CN102820458A - Synthetic method of nitrogen-enriched carbon coated lithium titanate composite material prepared by introduction of ionic liquid as carbon source - Google Patents

Synthetic method of nitrogen-enriched carbon coated lithium titanate composite material prepared by introduction of ionic liquid as carbon source Download PDF

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CN102820458A
CN102820458A CN2012101965188A CN201210196518A CN102820458A CN 102820458 A CN102820458 A CN 102820458A CN 2012101965188 A CN2012101965188 A CN 2012101965188A CN 201210196518 A CN201210196518 A CN 201210196518A CN 102820458 A CN102820458 A CN 102820458A
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carbon
lithium titanate
lithium
carry
coats
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CN2012101965188A
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杨茂萍
杨续来
郭钰静
王康平
谢佳
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合肥国轩高科动力能源有限公司
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a synthetic method of a nitrogen-enriched carbon coated lithium titanate composite material prepared by the introduction of an ionic liquid as a carbon source. The synthetic method comprises the following steps of: 1) weighing lithium salt, titanium dioxide and the carbon source in proportion, adding alcohol, carrying out ball milling dispersion, and carrying out vacuum drying to prepare a precursor; 2) sintering the prepared precursor at the temperature of 750-950 DEG C under the protection of an inert atmosphere so as to preliminarily obtain lithium titanate with a carbon material coated on the surface; and 3) adding the ionic liquid and deionized water in proportion into the preliminarily obtained carbon-coated lithium titanate, carrying out ball milling, stirring and sintering. The lithium titanate composite material has a spherical morphology of nano-primary particle composed micrometer secondary particles, and the surface of the lithium titanate composite material is uniformly coated with a layer of nitrogen-enriched carbon material. Its electronic conductivity is not only effectively raised, but surface stability of the material is also enhanced. The obtained material has excellent rate capability and cycle performance. In addition, gas expansion problem of lithium titanate cells is effectively improved. The nitrogen-enriched carbon coated lithium titanate composite material has a wide application prospect in the field of lithium ion battery.

