowly is added dropwise in the medium under stirring condition, is warming up to 80 ℃ after being added dropwise to complete, be incubated and stop heating after 20 minutes and stir gel precipitation is come out.Centrifugation obtains xerogel, with concentration be 0.5% soil temperature 80 aqueous solution 69 ℃ of washings once, at room temperature use the deionized water washed twice again, be 10% ammoniacal liquor ageing 48 hours with concentration again, dry after the centrifugation, promptly obtain spherical presoma.Li: Ti=4 in molar ratio: 5 ratio takes by weighing Li 2CO 3, even with the spherical presoma ground and mixed that obtains, promptly obtain spherical Li after 10 hours 900 ℃ of following heat treatments 4Ti 5O 12Product.The tap density that records this sample is 1.51g/cm 3Take by weighing this sample of 71.8mg, with sample powder, acetylene black and the PTFE mixed with 8: 1: 1, be pressed into electrode slice, as anodal, make negative pole with the pure metal lithium sheet after vacuumize, recording this sample is 0.16mA/cm in current density 2Specific discharge capacity when discharging and recharging is 166mAh/g.
Embodiment 4:
The method identical with embodiment 1 makes the TiO of about 2.9mol/L earlier 2NH 2The O Sol A takes by weighing the Co (CH of 0.27g 3COO) 24H 2O is dissolved in the Sol A, again by making the spherical Li that mixes Co with embodiment 1 identical step 4Ti 5O 12Product.The tap density that records this sample is 1.56g/cm 3Identical with the anode formula of embodiment 1, recording this sample is 0.8mA/cm in current density 2Specific discharge capacity when discharging and recharging is 165mAh/g.
Embodiment 5:
Method by embodiment 3 makes the spherical Li that mixes Mn 4Ti 5O 12The tap density that records this sample is 1.53g/cm 3Identical with the anode formula of embodiment 1, recording this sample is 0.8mA/cm in current density 2Specific discharge capacity when discharging and recharging is 160mAh/g.
Embodiment 6:
Method by embodiment 3 makes the spherical Li that mixes Cr 4Ti 5O 12The tap density that records this sample is 1.54g/cm 3Identical with the anode formula of embodiment 1, recording this sample is 0.8mA/cm in current density 2Specific discharge capacity when discharging and recharging is 162mAh/g.
Embodiment 7:
Method by embodiment 3 makes the spherical Li that mixes La 4Ti 5O 12The tap density that records this sample is 1.52g/cm 3Identical with the anode formula of embodiment 1, recording this sample is 0.8mA/cm in current density 2Specific discharge capacity when discharging and recharging is 161mAh/g.
Embodiment 8:
The method identical with embodiment 1 makes mixed sols earlier.Take by weighing 0.5g graphite and add in the colloidal sol, add 1% triton x-100 again, graphite is scattered in the colloidal sol equably as surfactant.Make the spherical Li of carbon dope again by the step identical with embodiment 1 4Ti 5O 12The tap density that records this sample is 1.46g/cm 3Identical with the anode formula of embodiment 1, recording this sample is 0.8mA/cm in current density 2Specific discharge capacity when discharging and recharging is 167mAh/g.
Comparing embodiment 1:
Take by weighing 17.4gTiO 2And 6.44gLi 2CO 3, insert in the crucible after ground and mixed is even, 800 ℃ of heat treatments made Li after 16 hours in Muffle furnace 4Ti 5O 12The tap density that records this sample is 0.72g/cm 3Identical with the anode formula of embodiment one, recording this sample is 0.16mA/cm in current density 2Specific discharge capacity when discharging and recharging is 163mAh/g.
Comparing embodiment 2:
Take by weighing 17.4gTiO 2, 6.44gLi 2CO 3With 1g graphite, ground and mixed is inserted in the crucible after evenly, and 800 ℃ of heat treatment makes the Li of carbon dope after 16 hours in the tube furnace of logical argon gas 4Ti 5O 12The tap density that records this sample is 0.65g/cm 3Identical with the anode formula of embodiment six, recording this sample is 0.8mA/cm in current density 2Specific discharge capacity when discharging and recharging is 165mAh/g.
