CN104037415A - Preparation method for lithium-ion battery cathode material Ni/Li3Ti4NiCrO12 - Google Patents

Preparation method for lithium-ion battery cathode material Ni/Li3Ti4NiCrO12 Download PDF

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CN104037415A
CN104037415A CN201410281167.XA CN201410281167A CN104037415A CN 104037415 A CN104037415 A CN 104037415A CN 201410281167 A CN201410281167 A CN 201410281167A CN 104037415 A CN104037415 A CN 104037415A
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nickel
lithium
ion battery
lithium titanate
titanium dioxide
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CN104037415B (en
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常程康
郭倩
蔡元元
王欣
陈茜
邓玲
王永强
史运伟
石明明
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Shanghai Institute of Technology
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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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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

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  • General Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method for lithium-ion battery cathode material Ni/Li3Ti4NiCrO12. The preparation method comprises the following steps: mixing titanium dioxide and de-ionized water in a certain ratio under stirring to obtain a suspension liquid; adding chromium trioxide to the suspension liquid of the titanium dioxide and stirring uniformly; dissolving lithium hydroxide in the de-ionized water to obtain lithium hydroxide aqueous solution; dissolving nickel acetate in the de-ionized water to prepare nickel acetate solution; mixing the suspension liquid and the solution, and grinding the mixed solution to obtain a precursor; performing spray-drying on the precursor; calcining the dried precursor at high temperature in an insert atmosphere mixed with a reducing gas to obtain the lithium-ion battery cathode material Ni/Li3Ti4NiCrO12. The profiles of the products obtained by the preparation method are uniform spheres; the particle size is nano-scale; certain nano-pores are reserved among the nano-particles. Meanwhile, the surface steric hindrance on the surface of the material is reduced by the nickel coating surface of the material; the electrical conductivity of the particles is increased; the cycling stability is enhanced; therefore, the lithium-ion battery cathode material Ni/Li3Ti4NiCrO12 has a good application prospect in the field of power batteries.

Description

The preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel
Technical field
The invention belongs to new energy materials field, relate in particular to a kind of lithium battery, is the coated chromium nickel lithium titanate (Ni/Li of a kind of lithium ion battery negative material nickel specifically 3ti 4niCrO 12) preparation method.
 