Description

A kind of ionic liquid of introducing prepares the synthetic method that nitrogenous carbon coats lithium titanate composite material as carbon source
Technical field
The present invention relates to the preparation method that the nitrogenous carbon of a kind of lithium ion battery negative material coats lithium titanate composite material; Be particularly related to the method for in the material building-up process, taking the secondary coating and introduce ionic liquid and the lithium titanate surface is coated processing as carbon source; This coating layer is nitrogenous material with carbon element; Realize the raising of the cycle performance and the high rate performance of material, and effectively improved the flatulence problem of lithium titanate system battery, belonged to electrochemical material technology of preparing and new energy field.
Background technology
Along with environmental problem and energy crisis paid more and more attention, the development clean energy resource is imperative.In new forms of energy development, lithium ion battery is just towards direction develop activelies such as power vehicle and electrical network energy storage, develops to have high security, and the long life can realize that the lithium ion battery of fast charging and discharging has become the emphasis problem of industry research.
Present commercial lithium ion battery adopts material with carbon element as negative material mostly, but material with carbon element itself has some shortcomings: (1) can form the SEI film, and its first charge-discharge efficiency is low; (2) it is approaching by current potential and lithium metal current potential, can form Li dendrite during over-charging of battery, causes short circuit, causes safety problem; (3) has tangible voltage delay phenomenon; (4) be easy to electrolyte and react, cause the loss of electrolyte; The spinel lithium titanate material comes into one's own as lithium ion battery negative material day by day, and it is compared with business-like material with carbon element has incomparable advantage: it has higher Ti 4+/ Ti 3+(1.55V vs Li +/ Li) redox potential, its surface can not form the SEI film; It has spinel structure, and volume changes hardly in charge and discharge process, thereby it has the cycle life that is superior to carbon negative pole material; It has three-dimensional lithium ion diffusion admittance, and the high rate charge-discharge excellent performance is reacted in the embedding of taking off fast that helps lithium ion; It also has desirable charge and discharge platform, and charging finishes to have tangible voltage jump characteristic; Wide, the cleaning of its preparation raw material sources.This shows that lithium titanate material has characteristics such as cycle life is longer, safer, charging process is faster as lithium ion battery negative material of future generation, it has huge researching value and commercial application prospect as lithium ion battery negative material.
But the electronic conductivity of pure phase lithium titanate is very low, has influenced the charge-discharge performance as lithium ion battery electrode material, and especially therefore the poor-performing of its fast charging and discharging will be realized with carrying out modification to it with level.The common modified measures of taking mainly comprises two aspects at present: (1) synthesis of nano size lithium titanate material, the specific area of increase electrode material, the migration path of shortening lithium ion.Can increase the diffusion velocity of lithium ion in embedding process, guarantee the fast charging and discharging ability of lithium ion battery; (2) lithium titanate material is carried out metal cation and mix, it is right in the solid structure of material, to increase the duplet hole, increases the carrier concentration of material, to improve the electronic conductivity of lithium titanate.Research shows the conductivity that can improve lithium titanate through cation doping preferably, obviously improves the high-rate charge-discharge capability of lithium titanate anode; (3) introduce high conductive materials; In lithium titanate powdery, introduce the material (like metal, carbon etc.) of high conductivity, serve as conducting medium, evenly disperse or be coated on the particle surface of lithium titanate material; Form conductive network, improve the electric conductivity of combination electrode material.
In the prior art; Patent CN101777645A discloses a kind of preparation method of lithium titanate of carbon modification; Titanium dioxide, lithium carbonate, coating are mixed pulverizing with organic carbon source, doping with inorganic carbon source; Sintering under atmosphere protection obtains the pre-burning product and obtains the carbon-modified lithium titanate material through pulverizing mixing and sintering processes again, can effectively improve the cycle performance and the high rate performance of material; Patent CN102013476A discloses and in the lithium titanate building-up process, has introduced solid-state nitrogenous source, obtains a kind of lithium titanate/titanium nitride composite material, has improved the high rate during charging-discharging of lithium titanate material; It is the logical superheated nitrogen of nitrogenous source one deck TiN film that has been reflected at the lithium titanate surface preparation that patent CN101728517A discloses with urea;
Above-mentioned preparation method has realized the modification of independent carbon or nitride, has certain feasibility, has realized among the present invention that kind nitrogen and carbon modifies the lithium titanate material surface simultaneously.
Summary of the invention
Technical problem to be solved by this invention provides a kind of nitrogen and material with carbon element is modified the lithium titanate material surface simultaneously; And owing to adopt the synthesis technique that secondary coats and introduced ionic liquid as carbon source, make lithium titanate material coated with uniform the nitrogenous material with carbon element of one deck.
In order to achieve the above object, the technical scheme taked of the present invention is:
A kind of ionic liquid of introducing prepares the synthetic method that nitrogenous carbon coats lithium titanate composite material as carbon source, and this lithium titanate composite material has the nanometer primary particle and forms a micron offspring spherical morphology, its coated with uniform the nitrogenous material with carbon element of one deck.
May further comprise the steps:
(1) mol ratio according to lithium, titanium, carbon is (4~4.4): 5: (greater than zero~2) takes by weighing lithium salts, titanium dioxide and organic carbon source; Adding dispersant places ball mill to carry out the stirring ball-milling processing; The ball milling time is 3-12 hour; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 80~120 degree, and be 8-16 hour drying time;
(2) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 750 ℃~950 ℃ with the heating rate of 2~25 ℃/min, is incubated 8~20 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats;
(3) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing ionic liquid according to 5%~30% the percentage that carbon coats the lithium titanate quality; And be blended into proper amount of deionized water and carry out once more Ball milling and handle; Slurries after finishing dealing with add appropriate amount of deionized water again or dispersant adjustment solid content of slurry is 10%~50%, carry out spray drying treatment again;
The dry powder that (4) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 500~900 ℃ of insulations 5-16 hour with the heating rate of 2~25 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
The described titanium dioxide of step (1) is the nanostructured anatase structure; Said lithium salts is selected from one or more combinations in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, the lithium fluoride; Said organic carbon source is selected from one or more combinations in glucose, sucrose, polyvinyl butyral resin, phenolic resins, epoxy resin, the polyvinyl alcohol.
Dispersant described in step (1) and the step (3) is selected from one or more combinations in absolute ethyl alcohol, acetone, the deionized water.
Ionic liquid described in the step (3) is selected from one or more combinations in the acetate, nitrate, dicyandiamide salt of acetate, nitrate, dicyandiamide salt or the 1-vinyl-3-methylimidazole of 1-ethyl-3-methylimidazole; The above ion liquid purity is more than or equal to 98%, and wherein the mol ratio of nitrogen and carbon is 2/8~5/8.
Protective atmosphere is selected from one or more combinations in helium, nitrogen, argon gas, the carbon dioxide described in step (2) and (4).
Nitrogenous carbon described in the step (4) coats lithium titanate material and has a nanometer primary particle composition micron offspring spherical morphology, the nitrogenous material with carbon element of coated with uniform one deck.
The present invention has not only effectively improved the electronic conductivity of lithium titanate material but also has strengthened the surface stability of this material, and the material that is obtained has excellent high rate performance and cycle performance, and has effectively improved the flatulence problem of lithium titanate system battery.
Description of drawings
Fig. 1 is that nitrogenous carbon coats the X-ray diffractogram of lithium titanate material and the comparison diagram of standard card.
(a) nitrogenous carbon coats lithium titanate composite material; (b) standard card (JCPD490207)
Fig. 2 is the SEM figure that the nitrogenous carbon that obtained among the embodiment 3 coats lithium titanate material.
Fig. 3 is the first charge-discharge curve (0.2C) that pure phase lithium titanate, carbon coat lithium titanate and nitrogenous carbon coating lithium titanate material, and voltage range is 1.0~2.5V.
The pure phase lithium titanate of Fig. 4, carbon coat lithium titanate and nitrogenous carbon coats the cycle performance comparison diagram of lithium titanate material under different multiplying, and charge-discharge magnification is 0.2C, 1.0C, 5.0C, 10.0C.
Embodiment
Embodiment 1
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:0.2 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 5 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 80 degree, and be 8 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 800 ℃ with the heating rate of 2 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 30% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 10% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 500 insulations 15 hours with the heating rate of 2 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
Embodiment 2
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:0.5 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 8 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 90 degree, and be 10 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 850 ℃ with the heating rate of 5 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 25% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 25% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 800 insulations 10 hours with the heating rate of 5 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
Embodiment 3
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:0.8 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 10 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 100 degree, and be 12 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 880 ℃ with the heating rate of 8 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 15% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 40% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 600 insulations 8 hours with the heating rate of 8 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
Embodiment 4
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:1.2 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 12 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 120 degree, and be 8 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 900 ℃ with the heating rate of 10 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 10% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 45% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 800 insulations 7 hours with the heating rate of 10 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
Embodiment 5
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:1.5 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 6 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 100 degree, and be 10 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 950 ℃ with the heating rate of 15 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 5% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 50% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 950 insulations 6 hours with the heating rate of 20 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
Embodiment 6
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:2 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 10 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 100 degree, and be 12 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 880 ℃ with the heating rate of 8 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats, add proper amount of deionized water and carry out once more the Ball milling processing, it is 40% that the slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 600 insulations 8 hours with the heating rate of 8 ℃/min, obtains carbon and coats lithium titanate material.
The comparative example
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:0.8 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 10 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 100 degree, and be 12 hours drying time.
B) drying is good presoma places air furnace to carry out sintering, is warming up to 880 ℃ with the heating rate of 8 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains lithium titanate material.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 15% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 40% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places air furnace to carry out sintering, rises to 600 insulations 8 hours with the heating rate of 8 ℃/min, obtains pure phase lithium titanate material.
 
