CN103956475A - Method for preparing lithium titanate of lithium ion battery cathode material - Google Patents
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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
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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
- 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
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- 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 method for preparing lithium titanate of a lithium ion battery cathode material. The method comprises the following steps of mixing a titanium source, a dispersing agent and deionized water to form a titanium-containing solution, stirring and hydrolyzing the titanium-containing solution, and collecting a product through centrifugation; adding the titanium-containing solution in the collected product and uniformly mixing, carrying out hydrothermal reaction on the collected product so as to obtain a precipitate which is a lithium titanate precursor of a nanostructure, wherein the mole ratio of Li and Ti is (4 to 5)-(5 to 1); and carrying out low temperature calcination on the obtained lithium titanate precursor in the atmosphere of a nitrogenous reducibility gas so as to obtain the lithium titanate of a N-doped nanoscale lithium ion battery cathode material. Compared with the prior art, the method provided by the invention has the advantages that an equipment requirement is low, the method is easy for industrial production a lithium titanate material prepared by the method provided by the invention has the advantages of a nanostructure and a doping vario-property, meanwhile, the ionic conductivity and electronic conductivity of the material are improved, and the material has the excellent specific capacity property and the cycling property.
Description
Technical field
The invention belongs to technical field of chemical power, especially relate to a kind of method of preparing lithium ionic cell cathode material lithium titanate.
Background technology
At present commercial Li-ion batteries negative material is mainly carbon-based material, although carbon negative pole material cost is low, but still the shortcoming such as thermal runaway while there is poor safety performance, first charge-discharge efficiency low and high temperature.Lithium titanate (the Li of spinel structure
4ti
5o
12) there is " the zero strain effect " of constancy of volume in lithium ion embeds and deviates from process, than advantages such as the chemical diffusion coefficients of the large order of magnitude of carbon negative pole material, being considered to has one of negative material of application prospect most.But low electronic conductivity is to restrict at present Li
4ti
5o
12the major obstacle of applying in electrokinetic cell, improves Li
4ti
5o
12conductivity, improve Li
4ti
5o
12high rate during charging-discharging particularly important.
Current Li
4ti
5o
12the main path of modification has: (1) ion doping: by mixing of other elements, change the valence state structure of material surface, form electron hole, the conductivity that improves material improves its chemical property.American Chemical Society's periodical (Journal oftheAmerican Chemical Society) 130 (2008) 14930-14931 use simple high temperature solid-state synthetic, prepare the lithium titanate material of nitrogen doping under ammonia atmosphere.CN201310359192.0 discloses the preparation method of the coated lithium titanate material of a kind of titanium nitride, and it adopts high temperature solid-state method high temperature sintering under nitrogenous reducing atmosphere to obtain material.High temperature solid-state doping is reunited material granule, material is contacted insufficient with electrolyte, ion transfer difficulty, heavy-current discharge weak effect.(2) nanometer: can shorten Li
+the evolving path, reduce Li
+diffusional resistance, slow down electrode polarization, can increase the contact area of electrode active material and electrolyte simultaneously, make Li
+de-/embedding reaction is carried out more fully.Hydrothermal synthesis method is a kind of method of simple nano materials, has been widely used in field of nanometer material technology.Materials chemistry periodical (Journal of Materials Chemistry) 19 (2009) 5980-5984 use TiO
2colloid and LiOH are reaction raw materials, and in ethanol/water mixed solution, hydro-thermal prepares the lithium titanate microballoon of meso-hole structure, and material property is good, but this complex technical process is higher to equipment requirement.
Application number is the preparation method that 201310432347.9 Chinese patent discloses a kind of lithium titanate, and titanium source, lithium source, inorganic additive, organic additive and water are made to slurry; Then atomization drying powdered in atomizing dryer; Finally, under nitrogen and hydrogen mixture atmosphere, the powder 700 that atomization drying is made is spent 5~10 hours cooling lithium titanates that obtain of above roasting.The method is easy to large-scale production, and reducing atmosphere is easy to generate a small amount of Ti
3+, improve the conductivity of material.But this technique 700 is spent above sintering, though have nano particle also easily in the time of high temperature sintering material granule become large, be difficult to reach the high rate capability of nano material.