Background technology
Along with the fast development of human society, the demand of the energy is sharply increased to linearly ascendant trend of energy resource consumption total amount.Along with day by day increasing the weight of of global energy crisis and problem of environmental pollution, new policy has been put into effect and has encouraged research and the application of new forms of energy in succession in countries in the world.Lithium ion battery is shown one's talent with advantages such as its volume are little, lightweight, pollution-free, more and more receives people's concern, in China's 863 Program, also classifies development electric motor car as important developing direction.Lithium (ion) battery, as the chemical power source of latest generation, becomes the focus that people pay close attention to.
Lithium ion battery is that Japanese SONY company in 1990 develops and starts to realize commercial a kind of high-efficiency energy-storage product, compared with other batteries, the advantage of lithium ion battery is operating voltage high (3.6V is cadmium-nickel, nickel-hydrogen battery three times), volume little (less by 30% than nickel-hydrogen battery), quality light (lighter by 50% than nickel-hydrogen battery), the high (140Whkg of specific energy -1, be 1 ~ 2 times of cadmium nickel battery), memory-less effect, pollution-free, self discharge is little, have extended cycle life.
At present, commercial lithium ion battery negative material adopts various embedding lithium material with carbon elements mostly, but material with carbon element also has some weakness that are difficult to overcome in actual applications as negative pole, for example, the current potential of carbon negative pole and the current potential of lithium metal are very approaching, in the time of battery overcharge, the easy precipitating metal lithium of carbon electrodes and cause safety issue; Easy and electrolyte is had an effect; There is obvious voltage delay.In order to solve the safety problem of lithium battery, people have done a large amount of research.Spinel-type Li 4ti 5o 12as a kind of novel ion secondary battery cathode material lithium, compared with material with carbon element, there is good cycle, do not react with electrolyte, the advantage such as security performance is high, charge and discharge platform is steady, be one of the most excellent lithium ion battery negative material receiving much concern in recent years.
Spinel-type Li 4ti 5o 12space lattice group be cubic system, in the time discharging and recharging, skeleton structure characteristic is " zero strain ".But, because Li4Ti5O12 is a kind of semi-conducting material, poorly conductive, density is low etc., and shortcoming causes its chemical property under high magnification poor.For the begin one's study modification of lithium titanate of a lot of scholars of this situation.
The people such as Hany El-Shinawi adopt sol-gel process to prepare double ion doped titanic acid lithium material (Li 3ti 4niMnO 12and Li 3ti 4niCrO 12: New substituted lithium titanium oxides, Solid State Sciences, 22 (2013) 65-70), prepared chromium nickel lithium titanate first discharge specific capacity under 0.5C multiplying power is 156mAh/g, approach theoretical specific capacity, there is higher discharge-rate, preferably chemical property.Be expected to have a good application prospect in electrokinetic cell field.But its cyclical stability is poor, after 10 charge and discharge cycles, the decay of specific capacity 20%.And the chromium nickel lithium titanate cycle that adopts sol-gel process to prepare is long, cost compare is high, is not suitable for industrialization and produces.
By above analysis, in existing double ion doping vario-property lithium titanate, there is charge and discharge cycles poor stability, manufacturing cycle is long, and cost compare is high, operating procedure complexity, is difficult for accomplishing scale production, controlling the problems such as the particle size of chromium nickel lithium titanate.
summary of the invention
For the defect existing in above-mentioned prior art, technical problem to be solved by this invention is to provide the coated chromium nickel lithium titanate (Ni/Li of a kind of lithium ion battery negative material nickel 3ti 4niCrO 12) preparation method; the preparation method of the coated chromium nickel lithium titanate of described this lithium ion battery negative material nickel will solve lithium titanate battery charge and discharge cycles poor stability prepared by the method for prior art; manufacturing cycle is long; cost compare is high, operating procedure complexity, the technical problem that is difficult for accomplishing scale production.
The preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel of the present invention, comprises the steps:
(1) first take titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:36 ~ 44:112 ~ 137:63 ~ 69;
(2) titanium dioxide is added 200 parts of deionized waters be configured to tio_2 suspension, chrome green is joined in tio_2 suspension, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, control pulp particle size between 200-400nm;
(3) lithium hydroxide is dissolved in 500 parts of deionized waters and obtains lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (2);
(4) nickel acetate is dissolved in to 800 parts of deionized waters and is configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (3), ball milling discharging in 0.5 ~ 1 hour;
(5) the green slurry of step (4) gained is sprayed under stirring and be dried, obtain presoma powder;
(6) by 700 DEG C of-900 DEG C of calcinings under the inert gas atmosphere that is mixed with reducibility gas of presoma powder, obtain the coated chromium nickel lithium titanate of nickel.
Further, described reducibility gas is hydrogen, and the concentration of reducibility gas in total gas is 1%-5%, and described inert gas is one or more the combination in argon gas, nitrogen, helium.
Further, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:36:137:63, and the concentration of reducibility gas in total gas is 1%, and calcining heat is 700 DEG C.
Further, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:40:125:63, and the concentration of reducibility gas in total gas is 3%, and calcining heat is 800 DEG C.
Further, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:112:63, and the concentration of reducibility gas in total gas is 5%, and calcining heat is 900 DEG C.
Further, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:36:137:66, and the concentration of reducibility gas in total gas is 1%, and calcining heat is 800 DEG C.
Further, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:112:66, and the concentration of reducibility gas in total gas is 3%, and calcining heat is 900 DEG C.
Further, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:36:137:69, and the concentration of reducibility gas in total gas is 5%, and calcining heat is 700 DEG C.
Further, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:125:69, and the concentration of reducibility gas in total gas is 1%, and calcining heat is 900 DEG C.
Further, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:112:69, and the concentration of reducibility gas in total gas is 3%, and calcining heat is 700 DEG C.
Further, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:125:66, and the concentration of reducibility gas in total gas is 5%, and calcining heat is 800 DEG C.
A kind of lithium ion battery negative material of the present invention has the preparation method of the coated chromium nickel lithium titanate of nickel, adopt nano ball grinding technique to control presoma size, high-temperature calcination by under reducing atmosphere obtains the lithium titanate material of nano-scale, finally obtains that initial specific capacity is high, the coated chromium nickel lithium titanate material of the nickel of good cycle.Its particle diameter is little and even, reduces Li +migration path, diffusional resistance reduces, better removal lithium embedded; Be coated owing to having carried out nickel on the surface of chromium nickel lithium titanate simultaneously, the surperficial steric hindrance of material is reduced, conductivity strengthens, and cyclical stability improves.Unified for spherical by method products obtained therefrom pattern of the present invention, primary particle is of a size of nanoscale, has certain nanoaperture between nano particle.The nanometer of material has reduced the distance of lithium ion migration, is expected to improve its multiplying power property; ; The capillary channel that the existence of nanoaperture provides lithium ion exchanged to need, is conducive to diffusion and the exchange of lithium ion.Such architectural feature increases the specific capacity of material, and cyclical stability improves.Under 0.5C multiplying power, test, first discharge specific capacity can reach 163mAh/g, and the material of preparing than people such as Hany El-Shinawi has improved 5%, and has good cyclical stability, and after 20 times charge and discharge cycles finishes, special capacity fade is faint.In addition, operation of the present invention is simple, can industrial applications.
Chromium nickel the lithium titanate material coated nickel of above-mentioned gained is assembled into button battery, charge-discharge performance to this battery under 0.5C multiplying power is tested, its average specific discharge capacity is 155.9 mAh/g, its first discharge specific capacity is 154.3mAh/g-163.1mAh/g, initial charge specific capacity is 145.3mAh/g-155.1mAh/g, coulomb efficiency is 95.1-98.3% first, and in electric discharge, threshold voltage is 1.48-1.53V.After 20 times charge and discharge cycles finishes, special capacity fade is faint.
The present invention compares with prior art, and its technological progress is significant.The preparation method of the coated chromium nickel lithium titanate of lithium ion battery negative material nickel of the present invention, for existing double ion doping vario-property lithium titanate there is the weak points such as particle diameter is large, cycle performance is bad, preparation section is complicated, replace lithium, titanium ion with nickel, chromium ion, make it to the inner doping vario-property of lithium titanate structure cell, after doped and substituted, the structure of crystal is still spinel structure, and metallic nickel coating layer is contained on the chromium nickel lithium titanate surface of preparation simultaneously.The nickel of material surface is coated its surperficial steric hindrance is reduced, and particle conductivity increases, and cyclical stability strengthens; Such architectural feature increases the specific capacity of material, and cyclical stability improves.Good electrochemical properties and stable circulation performance, make this Ni/Li 3ti 4niCrO 12material has good application prospect in electrokinetic cell field.
 