Comparing embodiment 3:
With LiOHH 2O is dissolved in the water and is mixed with concentration is 12% the aqueous solution, again with TiO 2Powder adds in the solution, and colloidal sol with spray-dired method drying, makes Li 800 ℃ of heat treatments after 3 hours again in the time of 110 ℃ 4Ti 5O 12The tap density that records this sample is 0.8g/cm 3Identical with the anode formula of embodiment one, recording this sample is 0.16mA/cm in current density 2Specific discharge capacity when discharging and recharging is 160mAh/g.

Claims (3)

1. the spherical Li of a lithium ion battery negative material 4Ti 5O 12The preparation method, it is characterized in that this method carries out according to the following steps:
1) takes by weighing a certain amount of TiCl 4, under stirring condition, drip deionized water, make its hydrolysis, make the TiO that concentration is 2～5mol/L 2NH 2The O Sol A;
2) be to take by weighing urea and hexamethylenetetramine at 1～5: 1 by mass ratio, add deionized water and make its dissolving, make the solution B that concentration is 200～400g/L;
3) in 0 ℃～10 ℃ temperature range and under the stirring condition, the B drips of solution is added in the A colloidal sol, make new colloidal sol;
4) with kerosene be medium, the class of department 80 that adds 0.1%-5% therein is as surfactant; With the 3rd) colloidal sol that makes of step slowly is added dropwise in the medium under stirring condition, is warming up to 70～80 ℃ after being added dropwise to complete, and be incubated to stop heating and stirring after 10～20 minutes, and gel precipitation is come out;
5) centrifugation of step 4) gained gel is obtained xerogel, with concentration be 0.5～0.7% soil temperature 80 aqueous solution 60～70 ℃ of washings once, more at normal temperatures with deionized water washed twice at least; Then with concentration be 1～10% ammoniacal liquor with gained xerogel ageing 24～48 hours, dry after the centrifugation, obtain spherical presoma;
6) be that 4: 5 ratio takes by weighing Li in lithium titanium mol ratio 2CO 3Or LiOH, mix with the spherical presoma of step 5) gained, make uniform powder;
7) powder with the step 6) gained promptly obtains spherical Li 700 ℃～900 ℃ following heat treatments after 10～20 hours 4Ti 5O 12Product.
2. the spherical Li that mixes of a lithium ion battery negative material 4Ti 5O 12The preparation method is characterized in that this method carries out according to the following steps:
1) takes by weighing a certain amount of TiCl 4, under stirring condition, drip deionized water, make its hydrolysis, make the TiO that concentration is 2～5mol/L 2NH 2The O Sol A takes by weighing M (CH for M/Ti=1%-10% more in molar ratio 3COO) 2, wherein M=Co, Mn, Cr, La or Y make in its colloidal sol that is dissolved in gained;
2) be to take by weighing urea and hexamethylenetetramine at 1～5: 1 by mass ratio, add deionized water and make its dissolving, make the solution B that concentration is 200～400g/L;
3) in 0 ℃～10 ℃ temperature range and under the stirring condition, the B drips of solution is added step 2) in the colloidal sol of preparation, make new colloidal sol;
4) with kerosene be medium, the class of department 80 that adds 0.1%-5% therein is as surfactant; With the 3rd) colloidal sol that makes of step slowly is added dropwise in the medium under stirring condition, is warming up to 70～80 ℃ after being added dropwise to complete, and be incubated to stop heating and stirring after 10～20 minutes, and gel precipitation is come out;
5) centrifugation of step 4) gained gel is obtained xerogel, with concentration be 0.5～0.7% soil temperature 80 aqueous solution 60～70 ℃ of washings once, more at normal temperatures with deionized water washed twice at least; Then with concentration be 1～10% ammoniacal liquor with gained xerogel ageing 24～48 hours, dry after the centrifugation, obtain spherical presoma;
6) be that 4: 5 ratio takes by weighing Li in lithium titanium mol ratio 2CO 3Or LiOH, mix with the spherical presoma of step 5) gained, make uniform powder;
7) powder of step 6) gained is promptly obtained the spherical Li that mixes after 10～20 hours 700 ℃～900 ℃ following heat treatments 1Ti 5O 12Product.
