CN103730648A - Preparation method of lithium titanate for negative electrode of lithium battery - Google Patents
Preparation method of lithium titanate for negative electrode of lithium battery Download PDFInfo
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- CN103730648A CN103730648A CN201310605946.6A CN201310605946A CN103730648A CN 103730648 A CN103730648 A CN 103730648A CN 201310605946 A CN201310605946 A CN 201310605946A CN 103730648 A CN103730648 A CN 103730648A
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- lithium
- titanate
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- suspension liquid
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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
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- 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
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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
- 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 invention relates to a preparation method of lithium titanate for a negative electrode of a lithium battery, and belongs to the technical field of battery manufacturing. The preparation method comprises steps as follows: step one, lithium hydroxide, metatitanic acid and potassium titanate whisker are taken and added into deionized water, the mixture is heated, and a suspension liquid is obtained; step two, silver-plated copper powder, a titanate coupling agent and a surface active agent are added into the suspension liquid, stirred uniformly and heated, and a modified suspension liquid is obtained; step three, a silver chloride solution is added into the modified suspension liquid under the action of ultrasonic dispersion and mixed uniformly, an ammonium hydrogen carbonate solution is added, the mixture is mixed uniformly, and a coated suspension liquid is obtained; and step four, the coated suspension liquid is filtered by a micro-filtration membrane, obtained particles are sintered and cooled to the room temperature, and the lithium titanate is obtained. According to the preparation method, through modification of lithium titanate, a better conductive coating is formed on the surface of lithium titanate, particles are more tightly combined, and high and excellent charge-discharge capacitance of the battery is ensured.
Description
Technical field
The preparation method who the present invention relates to a kind of lithium titanate of cathode of lithium battery use, belongs to battery manufacture technical field.
Background technology
The performance requirement of lithium ion battery negative material includes: 1., in the process of carrying out the embedding of lithium ion and deviate from, guarantee that electrode has good reversibility; 2. embed compound and there is good chemical stability higher voltage range planted agent; 3. embed compound and should there is good electronic conductivity and ionic conductivity; 4. lithium ion should be large as much as possible at the chemical diffusion coefficient embedding in compound; 5. there is a large amount of interfacial structures and apparent structure, be conducive to increase the locus of embedding lithium, improve embedding lithium capacity, can deviate from preferably again lithium ion simultaneously; 6. source is wider, and low price, does not produce larger pollution etc. to environment.
In negative material, spinel type lithium titanate charging times is more, charging process is faster.Its advantage has: 1. at lithium ion, embed, almost do not have change in volume to be called as " zero strain " material in deviating from process, thereby have good cycle performance and stable discharge voltage; 2. there is relatively high electrode voltage, avoided reacting with electrolyte and the negative material that produces decomposes; 3. compared with carbon negative pole material, lithium titanate has higher lithium ion diffusion coefficient, makes this negative material can be rapid, many cycle charge-discharges under high magnification; 4. the electromotive force of lithium titanate is higher than pure lithium metal, is difficult for producing Li dendrite, has improved the security performance of battery.Shortcoming has: 1. electronic conductivity is lower; 2. as negative material, the voltage platform of lithium titanate is too high, thereby the voltage that battery externally can be provided reduces; 3. charge/discharge capacity more than 1V is less than carbon negative pole material (200～400 mAh/g).
Spinel-type Li
4ti
5o
12preparation method mainly include: 1. high temperature solid-state method, its advantage is easy and simple to handle, is easy to suitability for industrialized production; Shortcoming is that synthesis temperature is high, and sintering time is long, and energy consumption is large, and production efficiency is low, and the particle diameter of product distributes and is not easy to control, uniformity, and consistency and reappearance are poor.2. the precipitation method, its advantage is simple; Shortcoming is that purity is low, and particle radius is large; 3. sol-gal process, its advantage be there is more uniform appearance, narrower particle diameter distributes, and causes it to have good chemical property; Shortcoming is that the method all can be introduced large weight organic compounds conventionally, makes building-up process become comparatively complicated, is not suitable for practical application; 4. hydro thermal method, its advantage is that particle size distribution is narrower, and particle surface is more even, and shortcoming is sometimes to react with container.