Brief description of the drawings
Fig. 1 is the XRD collection of illustrative plates that the lithium ion battery negative material of embodiment 1 gained has the coated chromium nickel lithium titanate of nickel;
Fig. 2 is the SEM figure that the lithium ion battery negative material of embodiment 1 gained has the coated chromium nickel lithium titanate of nickel;
Fig. 3 is the chemical property collection of illustrative plates that the lithium ion battery negative material of embodiment 1 gained has the coated chromium nickel lithium titanate of nickel.
Embodiment
Below by specific embodiment, also the present invention is described in detail by reference to the accompanying drawings, but do not limit the present invention.
The preparation of battery and the method for testing of chemical property
(1), the preparation of battery cathode sheet
The lithium ionic cell cathode material lithium titanate obtaining, conductive carbon powder, the poly-inclined to one side tetrafluoroethene (PVDF) of organic binder bond are calculated according to mass ratio, be lithium ion battery negative material chromium nickel lithium titanate: conductive carbon powder: the ratio that the poly-inclined to one side tetrafluoroethene of organic binder bond is 80:10:10 is mixed, after fully stirring, form slurry, be coated on aluminium foil surface, after oven dry, repeatedly rolling, obtains battery cathode sheet;
(2), battery assembling and performance test
Use 2016 type half-cell assessments to obtain the chemical property of chromium nickel lithium titanate.Battery pole piece punching press good rolling is become to the disk of 12 millimeters of diameters, accurately weigh after its quality, calculate the quality of the lithium titanate in pole piece according to formula composition, use the barrier film of 19 millimeters of diameters, use the metal lithium sheet of 15 millimeters of diameters as positive pole, in German Braun glove box, being assembled into can test battery.
The specific capacity test of battery is used Wuhan Lan electricity company cell tester (Land2000) to carry out.Under 0.5C condition, carry out repeatedly loop test.
embodiment 1
A preparation method for the coated chromium nickel lithium titanate of lithium ion battery negative material nickel, raw material used in building-up process, calculates by mass fraction, and its composition and content are as follows:
160 parts of titanium dioxide
1500 parts of deionized waters
36 parts of chrome greens
137 parts of nickel acetates
63 parts of lithium hydroxides
Its synthetic method specifically comprises the steps:
(1), taking 160 parts of titanium dioxide adds 200 parts of deionized waters to be configured to tio_2 suspension, taking 36 parts of chrome greens joins in tio_2 suspension again, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, be of a size of 330nm;
(2), 63 parts of lithium hydroxides are dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
(3), 137 parts of nickel acetates be dissolved in to 800 parts of deionized waters be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2) to ball milling discharging in 0.5 hour;
(4), the green slurry of step (3) gained is sprayed and is dried under stirring, acquisition presoma powder;
(5), last 700 DEG C of calcinings under the inert gas atmosphere that is mixed with 1% concentration reducibility gas, obtain having the coated chromium nickel lithium titanate (Ni/Li of nickel 3ti 4niCrO 12).
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel and detects by X-ray diffractometer (XRD, Rigaku Rigaku), and thing identification of phases result is as Fig. 1.In Fig. 1, can find out that diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, not have the peak position of other materials to occur, the diffraction maximum of chromium nickel lithium titanate is consistent with the diffraction maximum in document.Show that it is to have the coated chromium nickel lithium titanate of nickel that above-mentioned lithium ion battery negative material has the final material that the coated nickel chromium triangle double ion of nickel replaces the synthetic method gained of lithium titanate.
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel, uses ESEM (SEM, NEC 6700F) to carry out pattern detection, and the SEM observed result of gained is as Fig. 2.As can be seen from Figure 2, the lithium ion battery negative material of gained has the shape characteristic that the coated chromium nickel lithium titanate of nickel presents spherical porous structure.The size of nano particle is in 200-300 nanometers.Nanoaperture, as the capillary channel of electrolyte and material exchange lithium ion, has improved the chemical property of material.
By chromium nickel the lithium titanate material coated nickel of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, under 0.5C multiplying power, to test, result is as shown in Figure 3.Its average specific discharge capacity is 155.3 mAh/g, approaches the theoretical capacity of material.Its first discharge specific capacity is 163.1mAh/g, and initial charge specific capacity is 155.1mAh/g, and coulomb efficiency is 95.1% first, and in electric discharge, threshold voltage is 1.52V.After 20 circulations, charge ratio capacity is 153.4 mAh/g, and performance degradation is faint.Test result shows, the coated chromium nickel lithium titanate material of nickel of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in electrokinetic cell field.
embodiment 2
A preparation method for the coated chromium nickel lithium titanate of lithium ion battery negative material nickel, raw material used in building-up process, calculates by mass fraction, and its composition and content are as follows:
160 parts of titanium dioxide
1500 parts of deionized waters
40 parts of chrome greens
125 parts of nickel acetates
63 parts of lithium hydroxides
Its synthetic method specifically comprises the steps:
(1), taking 160 parts of titanium dioxide adds 200 parts of deionized waters to be configured to tio_2 suspension, taking 40 parts of chrome greens joins in tio_2 suspension again, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, be of a size of 300nm;
(2), 63 parts of lithium hydroxides are dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
(3), 125 parts of nickel acetates be dissolved in to 800 parts of deionized waters be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2) to ball milling discharging in 0.5 hour;
(4), the green slurry of step (3) gained is sprayed and is dried under stirring, acquisition presoma powder;
(5), last 800 DEG C of calcinings under the inert gas atmosphere that is mixed with 3% concentration reducibility gas, obtain having the coated chromium nickel lithium titanate (Ni/Li of nickel 3ti 4niCrO 12).
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel and detects by X-ray diffractometer (XRD, Rigaku Rigaku), and thing identification of phases result is similar to Fig. 1 result.In diffracting spectrum, all diffraction maximums can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, do not have the peak position of other materials to occur, the diffraction maximum of chromium nickel lithium titanate is consistent with the diffraction maximum in document.Show that it is to have the coated chromium nickel lithium titanate of nickel that above-mentioned lithium ion battery negative material has the final material that the coated nickel chromium triangle double ion of nickel replaces the synthetic method gained of lithium titanate.
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel, uses ESEM (SEM, NEC 6700F) to carry out pattern detection, and the SEM observed result of gained is also similar with Fig. 2 result.The lithium ion battery negative material of gained has the shape characteristic that the coated chromium nickel lithium titanate of nickel presents spherical porous structure.The size of nano particle is in 200-300 nanometers.Nanoaperture, as the capillary channel of electrolyte and material exchange lithium ion, has improved the chemical property of material.
By chromium nickel the lithium titanate material coated nickel of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, the charge-discharge performance to this battery under the multiplying power of 0.5C is tested.Its average specific discharge capacity is 154.6 mAh/g, approaches the theoretical capacity of material.Its first discharge specific capacity is 156.4mAh/g, and initial charge specific capacity is 148.7 mAh/g, and coulomb efficiency is 96.1% first, and in electric discharge, threshold voltage is 1.53V.After 20 circulations, charge ratio capacity is 147.4 mAh/g, and performance degradation is faint.Test result shows, the coated chromium nickel lithium titanate material of nickel of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in electrokinetic cell field.
embodiment 3
A preparation method for the coated chromium nickel lithium titanate of lithium ion battery negative material nickel, raw material used in building-up process, calculates by mass fraction, and its composition and content are as follows:
160 parts of titanium dioxide
1500 parts of deionized waters
44 parts of chrome greens
112 parts of nickel acetates
63 parts of lithium hydroxides
Its synthetic method specifically comprises the steps:
(1), taking 160 parts of titanium dioxide adds 200 parts of deionized waters to be configured to tio_2 suspension, taking 44 parts of chrome greens joins in tio_2 suspension again, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, be of a size of 330nm;
(2), 63 parts of lithium hydroxides are dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
(3), 112 parts of nickel acetates be dissolved in to 800 parts of deionized waters be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2) to ball milling discharging in 0.5 hour;
(4), the green slurry of step (3) gained is sprayed and is dried under stirring, acquisition presoma powder;
(5), last 900 DEG C of calcinings under the inert gas atmosphere that is mixed with 5% concentration reducibility gas, obtain having the coated chromium nickel lithium titanate (Ni/Li of nickel 3ti 4niCrO 12).
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel and detects by X-ray diffractometer (XRD, Rigaku Rigaku), and thing identification of phases result is similar to Fig. 1 result.In diffracting spectrum, all diffraction maximums can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, do not have the peak position of other materials to occur, the diffraction maximum of chromium nickel lithium titanate is consistent with the diffraction maximum in document.Show that it is to have the coated chromium nickel lithium titanate of nickel that above-mentioned lithium ion battery negative material has the final material that the coated nickel chromium triangle double ion of nickel replaces the synthetic method gained of lithium titanate.
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel, uses ESEM (SEM, NEC 6700F) to carry out pattern detection, and the SEM observed result of gained is also similar with Fig. 2 result.The lithium ion battery negative material of gained has the shape characteristic that the coated chromium nickel lithium titanate of nickel presents spherical porous structure.The size of nano particle is in 200-300 nanometers.Nanoaperture, as the capillary channel of electrolyte and material exchange lithium ion, has improved the chemical property of material.
By chromium nickel the lithium titanate material coated nickel of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, the charge-discharge performance to this battery under the multiplying power of 0.5C is tested.Its average specific discharge capacity is 146.5 mAh/g, and its first discharge specific capacity is 153.0mAh/g, and initial charge specific capacity is 145.8mAh/g, and coulomb efficiency is 95.3% first, and in electric discharge, threshold voltage is 1.48V.After 20 circulations, charge ratio capacity is 144.3 mAh/g, and performance degradation is faint.Test result shows, the coated chromium nickel lithium titanate material of nickel of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in electrokinetic cell field.
 