3. the spherical Li of a lithium ion battery negative material carbon dope 4Ti 5O 12The preparation method is characterized in that this method carries out according to the following steps:
1) takes by weighing a certain amount of TiCl 4, under stirring condition, drip deionized water, make its hydrolysis, make the TiO that concentration is 2～5mol/L 2NH 2The O Sol A;
2) be to take by weighing certain amount of urea and hexamethylenetetramine at 1～5: 1 by mass ratio, add deionized water and make its dissolving, make the solution B that concentration is 200～400g/L;
3) in 0 ℃～10 ℃ temperature range and under the stirring condition, the B drips of solution is added in the A colloidal sol, make new colloidal sol, the mole according to institute's titaniferous in the colloidal sol calculates Li by stoichiometric proportion earlier 4Ti 5O 12Amount, will account for Li 4Ti 5O 12Mass percent be that 1%～10% graphite adds in the colloidal sol, the triton x-100 that adds 0.1%-5% simultaneously is as surfactant, stirs to make graphite be scattered in the colloidal sol equably;
4) with kerosene be medium, the class of department 80 that adds 0.1%-5% therein is as surfactant; With the 3rd) colloidal sol that makes of step slowly is added dropwise in the medium under stirring condition, is warming up to 70～80 ℃ after being added dropwise to complete, and be incubated to stop heating and stirring after 10～20 minutes, and gel precipitation is come out;
5) centrifugation of step 4) gained gel is obtained xerogel, with concentration be 0.5～0.7% soil temperature 80 aqueous solution 60～70 ℃ of washings once, more at normal temperatures with deionized water washed twice at least; Then with concentration be 1～10% ammoniacal liquor with gained xerogel ageing 24～48 hours, dry after the centrifugation, obtain spherical presoma;
6) be that 4: 5 ratio takes by weighing Li in lithium titanium mol ratio 2CO 3Or LiOH, mix with the spherical presoma of step 5) gained, make uniform powder;
7) with the powder of step 6) gained in the tube furnace of logical argon gas or nitrogen 700 ℃ promptly obtain carbon-doped spherical Li after-900 ℃ of following heat treatment 10-20 hours 4Ti 5O 12Product.
CNB2004100989443A 2004-12-17 2004-12-17 Preparation method of spherical Li4Ti5O12 as lithium ion cell cathode material Expired - Fee Related CN1275342C (en)

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JP4213688B2 (en) * 2005-07-07 2009-01-21 株式会社東芝 Nonaqueous electrolyte battery and battery pack
CN1305166C (en) * 2005-07-28 2007-03-14 黑龙江中强能源科技有限公司 Nano-lithium ion cell and mfg. method thereof
CN100411994C (en) * 2006-07-07 2008-08-20 清华大学 Process for preparing carbon-doped spherical Li4Ti5O12
DE102007058674A1 (en) 2007-12-06 2009-07-02 Süd-Chemie AG Nanoparticulate composition and process for its preparation
CN101373829B (en) * 2008-10-07 2011-05-11 深圳市贝特瑞新能源材料股份有限公司 Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery
CN101656310B (en) * 2009-09-10 2011-05-04 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing spinel-type lithium titanate as negative electrode material of lithium-ion battery
CN102104142B (en) * 2009-12-16 2013-11-06 清华大学 Ion-doped spherical Li4Ti5O12/C lithium ion battery anode material and preparation method thereof
CN101847716B (en) * 2010-05-14 2013-07-10 北大先行科技产业有限公司 Method for preparing spherical lithium titanate cathode material
KR20130080019A (en) * 2010-05-21 2013-07-11 이 아이 듀폰 디 네모아 앤드 캄파니 Process for making titanium compounds
WO2013002729A1 (en) * 2011-06-27 2013-01-03 National University Of Singapore Production of nanostructured li4ti5o12 with superior high rate performance
CN103579597B (en) * 2012-07-24 2015-09-09 上海纳米技术及应用国家工程研究中心有限公司 Lithium ion secondary battery cathode material lithium titanate composite material and preparation method
JP6299871B2 (en) * 2014-07-30 2018-03-28 セントラル硝子株式会社 Lithium titanate composite product precursor and method for producing the same
CN104505504B (en) * 2014-12-12 2017-04-12 中国科学院上海硅酸盐研究所 Gel-solid phase synthesis method for nanometer lithium titanate
CN110627114B (en) * 2019-08-23 2022-06-03 江门市宏力能源有限公司 Modified lithium titanate negative electrode material and preparation method thereof

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