The lithium titanate material of gained in the foregoing description is assembled into button cell, and material proportion is Li in the button cell 4Ti 5O 12: SP:PVDF=80:10:10; Adopting Clgard2300 type barrier film, is metal lithium sheet to electrode, carries out the charge-discharge performance test; Pure phase lithium titanate, carbon coat lithium titanate and nitrogenous carbon coating lithium titanate material 0.2C charging and discharging curve is as shown in Figure 3, and the charging/discharging voltage scope is 1.0-2.5V.Fig. 4 is that pure phase lithium titanate, carbon coat lithium titanate and nitrogenous carbon coats the cycle performance comparison diagram of lithium titanate material under different multiplying; From above-mentioned two width of cloth figure, can find out; Though the charge/discharge capacity under the pure phase lithium titanate 0.2C multiplying power is higher; It is less that but nitrogenous carbon coats the polarization of lithium titanate, and the charge/discharge capacity conservation rate is higher under high magnification.Shown in Figure 1 is the XRD figure that nitrogenous carbon coats lithium titanate material, and the result shows that the coating of nitrogenous carbon does not change the spinel structure of lithium titanate; Shown in Figure 2 is the sem photograph that nitrogenous carbon coats lithium titanate composite material, can find out that material demonstrates the pattern of micron-size spherical second particle;
Embodiment result shows, the synthesis technique that coats through secondary is also introduced ionic liquid as the part carbon source, obtains the surface and coats uniform nitrogenous carbon and coat lithium titanate material.This lithium titanate material has the nanometer primary particle and forms micron offspring spherical morphology; Its coated with uniform the nitrogenous material with carbon element of one deck; Not only effectively improved its electronic conductivity but also strengthened the surface stability of this material, the material that is obtained has excellent high rate performance and cycle performance.Use the battery system of this material and since the coated with uniform of this lithium titanate composite material the nitrogenous material with carbon element of one deck, avoided lithium titanate material directly and the haptoreaction of electrolyte, can effectively improve the flatulence problem of lithium titanate system battery.
Organic carbon source has only been enumerated polyvinyl alcohol in the foregoing description, selects one or more combinations in other the organic carbon source glucose, sucrose, polyvinyl butyral resin, phenolic resins, epoxy resin for use, and experimental result is similar; Ionic liquid has only been enumerated 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA); Select one or more combinations in the acetate, nitrate, dicyandiamide salt of acetate, nitrate or the 1-vinyl-3-methylimidazole of other ionic liquids 1-ethyl-3-methylimidazole for use, experimental result is similar.