embodiment 4
A preparation method for the coated chromium nickel lithium titanate of lithium ion battery negative material nickel, raw material used in building-up process, calculates by mass fraction, and its composition and content are as follows:
160 parts of titanium dioxide
1500 parts of deionized waters
36 parts of chrome greens
137 parts of nickel acetates
66 parts of lithium hydroxides
Its synthetic method specifically comprises the steps:
(1), taking 160 parts of titanium dioxide adds 200 parts of deionized waters to be configured to tio_2 suspension, taking 36 parts of chrome greens joins in tio_2 suspension again, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, be of a size of 270nm;
(2), 66 parts of lithium hydroxides are dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
(3), 137 parts of nickel acetates be dissolved in to 800 parts of deionized waters be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2) to ball milling discharging in 0.5 hour;
(4), the green slurry of step (3) gained is sprayed and is dried under stirring, acquisition presoma powder;
(5), last 800 DEG C of calcinings under the inert gas atmosphere that is mixed with 1% concentration reducibility gas, obtain having the coated chromium nickel lithium titanate (Ni/Li of nickel 3ti 4niCrO 12).
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel and detects by X-ray diffractometer (XRD, Rigaku Rigaku), and thing identification of phases result is similar to Fig. 1 result.In diffracting spectrum, all diffraction maximums can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, do not have the peak position of other materials to occur, the diffraction maximum of chromium nickel lithium titanate is consistent with the diffraction maximum in document.Show that it is to have the coated chromium nickel lithium titanate of nickel that above-mentioned lithium ion battery negative material has the final material that the coated nickel chromium triangle double ion of nickel replaces the synthetic method gained of lithium titanate.
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel, uses ESEM (SEM, NEC 6700F) to carry out pattern detection, and the SEM observed result of gained is also similar with Fig. 2 result.The lithium ion battery negative material of gained has the shape characteristic that the coated chromium nickel lithium titanate of nickel presents spherical porous structure.The size of nano particle is in 200-300 nanometers.Nanoaperture, as the capillary channel of electrolyte and material exchange lithium ion, has improved the chemical property of material.
By chromium nickel the lithium titanate material coated nickel of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, charge-discharge performance to this battery under 0.5C multiplying power is tested, its average specific discharge capacity is 146.7 mAh/g, its first discharge specific capacity is 154.1mAh/g, initial charge specific capacity is 146.7mAh/g, and coulomb efficiency is 95.2% first, and in electric discharge, threshold voltage is 1.49V.After 20 circulations, charge ratio capacity is 146.1mAh/g, and performance degradation is faint.Test result shows, the coated chromium nickel lithium titanate material of nickel of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in electrokinetic cell field.
 