Summary of the invention
Object of the present invention is exactly to provide a kind of method of preparing lithium ionic cell cathode material lithium titanate in order to overcome the defect that above-mentioned prior art exists, the method realizes nanometer in promoting material conductivity by doping, shorten the evolving path of ion, thereby the performance while improving its large multiplying power discharging, to meet the current demand to lithium ion battery.
Object of the present invention can be achieved through the following technical solutions:
A method of preparing lithium ionic cell cathode material lithium titanate, comprises the following steps:
(1) titanium source, dispersant, deionized water are mixed to form to titaniferous solution, stir lower hydrolysis, centrifugal collection product;
(2) in the product of collecting to step (1), add lithium-containing solution and mix, then carrying out hydro-thermal reaction, the lithium titanate precursor that the sediment obtaining is nanostructure, wherein Li and Ti mol ratio are 4: 5~5: 1;
(3) lithium titanate precursor step (2) being obtained low temperature calcination in the atmosphere of nitrogenous reducibility gas, obtains nitrogen-doped nanometer level lithium ionic cell cathode material lithium titanate.
Titanium source described in step (1) is selected from one or more in butyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetrachloride or titanyl sulfate.
Dispersant described in step (1) is selected from ethanol, ethylene glycol or cyclohexane.
The proportionate relationship of titanium source and dispersant is 0.002mol: 1L~5mol: 1L, and the volume ratio of dispersant and deionized water is 10: 1~1000: 1.The too low production cost that makes of the ratio of titanium source and dispersant strengthens, and too highly causes the hydrolysis of titanium source too fast, and the material particle size of producing is increased.
As preferred embodiment, the proportionate relationship of titanium source and dispersant is 0.005mol: 1L~0.05mol: 1L, and absolute ethyl alcohol and deionized water ratio are 400: 1~600: 1.
Lithium-containing solution described in step (2) is dissolved in deionized water by lithium-containing compound and makes, and lithium-containing compound is lithium hydroxide, lithium acetate, lithium nitrate, lithium carbonate or lithium chloride.
In described lithium-containing solution, the concentration of lithium is 0.1~1mol/L.
Temperature when hydro-thermal reaction described in step (2) is 80~180 DEG C, and the time of hydro-thermal reaction is 10~72 hours.The too low meeting of temperature causes the hydro-thermal time to increase, and is unfavorable for industrial production; Excess Temperature is also higher to the equipment requirement of producing.
As preferred embodiment, hydrothermal temperature is 130~150 DEG C, and the hydro-thermal time is 14~24 hours.
The described nitrogenous reducibility gas of step (3) is ammonia or ammonia and the gaseous mixture of nitrogen, argon gas, hydrogen, and calcining heating rate is 2~10 DEG C/min, and the temperature of calcining is 350~600 DEG C, and the time of calcining is 2~10 hours.Heating rate is too fast, and calcining heat is too high, and calcination time is oversize, all can cause material to be reunited, and be difficult to keep nanostructure, and heating rate is excessively slow, and calcining heat is too low, and the too short material crystallinity that can cause of calcination time is bad, affects performance.
As preferred embodiment, heating rate is 3 DEG C/min, and the temperature of calcining is 500~550 DEG C, and the time of calcining is 5~7 hours.
The lithium ionic cell cathode material lithium titanate that step (3) makes is spinel structure.
To adopt the synthetic lithium ionic cell cathode material lithium titanate of the inventive method to mix at 80: 10: 10 in mass ratio with conductive carbon black and binding agent polyvinylidene fluoride (PVDF) respectively, be coated on Copper Foil, after dry, be cut into cathode pole piece, in 100 DEG C of vacuumizes 24 hours.Taking lithium metal as to electrode, by electrolyte LiPF
6it is to form electrolyte in the mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC) of 1: 1: 1 that salt is dissolved in mass ratio, the concentration of electrolyte is 1mol/L, in argon gas glove box, is assembled into button cell.Adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test, charging/discharging voltage scope is 1.0V-2.5V (vs.Li
+/ Li).