Summary of the invention
The object of the invention is: the lithium titanate that provides a kind of cathode of lithium battery with high charge-discharge capacity to use, adopts following technical scheme:
A preparation method for the lithium titanate that cathode of lithium battery is used, comprises the steps:
The 1st step, by weight, gets 2～3 parts of lithium hydroxides, 4～5 parts of metatitanic acids, 0.2～0.4 part of potassium titanate crystal whisker, adds the deionized water of 50～80 parts, is heated to 40～50 ℃, keeps 4～6 hours, obtains suspension;
The 2nd step, in suspension, add silver-plated copper powder 2～4 weight portions, titanate coupling agent 4～8 weight portions, surfactant 1～4 weight portion, stir, be heated to 50～60 ℃, keep 3～5 hours, obtain modified suspension;
The 3rd step, by modified suspension under the effect of ultrasonic dispersion, add the silver chlorate solution of 1～2 weight portion, after mixing, add again ammonium bicarbonate soln 5～10 weight portions of mass concentration 5%, after mixing, place 12～20 hours, obtain coated suspension;
The 4th step, will be coated suspension micro-filtrate membrane filtration, the particle of gained sintering 3～6 hours at 800～1200 ℃, is cooled to room temperature.
Preferably, described anion surfactant is neopelex.
Preferably, the particle diameter of described silver-plated copper powder is between 50～200 microns.
Described titanate coupling agent is NDZ-401.
beneficial effect
The present invention, by lithium titanate is carried out to modification, makes its surface have the coated coating of better conduction, between particle, in conjunction with tightr, has guaranteed that battery has good high charge-discharge capacity.
Embodiment
Embodiment 1
The 1st step, get lithium hydroxide 2Kg, metatitanic acid 4Kg, potassium titanate crystal whisker 0.2Kg, add the deionized water of 50Kg, be heated to 40 ℃, keep 4 hours, obtain suspension;
The 2nd step, in suspension, add silver-plated copper powder 2Kg, titanate coupling agent 4Kg, surfactant 1Kg, stir, be heated to 50 ℃, keep 3 hours, obtain modified suspension;
The 3rd step, by modified suspension under the effect of ultrasonic dispersion, add the silver chlorate solution of 1Kg, after mixing, then add the ammonium bicarbonate soln 5Kg of mass concentration 5%, after mixing, place 12 hours, obtain coated suspension;
The 4th step, will be coated suspension micro-filtrate membrane filtration, the particle of gained sintering 3 hours at 800 ℃, is cooled to room temperature.
Described anion surfactant is neopelex, and the particle diameter of described silver-plated copper powder is between 50～200 microns, and described titanate coupling agent is NDZ-401.
Embodiment 2
The 1st step, get lithium hydroxide 3Kg, metatitanic acid 5Kg, potassium titanate crystal whisker 0.4Kg, add the deionized water of 80Kg, be heated to 50 ℃, keep 6 hours, obtain suspension;
The 2nd step, in suspension, add silver-plated copper powder 4Kg, titanate coupling agent 8Kg, surfactant 4Kg, stir, be heated to 60 ℃, keep 5 hours, obtain modified suspension;
The 3rd step, by modified suspension under the effect of ultrasonic dispersion, add the silver chlorate solution of 2Kg, after mixing, then add the ammonium bicarbonate soln 10Kg of mass concentration 5%, after mixing, place 20 hours, obtain coated suspension;
The 4th step, will be coated suspension micro-filtrate membrane filtration, the particle of gained sintering 6 hours at 1200 ℃, is cooled to room temperature.
Described anion surfactant is neopelex, and the particle diameter of described silver-plated copper powder is between 50～200 microns, and described titanate coupling agent is NDZ-401.
Embodiment 3
The 1st step, get lithium hydroxide 3Kg, metatitanic acid 5Kg, potassium titanate crystal whisker 0.3Kg, add the deionized water of 70Kg, be heated to 45 ℃, keep 5 hours, obtain suspension;
The 2nd step, in suspension, add silver-plated copper powder 3Kg, titanate coupling agent 7Kg, surfactant 3Kg, stir, be heated to 55 ℃, keep 4 hours, obtain modified suspension;
The 3rd step, by modified suspension under the effect of ultrasonic dispersion, add the silver chlorate solution of 1Kg, after mixing, then add the ammonium bicarbonate soln 6Kg of mass concentration 5%, after mixing, place 15 hours, obtain coated suspension;
The 4th step, will be coated suspension micro-filtrate membrane filtration, the particle of gained sintering 4 hours at 1000 ℃, is cooled to room temperature.
Described anion surfactant is neopelex, and the particle diameter of described silver-plated copper powder is between 50～200 microns, and described titanate coupling agent is NDZ-401.