embodiment 5
A preparation method for the coated chromium nickel lithium titanate of lithium ion battery negative material nickel, raw material used in building-up process, calculates by mass fraction, and its composition and content are as follows:
160 parts of titanium dioxide
1500 parts of deionized waters
44 parts of chrome greens
112 parts of nickel acetates
66 parts of lithium hydroxides
Its synthetic method specifically comprises the steps:
(1), taking 160 parts of titanium dioxide adds 200 parts of deionized waters to be configured to tio_2 suspension, taking 44 parts of chrome greens joins in tio_2 suspension again, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, be of a size of 250nm;
(2), 66 parts of lithium hydroxides are dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
(3), 112 parts of nickel acetates be dissolved in to 800 parts of deionized waters be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2) to ball milling discharging in 0.5 hour;
(4), the green slurry of step (3) gained is sprayed and is dried under stirring, acquisition presoma powder;
(5), last 900 DEG C of calcinings under the inert gas atmosphere that is mixed with 3% concentration reducibility gas, obtain having the coated chromium nickel lithium titanate (Ni/Li of nickel 3ti 4niCrO 12).
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel and detects by X-ray diffractometer (XRD, Rigaku Rigaku), and thing identification of phases result is similar to Fig. 1 result.In diffracting spectrum, all diffraction maximums can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, do not have the peak position of other materials to occur, the diffraction maximum of chromium nickel lithium titanate is consistent with the diffraction maximum in document.Show that it is to have the coated chromium nickel lithium titanate of nickel that above-mentioned lithium ion battery negative material has the final material that the coated nickel chromium triangle double ion of nickel replaces the synthetic method gained of lithium titanate.
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel, uses ESEM (SEM, NEC 6700F) to carry out pattern detection, and the SEM observed result of gained is also similar with Fig. 2 result.The lithium ion battery negative material of gained has the shape characteristic that the coated chromium nickel lithium titanate of nickel presents spherical porous structure.The size of nano particle is in 200-300 nanometers.Nanoaperture, as the capillary channel of electrolyte and material exchange lithium ion, has improved the chemical property of material.
By chromium nickel the lithium titanate material coated nickel of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, charge-discharge performance to this battery under 0.5C multiplying power is tested, its average specific discharge capacity is 145.3 mAh/g, its first discharge specific capacity is 153.1mAh/g, initial charge specific capacity is 146.8mAh/g, and coulomb efficiency is 95.9% first, and in electric discharge, threshold voltage is 1.51V.After 20 circulations, charge ratio capacity is 144.8mAh/g, and performance degradation is faint.Test result shows, the coated chromium nickel lithium titanate material of nickel of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in electrokinetic cell field.
 