Compared with prior art, the present invention prepares the lithium titanate precursor of nanostructure by traditional hydro thermal method, then low temperature calcination in the atmosphere of nitrogenous reducibility gas, lower calcining heat can not cause excessively growing up of nanometer granular precursor, keep nanostructure, and in the atmosphere of nitrogenous reducibility gas, realize nitrogen doping.Nanostructure can increase the contact area of material and electrolyte, shortens the evolving path of lithium ion at material internal, is more conducive to ion and conducts at material internal; Nitrogen doping can change the valence state structure of material surface, forms electron hole, improves the conductivity of material, thereby promotes the large multiplying power discharging property of material.The material of preparation of the present invention, combines the advantage of nanostructure and nitrogen-doped modified two aspects, has improved the high-rate discharge ability of material, can meet the current requirement to electrokinetic cell fast charging and discharging.
Brief description of the drawings
Fig. 1 is the lithium ionic cell cathode material lithium titanate SEM figure that embodiment 1 makes;
Fig. 2 is the Capacitance reserve performance chart of the lithium ionic cell cathode material lithium titanate that makes of embodiment 1 and comparative example 1 under different multiplying;
Fig. 3 is the cycle performance curve chart of the lithium ionic cell cathode material lithium titanate that makes of embodiment 1 under different multiplying.
Embodiment
The method of preparing lithium ionic cell cathode material lithium titanate can adopt following steps:
(1) titanium source, dispersant, deionized water are mixed to form to titaniferous solution, stir lower hydrolysis, and by centrifugal product collection;
(2) the centrifugal product obtaining is added in lithium-containing solution and mixed, carry out hydro-thermal reaction, the temperature of hydro-thermal reaction is 80~180 DEG C, and the reaction time is 10~72 hours, the lithium titanate precursor that the sediment generating after reaction is nanostructure; Wherein Li and Ti mol ratio are 4: 5~5: 1;
(3) lithium titanate precursor of step (2) gained nanostructure is warming up to 350~600 DEG C with the speed of 2~10 DEG C/min in the atmosphere of nitrogenous reducibility gas, calcine 2~10 hours, then naturally cool to room temperature, obtain nanoscale nitrogen doped lithium ion battery negative material lithium titanate.
In step (1), titanium source is selected from one or more in butyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetrachloride or titanyl sulfate, dispersant is selected from ethanol, ethylene glycol or cyclohexane, in step (1), the proportionate relationship of titanium source and dispersant is 0.002mol: 1L~5mol: 1L, and the volume ratio of dispersant and deionized water is 10: 1~1000: 1.
The middle lithium-containing solution of step (2) is dissolved in deionized water by lithium-containing compound and makes, and lithium-containing compound is lithium hydroxide, lithium acetate, lithium nitrate, lithium carbonate or lithium chloride.In lithium-containing solution, the concentration of lithium is 0.1~1mol/L.
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Select lithium hydroxide as lithium source, butyl titanate do titanium source, ethanol does dispersant, it is 1: 1 according to the mol ratio of Li, Ti, 0.004mol butyl titanate, 20mL ethanol, 2mL water are mixed to formation titaniferous solution, stir lower hydrolysis, the centrifugal collection of hydrolysate; Hydrolysate adds in lithium-containing solution and mixes, and wherein lithium-containing solution is dissolved in 20mL water by 0.004mol lithium hydroxide and obtains; At 150 DEG C, react and within 14 hours, generate nanostructure metatitanic acid lithium presoma; The lithium titanate precursor obtaining is warming up to 550 DEG C and constant temperature 6 hours with 3 DEG C/min speed under ammonia atmosphere, then naturally cools to room temperature, obtain lithium titanate material of the present invention.
The SEM of the nanoscale lithium nitrogen doping ion battery negative material lithium titanate that the present embodiment makes schemes as shown in Figure 1, and as can be seen from the figure this material is nano-sheet structure, and area is in 200nm left and right, its distribution uniform.
Embodiment 2
Select lithium acetate as lithium source, tetraethyl titanate do titanium source, cyclohexane does dispersant, it is 0.8: 1 according to the mol ratio of Li, Ti, 0.004mol tetraethyl titanate, 20mL acetone, 2mL water are mixed to formation titaniferous solution, stir lower hydrolysis, the centrifugal collection of hydrolysate; ; Hydrolysate adds in lithium-containing solution and mixes, and wherein lithium-containing solution is dissolved in 20mL water by 0.0032mol lithium acetate and obtains; At 80 DEG C, react 72h and generate nanostructure metatitanic acid lithium presoma; The lithium titanate precursor obtaining is warming up to 600 DEG C and constant temperature 2 hours with 5 DEG C/min speed under the mixed atmosphere of ammonia and nitrogen, then naturally cools to room temperature, obtain lithium titanate material of the present invention.