Claims (6)

1. introduce ionic liquid and prepare the synthetic method that nitrogenous carbon coats lithium titanate composite material for one kind, it is characterized in that may further comprise the steps as carbon source:
(1) mol ratio according to lithium, titanium, carbon is (4~4.4): 5: (greater than zero~2) takes by weighing lithium salts, titanium dioxide and organic carbon source; Adding dispersant places ball mill to carry out the stirring ball-milling processing; The ball milling time is 3-12 hour; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 80~120 degree, and be 8-16 hour drying time;
(2) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 750 ℃~950 ℃ with the heating rate of 2~25 ℃/min, is incubated 8~20 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats;
(3) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing ionic liquid according to 5%~30% the percentage that carbon coats the lithium titanate quality; And be blended into proper amount of deionized water and carry out once more Ball milling and handle; Slurries after finishing dealing with add appropriate amount of deionized water again or dispersant adjustment solid content of slurry is 10%~50%, carry out spray drying treatment again;
The dry powder that (4) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 500~900 ℃ of insulations 5-16 hour with the heating rate of 2~25 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
2. preparation method according to claim 1 is characterized in that: the described titanium dioxide of step (1) is the nanostructured anatase structure; Said lithium salts is selected from one or more combinations in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, the lithium fluoride; Said organic carbon source is selected from one or more combinations in glucose, sucrose, polyvinyl butyral resin, phenolic resins, epoxy resin, the polyvinyl alcohol.
3. preparation method according to claim 1 is characterized in that the dispersant described in step (1) and the step (3) is selected from one or more combinations in absolute ethyl alcohol, acetone, the deionized water.
4. preparation method according to claim 1; It is characterized in that: the ionic liquid described in the step (3) is selected from one or more combinations in the acetate, nitrate, dicyandiamide salt of acetate, nitrate, dicyandiamide salt or the 1-vinyl-3-methylimidazole of 1-ethyl-3-methylimidazole; The above ion liquid purity is more than or equal to 98%, and wherein the mol ratio of nitrogen and carbon is 2/8~5/8.
5. preparation method according to claim 1 is characterized in that: protective atmosphere is selected from one or more combinations in helium, nitrogen, argon gas, the carbon dioxide described in step (2) and (4).
6. preparation method according to claim 1,, it is characterized in that: nitrogenous carbon described in the step (4) coats lithium titanate material and has a nanometer primary particle composition micron offspring spherical morphology, the nitrogenous material with carbon element of coated with uniform one deck.
CN2012101965188A 2012-06-14 2012-06-14 Synthetic method of nitrogen-enriched carbon coated lithium titanate composite material prepared by introduction of ionic liquid as carbon source CN102820458A (en)

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CN107863516A (en) * 2017-11-02 2018-03-30 洛阳月星新能源科技有限公司 A kind of nitrogenous nano lithium titanate composite and preparation method thereof, lithium ion battery
TWI640121B (en) * 2017-05-15 2018-11-01 國立成功大學 Anode material with high oxygen vacancy, method of producing the same and application thereof
TWI659558B (en) * 2018-03-20 2019-05-11 中原大學 Method of fabricating anode material for secondary battery
CN110416517A (en) * 2019-07-29 2019-11-05 卢昌琴 A kind of negative electrode material and preparation method thereof of lithium-ion-power cell double-coating structure

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