embodiment 6
A preparation method for the coated chromium nickel lithium titanate of lithium ion battery negative material nickel, raw material used in building-up process, calculates by mass fraction, and its composition and content are as follows:
160 parts of titanium dioxide
1500 parts of deionized waters
36 parts of chrome greens
137 parts of nickel acetates
69 parts of lithium hydroxides
Its synthetic method specifically comprises the steps:
(1), taking 160 parts of titanium dioxide adds 200 parts of deionized waters to be configured to tio_2 suspension, taking 36 parts of chrome greens joins in tio_2 suspension again, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, be of a size of 350nm;
(2), 69 parts of lithium hydroxides are dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
(3), 137 parts of nickel acetates be dissolved in to 800 parts of deionized waters be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2) to ball milling discharging in 0.5 hour;
(4), the green slurry of step (3) gained is sprayed and is dried under stirring, acquisition presoma powder;
(5), last 700 DEG C of calcinings under the inert gas atmosphere that is mixed with 5% concentration reducibility gas, obtain having the coated chromium nickel lithium titanate (Ni/Li of nickel 3ti 4niCrO 12).
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel and detects by X-ray diffractometer (XRD, Rigaku Rigaku), and thing identification of phases result is similar to Fig. 1 result.In diffracting spectrum, all diffraction maximums can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, do not have the peak position of other materials to occur, the diffraction maximum of chromium nickel lithium titanate is consistent with the diffraction maximum in document.Show that it is to have the coated chromium nickel lithium titanate of nickel that above-mentioned lithium ion battery negative material has the final material that the coated nickel chromium triangle double ion of nickel replaces the synthetic method gained of lithium titanate.
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel, uses ESEM (SEM, NEC 6700F) to carry out pattern detection, and the SEM observed result of gained is also similar with Fig. 2 result.The lithium ion battery negative material of gained has the shape characteristic that the coated chromium nickel lithium titanate of nickel presents spherical porous structure.The size of nano particle is in 200-300 nanometers.Nanoaperture, as the capillary channel of electrolyte and material exchange lithium ion, has improved the chemical property of material.
By chromium nickel the lithium titanate material coated nickel of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, charge-discharge performance to this battery under 0.5C multiplying power is tested, its average specific discharge capacity is 154.4 mAh/g, its first discharge specific capacity is 154.3mAh/g, initial charge specific capacity is 151.7mAh/g, and coulomb efficiency is 98.3% first, and in electric discharge, threshold voltage is 1.50V.After 20 circulations, charge ratio capacity is 150.2mAh/g, and performance degradation is faint.Test result shows, the coated chromium nickel lithium titanate material of nickel of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in electrokinetic cell field.
 