Embodiment 3
Select lithium nitrate as lithium source, isopropyl titanate do titanium source, ethylene glycol does dispersant, it is 5: 1 according to the mol ratio of Li, Ti, 0.004mol isopropyl titanate, 20mL ethylene glycol, 2mL water are mixed to formation titaniferous solution, stir lower hydrolysis, the centrifugal collection of hydrolysate; Hydrolysate adds in lithium-containing solution and mixes, and wherein lithium-containing solution is dissolved in 20mL water by 0.02mol lithium nitrate and obtains; At 180 DEG C, react 12h and generate nanostructure metatitanic acid lithium presoma; The lithium titanate precursor obtaining is warming up to 500 DEG C and constant temperature 8 hours with 5 DEG C/min speed under ammonia and argon atmospher, then naturally cools to room temperature, obtain lithium titanate material of the present invention.
Embodiment 4
Select lithium carbonate as lithium source, titanium tetrachloride do titanium source, ethanol does dispersant, it is 2: 1 according to the mol ratio of Li, Ti, 0.004mol titanium tetrachloride, 20mL ethanol, 2mL water are mixed to formation titaniferous solution, stir lower By Hydrolysis At Room Temperature, the centrifugal collection of hydrolysate; Hydrolysate adds in lithium-containing solution and mixes, and wherein lithium-containing solution is dissolved in 20mL water by 0.004mol lithium carbonate and obtains; At 200 DEG C, react 10h and generate nanostructure metatitanic acid lithium presoma; The lithium titanate precursor obtaining is warming up to 400 DEG C and constant temperature 10 hours with 2 DEG C/min speed under ammonia atmosphere, then naturally cools to room temperature, obtain lithium titanate material of the present invention.
Embodiment 5
Select lithium hydroxide as lithium source, butyl titanate do titanium source, ethylene glycol does dispersant, it is 4: 1 according to the mol ratio of Li, Ti, 0.004mol butyl titanate, 20mL ethylene glycol, 2mL water are mixed to formation titaniferous solution, stir lower By Hydrolysis At Room Temperature, the centrifugal collection of hydrolysate; Hydrolysate adds in lithium-containing solution and mixes, and wherein lithium-containing solution is dissolved in 20mL water by 0.016mol lithium hydroxide and obtains; At 180 DEG C, react 12h and generate nanostructure metatitanic acid lithium presoma; The lithium titanate precursor obtaining is warming up to 600 DEG C and constant temperature 4 hours with 8 DEG C/min speed under ammonia, nitrogen and argon gas mixed atmosphere, then naturally cools to room temperature, obtain lithium titanate material of the present invention.
Embodiment 6
Select lithium chloride as lithium source, titanyl sulfate do titanium source, ethanol does dispersant, it is 3: 1 according to the mol ratio of Li, Ti, 0.004mol titanyl sulfate, 20mL ethanol, 2mL water are mixed to formation titaniferous solution, stir lower By Hydrolysis At Room Temperature, the centrifugal collection of hydrolysate; Hydrolysate adds in lithium-containing solution and mixes, and wherein lithium-containing solution is dissolved in 20mL water by 0.016mol lithium chloride and obtains; At 150 DEG C, react 48h and generate nanostructure metatitanic acid lithium presoma; The lithium titanate precursor obtaining is warming up to 600 DEG C and constant temperature 4 hours with 6 DEG C/min speed under ammonia atmosphere, then naturally cools to room temperature, obtain lithium titanate material of the present invention.
Comparative example 1
Select lithium hydroxide as lithium source, butyl titanate do titanium source, ethanol does dispersant, it is 1: 1 according to the mol ratio of Li, Ti, 0.004mol butyl titanate, 20mL ethanol, 2mL water are mixed to formation titaniferous solution, stir lower hydrolysis, the centrifugal collection of hydrolysate; Hydrolysate adds in lithium-containing solution and mixes, and wherein lithium-containing solution is dissolved in 20mL water by 0.004mol lithium hydroxide and obtains; At 150 DEG C, react and within 14 hours, generate nanostructure metatitanic acid lithium presoma; The lithium titanate precursor obtaining is warming up to 550 DEG C and constant temperature 6 hours with 3 DEG C/min speed under air atmosphere, then naturally cools to room temperature, obtain not doped titanic acid lithium material.