Performance test
The negative electrode active material powder, acetylene black and the PVDF that make are mixed according to mass ratio 80:10:10, add appropriate organic solvent 1-METHYLPYRROLIDONE, be mixed into pasty state, on Copper Foil, paint the uniform films that thickness is 100 μ m, be put in dry 10h in 90 ℃ of baking ovens, after compressing tablet, make negative plate.Take commercial LiCo0 pole piece as anodal, electrolyte is by electrolyte LiPF6 and ethylene carbonate/1,2-dimethyl carbonate is according to the mixed solution composition of volume ratio 1:1, take microporous polypropylene membrane as barrier film, be assembled into button cell and test, at 2.8～3.4V, at room temperature with the constant current of 20mA/g, discharge and recharge, carry out charge-discharge performance test, take the lithium ion battery negative material in patent CN1549363 as contrast.Result is as shown in the table.
As can be seen from the table, the present invention makes the lithium titanate obtaining when as negative material, and its discharge capacity is obviously better than like product, and after multiple discharge, its discharge capacity loss is little.
Claims (4)
1. a preparation method for the lithium titanate that cathode of lithium battery is used, is characterized in that, comprises the steps:
The 1st step, by weight, gets 2～3 parts of lithium hydroxides, 4～5 parts of metatitanic acids, 0.2～0.4 part of potassium titanate crystal whisker, adds the deionized water of 50～80 parts, is heated to 40～50 ℃, keeps 4～6 hours, obtains suspension;
The 2nd step, in suspension, add silver-plated copper powder 2～4 weight portions, titanate coupling agent 4～8 weight portions, surfactant 1～4 weight portion, stir, be heated to 50～60 ℃, keep 3～5 hours, obtain modified suspension;
The 3rd step, by modified suspension under the effect of ultrasonic dispersion, add the silver chlorate solution of 1～2 weight portion, after mixing, add again ammonium bicarbonate soln 5～10 weight portions of mass concentration 5%, after mixing, place 12～20 hours, obtain coated suspension;
The 4th step, will be coated suspension micro-filtrate membrane filtration, the particle of gained sintering 3～6 hours at 800～1200 ℃, is cooled to room temperature.
2. the preparation method of the lithium titanate that cathode of lithium battery according to claim 1 is used, is characterized in that: described anion surfactant is neopelex.
3. the preparation method of the lithium titanate that cathode of lithium battery according to claim 1 is used, is characterized in that: the particle diameter of described silver-plated copper powder is between 50～200 microns.
4. the preparation method of the lithium titanate that cathode of lithium battery according to claim 1 is used, is characterized in that: described titanate coupling agent is NDZ-401.
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| CN103730648B CN103730648B (en) | 2016-04-27 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6350570A (en) * | 1986-08-12 | 1988-03-03 | ニツカン工業株式会社 | Metal plated alkali titanate and its production |
| JP2008103118A (en) * | 2006-10-17 | 2008-05-01 | Nissan Motor Co Ltd | Electrode for battery |
| CN101462765A (en) * | 2008-11-24 | 2009-06-24 | 万向电动汽车有限公司 | Method for preparing lithium ionic cell cathode material spinelle lithium titanate |
| CN102610824A (en) * | 2012-03-26 | 2012-07-25 | 上海大学 | Preparation method of lithium titanate (Li4Ti5O12)/Ag composite lithium-ion negative electrode materials |
-
2013
- 2013-11-26 CN CN201310605946.6A patent/CN103730648B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6350570A (en) * | 1986-08-12 | 1988-03-03 | ニツカン工業株式会社 | Metal plated alkali titanate and its production |
| JP2008103118A (en) * | 2006-10-17 | 2008-05-01 | Nissan Motor Co Ltd | Electrode for battery |
| CN101462765A (en) * | 2008-11-24 | 2009-06-24 | 万向电动汽车有限公司 | Method for preparing lithium ionic cell cathode material spinelle lithium titanate |
| CN102610824A (en) * | 2012-03-26 | 2012-07-25 | 上海大学 | Preparation method of lithium titanate (Li4Ti5O12)/Ag composite lithium-ion negative electrode materials |
Non-Patent Citations (1)
| Title |
|---|
| 邓昭平等: "含部分晶须的钛酸锂的制备及其性能表征", 《矿物岩石》 * |
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Address after: 226100 No.888, Jiuhua Road, high tech Zone, Nantong City, Jiangsu Province Patentee after: Wotai Energy Co.,Ltd. Address before: 226300 Yingcai building, Dongda science and Technology Park, 788 Century Avenue, high tech Zone, Nantong City, Jiangsu Province Patentee before: NEOVOLTAIC ENERGY NANTONG Co.,Ltd. |