embodiment 7
A preparation method for the coated chromium nickel lithium titanate of lithium ion battery negative material nickel, raw material used in building-up process, calculates by mass fraction, and its composition and content are as follows:
160 parts of titanium dioxide
1500 parts of deionized waters
40 parts of chrome greens
125 parts of nickel acetates
69 parts of lithium hydroxides
Its synthetic method specifically comprises the steps:
(1), taking 160 parts of titanium dioxide adds 200 parts of deionized waters to be configured to tio_2 suspension, taking 40 parts of chrome greens joins in tio_2 suspension again, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, be of a size of 370nm;
(2), 69 parts of lithium hydroxides are dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
(3), 125 parts of nickel acetates be dissolved in to 800 parts of deionized waters be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2) to ball milling discharging in 0.5 hour;
(4), the green slurry of step (3) gained is sprayed and is dried under stirring, acquisition presoma powder;
(5), last 900 DEG C of calcinings under the inert gas atmosphere that is mixed with 1% concentration reducibility gas, obtain having the coated chromium nickel lithium titanate (Ni/Li of nickel 3ti 4niCrO 12).
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel and detects by X-ray diffractometer (XRD, Rigaku Rigaku), and thing identification of phases result is similar to Fig. 1 result.In diffracting spectrum, all diffraction maximums can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, do not have the peak position of other materials to occur, the diffraction maximum of chromium nickel lithium titanate is consistent with the diffraction maximum in document.Show that it is to have the coated chromium nickel lithium titanate of nickel that above-mentioned lithium ion battery negative material has the final material that the coated nickel chromium triangle double ion of nickel replaces the synthetic method gained of lithium titanate.
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel, uses ESEM (SEM, NEC 6700F) to carry out pattern detection, and the SEM observed result of gained is also similar with Fig. 2 result.The lithium ion battery negative material of gained has the shape characteristic that the coated chromium nickel lithium titanate of nickel presents spherical porous structure.The size of nano particle is in 200-300 nanometers.Nanoaperture, as the capillary channel of electrolyte and material exchange lithium ion, has improved the chemical property of material.
By chromium nickel the lithium titanate material coated nickel of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, charge-discharge performance to this battery under 0.5C multiplying power is tested, its average specific discharge capacity is 150.4 mAh/g, its first discharge specific capacity is 156.7mAh/g, initial charge specific capacity is 149.3mAh/g, and coulomb efficiency is 95.3% first, and in electric discharge, threshold voltage is 1.50V.After 20 circulations, charge ratio capacity is 147.6mAh/g, and performance degradation is faint.Test result shows, the coated chromium nickel lithium titanate material of nickel of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in electrokinetic cell field.
embodiment 8
A preparation method for the coated chromium nickel lithium titanate of lithium ion battery negative material nickel, raw material used in building-up process, calculates by mass fraction, and its composition and content are as follows:
160 parts of titanium dioxide
1500 parts of deionized waters
44 parts of chrome greens
112 parts of nickel acetates
69 parts of lithium hydroxides
Its synthetic method specifically comprises the steps:
(1), taking 160 parts of titanium dioxide adds 200 parts of deionized waters to be configured to tio_2 suspension, taking 44 parts of chrome greens joins in tio_2 suspension again, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, be of a size of 310nm;
(2), 69 parts of lithium hydroxides are dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
(3), 112 parts of nickel acetates be dissolved in to 800 parts of deionized waters be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2) to ball milling discharging in 0.5 hour;
(4), the green slurry of step (3) gained is sprayed and is dried under stirring, acquisition presoma powder;
(5), last 700 DEG C of calcinings under the inert gas atmosphere that is mixed with 3% concentration reducibility gas, obtain having the coated chromium nickel lithium titanate (Ni/Li of nickel 3ti 4niCrO 12).
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel and detects by X-ray diffractometer (XRD, Rigaku Rigaku), and thing identification of phases result is similar to Fig. 1 result.In diffracting spectrum, all diffraction maximums can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, do not have the peak position of other materials to occur, the diffraction maximum of chromium nickel lithium titanate is consistent with the diffraction maximum in document.Show that it is to have the coated chromium nickel lithium titanate of nickel that above-mentioned lithium ion battery negative material has the final material that the coated nickel chromium triangle double ion of nickel replaces the synthetic method gained of lithium titanate.
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel, uses ESEM (SEM, NEC 6700F) to carry out pattern detection, and the SEM observed result of gained is also similar with Fig. 2 result.The lithium ion battery negative material of gained has the shape characteristic that the coated chromium nickel lithium titanate of nickel presents spherical porous structure.The size of nano particle is in 200-300 nanometers.Nanoaperture, as the capillary channel of electrolyte and material exchange lithium ion, has improved the chemical property of material.
By chromium nickel the lithium titanate material coated nickel of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, charge-discharge performance to this battery under 0.5C multiplying power is tested, and its average specific discharge capacity is 153.4 mAh/g, approaches the theoretical capacity of material.Its first discharge specific capacity is 160.2mAh/g, and initial charge specific capacity is 152.8mAh/g, and coulomb efficiency is 95.2% first, and in electric discharge, threshold voltage is 1.50V.After 20 circulations, charge ratio capacity is 149.7mAh/g, and performance degradation is faint.Test result shows, the coated chromium nickel lithium titanate material of nickel of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in electrokinetic cell field.
 