Electrochemical property test: respectively the lithium ionic cell cathode material lithium titanate making in embodiment 1 and comparative example 1 is mixed in mass ratio with conductive carbon black and binding agent polyvinylidene fluoride (PVDF) at 80: 10: 10, be coated on Copper Foil, after dry, be cut into cathode pole piece, in 100 DEG C of vacuumizes 24 hours.Taking lithium metal as to electrode, by electrolyte LiPF
6it is to form electrolyte in the mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC) of 1: 1: 1 that salt is dissolved in mass ratio, the concentration of electrolyte is 1mol/L, in argon gas glove box, is assembled into button cell.Adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test, as shown in Figure 2 and Figure 3, charging/discharging voltage scope is 1.0V-2.5V (vs.Li to test result
+/ Li).The Capacitance reserve performance chart of Fig. 2 lithium ionic cell cathode material lithium titanate that to be embodiment 1 make with comparative example 1 under different multiplying.Under the condition that lithium ionic cell cathode material lithium titanate of the present invention is 1C in multiplying power as can be seen from Figure 2, initial discharge specific capacity is 173.3mAh/g, approaches theoretical specific capacity.Multiplying power rises to after 2C, 5C, 10C, circulates respectively 20 times, and capacity remains on respectively 165.1,162.3,151.8mAh/g.And the obtained lithium ionic cell cathode material lithium titanate of comparative example 1 capacity under 1C, 2C, 5C, 10C remains on respectively 170.6,163,156.9,139.1mAh/g.Fig. 3 is that lithium ionic cell cathode material lithium titanate of the present invention is respectively the cycle performance figure under 1C and 10C in multiplying power, and its capability retention is respectively 95.8% and 90.3%.Appeal result shows that this material has excellent chemical property.
In sum, the preparation method of a kind of ion cathode material lithium lithium titanate of the present invention, when the method realizes doping N, has also prepared the structure of nano-sheet.Can shorten the conductivity of ion transfer path and lifting material simultaneously, improve the ion diffusion rate of material.The material making has excellent specific capacity performance and cycle performance, and relatively suitability for industrialized is produced.
Above said content is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (9)
1. a method of preparing lithium ionic cell cathode material lithium titanate, is characterized in that, the method comprises the following steps:
(1) titanium source, dispersant, deionized water are mixed to form to titaniferous solution, stir lower hydrolysis, centrifugal collection product;
(2) in the product of collecting to step (1), add lithium-containing solution and mix, then carrying out hydro-thermal reaction, the lithium titanate precursor that the sediment obtaining is nanostructure, wherein Li and Ti mol ratio are 4: 5~5: 1;
(3) lithium titanate precursor step (2) being obtained low temperature calcination in the atmosphere of nitrogenous reducibility gas, obtains nitrogen-doped nanometer level lithium ionic cell cathode material lithium titanate.
2. a kind of method of preparing lithium ionic cell cathode material lithium titanate according to claim 1, it is characterized in that, the titanium source described in step (1) is selected from one or more in butyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetrachloride or titanyl sulfate.
3. a kind of method of preparing lithium ionic cell cathode material lithium titanate according to claim 1, is characterized in that, the dispersant described in step (1) is selected from ethanol, ethylene glycol or cyclohexane.
4. according to a kind of method of preparing lithium ionic cell cathode material lithium titanate described in any one in claim 1-3, it is characterized in that, the proportionate relationship of titanium source and dispersant is 0.002mol: 1L~5mol: 1L, and the volume ratio of dispersant and deionized water is 10: 1~1000: 1.Preferably the proportionate relationship of titanium source and dispersant is 0.005mol: 1L~0.05mol: 1L, and absolute ethyl alcohol and deionized water ratio are 400: 1~600: 1.