embodiment 9
Lithium ion battery negative material nickel chromium triangle double ion replaces the synthetic method of lithium titanate, raw material used in building-up process, and by mass fraction calculating, its composition and content are as follows:
160 parts of titanium dioxide
1500 parts of deionized waters
40 parts of chrome greens
125 parts of nickel acetates
66 parts of lithium hydroxides
Its synthetic method specifically comprises the steps:
(1), taking 160 parts of titanium dioxide adds 200 parts of deionized waters to be configured to tio_2 suspension, taking 40 parts of chrome greens joins in tio_2 suspension again, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, be of a size of 300nm;
(2), 66 parts of lithium hydroxides are dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
(3), 125 parts of nickel acetates be dissolved in to 800 parts of deionized waters be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2) to ball milling discharging in 0.5 hour;
(4), the green slurry of step (3) gained is sprayed and is dried under stirring, acquisition presoma powder;
(5), last 800 DEG C of calcinings under the inert gas atmosphere that is mixed with 5% concentration reducibility gas, obtain having the coated chromium nickel lithium titanate (Ni/Li of nickel 3ti 4niCrO 12).
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel and detects by X-ray diffractometer (XRD, Rigaku Rigaku).Thing identification of phases result is similar to Fig. 1 result.In diffracting spectrum, all diffraction maximums can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, do not have the peak position of other materials to occur, the diffraction maximum of chromium nickel lithium titanate is consistent with the diffraction maximum in document.Show that it is to have the coated chromium nickel lithium titanate of nickel that above-mentioned lithium ion battery negative material has the final material that the coated nickel chromium triangle double ion of nickel replaces the synthetic method gained of lithium titanate.
The lithium ion battery negative material of above-mentioned gained has the coated chromium nickel lithium titanate of nickel, uses ESEM (SEM, NEC 6700F) to carry out pattern detection, and the SEM observed result of gained is also similar with Fig. 2 result.The lithium ion battery negative material of gained has the shape characteristic that the coated chromium nickel lithium titanate of nickel presents spherical porous structure.The size of nano particle is in 200-300 nanometers.Nanoaperture, as the capillary channel of electrolyte and material exchange lithium ion, has improved the chemical property of material.
By chromium nickel the lithium titanate material coated nickel of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, the charge-discharge performance to this battery under the multiplying power of 0.5C is tested.Its average specific discharge capacity is 156 mAh/g, approaches the theoretical capacity of material.Its first discharge specific capacity is 162.4mAh/g, and initial charge specific capacity is 155.6mAh/g, and coulomb efficiency is 95.8% first, and in electric discharge, threshold voltage is 1.50V.After 20 circulations, charge ratio capacity is 153.2mAh/g, and performance degradation is faint.Test result shows, the coated chromium nickel lithium titanate material of nickel of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in electrokinetic cell field.

Claims (11)

1. a preparation method for the coated chromium nickel lithium titanate of lithium ion battery negative material nickel, is characterized in that comprising the steps:
First take titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide, the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:36 ~ 44:112 ~ 137:63 ~ 69;
Add 200 parts of deionized waters to be configured to tio_2 suspension titanium dioxide, chrome green is joined in tio_2 suspension, pour in ball mill suspension into while stirring ball milling, obtain the slurry of nano-scale, control pulp particle size between 200-400nm;
Lithium hydroxide is dissolved in 500 parts of deionized waters and obtains lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the ball mill of step (2);
Nickel acetate is dissolved in to 800 parts of deionized waters and is configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (3), ball milling discharging in 0.5 ~ 1 hour;
The green slurry of step (4) gained is sprayed under stirring dry, obtain presoma powder;
By 700 DEG C of-900 DEG C of calcinings under the inert gas atmosphere that is mixed with reducibility gas of presoma powder, obtain the coated chromium nickel lithium titanate of nickel.
2. the preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: described reducibility gas is hydrogen, the concentration of reducibility gas in total gas is 1%-5%, and described inert gas is one or more the combination in argon gas, nitrogen, helium.
3. the preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:36:137:63, the concentration of reducibility gas in total gas is 1%, and calcining heat is 700 DEG C.
4. the preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:40:125:63, the concentration of reducibility gas in total gas is 3%, and calcining heat is 800 DEG C.
5. the preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:112:63, the concentration of reducibility gas in total gas is 5%, and calcining heat is 900 DEG C.
6. the preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:36:137:66, the concentration of reducibility gas in total gas is 1%, and calcining heat is 800 DEG C.
7. the preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:112:66, the concentration of reducibility gas in total gas is 3%, and calcining heat is 900 DEG C.
8. the preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:36:137:69, the concentration of reducibility gas in total gas is 5%, and calcining heat is 700 DEG C.
9. the preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:125:69, the concentration of reducibility gas in total gas is 1%, and calcining heat is 900 DEG C.
10. the preparation method of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:112:69, the concentration of reducibility gas in total gas is 3%, and calcining heat is 700 DEG C.
11. preparation methods of the coated chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel as described in claim 1, it is characterized in that: the weight ratio of described titanium dioxide, deionized water, chrome green, nickel acetate and lithium hydroxide is 160:1500:44:125:66, the concentration of reducibility gas in total gas is 5%, and calcining heat is 800 DEG C.
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CN104600288A (en) * 2014-12-29 2015-05-06 上海应用技术学院 Lithium ion battery porous negative electrode material cobalt coated cobalt chromium lithium titanate and synthetic method thereof

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JP2008243674A (en) * 2007-03-28 2008-10-09 Toshiba Corp Active material, nonaqueous electrolyte battery, battery pack, and automobile
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Publication number Priority date Publication date Assignee Title
CN104505489A (en) * 2014-12-29 2015-04-08 上海应用技术学院 Lithium ion battery negative electrode material Li3Ti4CoCrO12 and synthetic method thereof
CN104600288A (en) * 2014-12-29 2015-05-06 上海应用技术学院 Lithium ion battery porous negative electrode material cobalt coated cobalt chromium lithium titanate and synthetic method thereof

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