5. a kind of method of preparing lithium ionic cell cathode material lithium titanate according to claim 1, it is characterized in that, lithium-containing solution described in step (2) is dissolved in deionized water by lithium-containing compound and makes, and lithium-containing compound is lithium hydroxide, lithium acetate, lithium nitrate, lithium carbonate or lithium chloride.
6. a kind of method of preparing lithium ionic cell cathode material lithium titanate according to claim 5, is characterized in that, in described lithium-containing solution, the concentration of lithium is 0.1~1mol/L.
7. a kind of method of preparing lithium ionic cell cathode material lithium titanate according to claim 1, is characterized in that, temperature when hydro-thermal reaction described in step (2) is 80~180 DEG C, and the time of hydro-thermal reaction is 10~72 hours.Preferably hydrothermal temperature is 130~150 DEG C, and the hydro-thermal time is 14~24 hours.
8. a kind of method of preparing lithium ionic cell cathode material lithium titanate according to claim 1, it is characterized in that, the described nitrogenous reducibility gas of step (3) is the gaseous mixture of ammonia or ammonia and nitrogen, argon gas, hydrogen, calcining heating rate is 2~10 DEG C/min, the temperature of calcining is 350~600 DEG C, and the time of calcining is 2~10 hours.Preferably heating rate is 3 DEG C/min, and the temperature of calcining is 500~550 DEG C, and the time of calcining is 5~7 hours.
9. a kind of method of preparing lithium ionic cell cathode material lithium titanate according to claim 1, is characterized in that, the lithium ionic cell cathode material lithium titanate that step (3) makes is spinel structure.
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CN104300120A (en) * | 2014-09-17 | 2015-01-21 | 山东精工电子科技有限公司 | Hydrothermal synthesis method of nano-lithium titanate material |
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CN106207089A (en) * | 2016-07-19 | 2016-12-07 | 青海大学 | A kind of used as negative electrode of Li-ion battery lithium titanate nano-tube material and preparation method thereof |
CN107492647A (en) * | 2017-08-16 | 2017-12-19 | 深圳市比克动力电池有限公司 | Lithium ion battery negative material, cathode material preparation method and lithium ion battery |
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CN111342023A (en) * | 2020-03-13 | 2020-06-26 | 中国科学院过程工程研究所 | Positive electrode material and preparation method and application thereof |
CN111410227A (en) * | 2020-03-25 | 2020-07-14 | 上海电力大学 | Lithium titanate negative electrode material and preparation method thereof |
CN111710854A (en) * | 2020-06-18 | 2020-09-25 | 电子科技大学 | Lithium titanate electrode material with oxygen defect and preparation method and application thereof |
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CN105845924A (en) * | 2016-05-23 | 2016-08-10 | 扬州大学 | Preparation method for fluorine-doping Li4Ti5O12 nanosheet |
CN106207089A (en) * | 2016-07-19 | 2016-12-07 | 青海大学 | A kind of used as negative electrode of Li-ion battery lithium titanate nano-tube material and preparation method thereof |
CN107492647A (en) * | 2017-08-16 | 2017-12-19 | 深圳市比克动力电池有限公司 | Lithium ion battery negative material, cathode material preparation method and lithium ion battery |
CN108520953A (en) * | 2018-04-17 | 2018-09-11 | 吉林大学 | A kind of carbon coating lithium titanate negative material and preparation method thereof |
CN109273705A (en) * | 2018-08-29 | 2019-01-25 | 昆明理工大学 | A kind of preparation method of lithium titanate anode material for lithium ion battery |
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CN111342023A (en) * | 2020-03-13 | 2020-06-26 | 中国科学院过程工程研究所 | Positive electrode material and preparation method and application thereof |
CN111342023B (en) * | 2020-03-13 | 2021-08-10 | 中国科学院过程工程研究所 | Positive electrode material and preparation method and application thereof |
CN111410227A (en) * | 2020-03-25 | 2020-07-14 | 上海电力大学 | Lithium titanate negative electrode material and preparation method thereof |
CN111410227B (en) * | 2020-03-25 | 2022-08-05 | 上海电力大学 | Lithium titanate negative electrode material and preparation method thereof |
CN111710854A (en) * | 2020-06-18 | 2020-09-25 | 电子科技大学 | Lithium titanate electrode material with oxygen defect and preparation method and application thereof |
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