CN104037415B - A kind of preparation method of chromium nickel lithium titanate of lithium ion battery negative material nickel coated - Google Patents

A kind of preparation method of chromium nickel lithium titanate of lithium ion battery negative material nickel coated Download PDF

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CN104037415B
CN104037415B CN201410281167.XA CN201410281167A CN104037415B CN 104037415 B CN104037415 B CN 104037415B CN 201410281167 A CN201410281167 A CN 201410281167A CN 104037415 B CN104037415 B CN 104037415B
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nickel
lithium
chromium
lithium titanate
ion battery
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CN104037415A (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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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/626Metals
    • 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 preparation method of the chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated of the present invention, titanium dioxide and deionized water are under agitation mixed to get suspension according to a certain percentage, chrome green is joined in the suspension of titanium dioxide and stir, lithium hydroxide is dissolved and obtains lithium hydroxide aqueous solution in deionized water, nickel acetate is dissolved and is configured to nickel acetate solution in deionized water, by above-mentioned suspension, solution mixing, ball milling obtains precursor liquid.Precursor liquid is carried out spraying dry, obtains through high-temperature calcination under the inert gas atmosphere being mixed with reducibility gas and there is the coated negative material chromium nickel lithium titanate of metallic nickel.The product pattern obtained by the present invention is unified for spherical, and particle size is nanoscale, there is certain nanoaperture between nano particle.The nickel coated of material surface makes its surperficial steric hindrance reduce simultaneously, and particle conductivity increases, and cyclical stability strengthens, and makes this chromium nickel lithium titanate material have good application prospect in electrokinetic cell field.

Description

A kind of preparation method of chromium nickel lithium titanate of lithium ion battery negative material nickel coated
Technical field
The invention belongs to new energy materials field, particularly relate to a kind of lithium battery, specifically a kind of chromium nickel lithium titanate (Ni/Li of lithium ion battery negative material nickel coated 3ti 4niCrO 12) preparation method.
Background technology
Along with the fast development of human society, the demand of the energy is sharply increased, energy resource consumption total amount linearly ascendant trend.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 in succession to encourage the research and apply of new forms of energy 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 the concern of people, also development electric motor car is classified as important developing direction in China's 863 Program.Lithium (ion) battery, as the chemical power source of latest generation, becomes the focus that people pay close attention to.
Lithium ion battery be nineteen ninety Japan Sony Corporation develop and start to realize commercial a kind of high-efficiency energy-storage product, compared with other batteries, the advantage of lithium ion battery be operating voltage high (3.6V, be cadmium-nickel, three times of nickel-hydrogen battery), volume little (less than nickel-hydrogen battery 30%), quality light (lighter than nickel-hydrogen battery 50%), 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 element mostly, but material with carbon element also has some to be difficult to the weakness overcome as negative pole in actual applications, such as, the current potential of Carbon anode and the current potential of lithium metal very close, when the battery is overcharged, 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 large quantifier elimination.Spinel-type Li 4ti 5o 12as a kind of novel ion secondary battery cathode material lithium, compared with material with carbon element, advantages such as having good cycle, do not react with electrolyte, security performance is high, charge and discharge platform is steady is one of the most excellent lithium ion battery negative material received much concern in recent years.
Spinel-type Li 4ti 5o 12space lattice group be cubic system, when discharge and recharge, skeleton structure characteristic is " zero strain ".But because Li4Ti5O12 is a kind of semi-conducting material, poorly conductive, the shortcomings such as density is low cause its chemical property under high magnification poor.Begin one's study for a lot of scholar of this situation the modification of lithium titanate.
The people such as HanyEl-Shinawi adopt sol-gel process to prepare double ion doped titanic acid lithium material (Li 3ti 4niMnO 12andLi 3ti 4niCrO 12: Newsubstitutedlithiumtitaniumoxides, SolidStateSciences, 22 (2013) 65-70), prepared chromium nickel lithium titanate first discharge specific capacity under 0.5C multiplying power is 156mAh/g, close to theoretical specific capacity, there is higher discharge-rate, good 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 adopting sol-gel process to prepare is long, cost compare is high, is not suitable for industrialization and produces.
By above analysis, there is charge and discharge cycles poor stability in existing double ion doping vario-property lithium titanate, manufacturing cycle is long, and cost compare is high, the problems such as operating procedure is complicated, the particle size of chromium nickel lithium titanate of not easily accomplishing scale production, control.
Summary of the invention
For the defect existed in above-mentioned prior art, technical problem to be solved by this invention is to provide a kind of chromium nickel lithium titanate (Ni/Li of lithium ion battery negative material nickel coated 3ti 4niCrO 12) preparation method; lithium titanate battery charge and discharge cycles poor stability prepared by the method that the preparation method of the chromium nickel lithium titanate of described this lithium ion battery negative material nickel coated will solve prior art; manufacturing cycle is long; cost compare is high, operating procedure complexity, the technical problem of not easily accomplishing scale production.
The preparation method of the chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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 and be configured to tio_2 suspension, chrome green is joined in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, 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 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) green slurry of step (4) gained is carried out spraying dry under stirring, obtain presoma powder;
(6) by 700 DEG C-900 DEG C calcinings under the inert gas atmosphere being mixed with reducibility gas of presoma powder, the chromium nickel lithium titanate of nickel coated is namely obtained.
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 chromium nickel lithium titanate of nickel coated, nano ball grinding technique is adopted to control presoma size, by the lithium titanate material of the high-temperature calcination acquisition nano-scale under reducing atmosphere, final acquisition initial specific capacities is high, the nickel coated chromium nickel lithium titanate material of good cycle.Its particle diameter is little and even, reduces Li +migration path, diffusional resistance reduces, can removal lithium embedded better; Simultaneously owing to having carried out nickel coated on the surface of chromium nickel lithium titanate, the surperficial steric hindrance of material is reduced, and 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, there is certain nanoaperture between nano particle.The nanometer of material decreases the distance of lithium ion mobility, is expected to improve its multiplying power property; ; The existence of nanoaperture provides the capillary channel of lithium ion exchanged needs, is conducive to diffusion and the exchange of lithium ion.Such architectural feature makes the specific capacity of material increase, and cyclical stability improves.Test under 0.5C multiplying power, first discharge specific capacity can reach 163mAh/g, and the material prepared than people such as HanyEl-Shinawi improves 5%, and has good cyclical stability, and after 20 times charge and discharge cycles terminates, special capacity fade is faint.In addition, operation of the present invention is simple, can industrial applications.
The chromium nickel lithium titanate material of the nickel coated of above-mentioned gained is assembled into button battery, under 0.5C multiplying power, the charge-discharge performance of this battery is tested, its averaged discharge specific capacity is 155.9mAh/g, its first discharge specific capacity is 154.3mAh/g-163.1mAh/g, initial charge specific capacity is 145.3mAh/g-155.1mAh/g, coulombic efficiency is 95.1-98.3% first, and electric discharge mean voltage is 1.48-1.53V.After 20 times charge and discharge cycles terminates, special capacity fade is faint.
The present invention compares with prior art, and its technological progress is significant.The preparation method of the chromium nickel lithium titanate of lithium ion battery negative material nickel coated 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, lithium, titanium ion is replaced 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 the chromium nickel lithium titanate surface of simultaneously preparing is containing metallic nickel coating layer.The nickel coated of material surface makes its surperficial steric hindrance reduce, and particle conductivity increases, and cyclical stability strengthens; Such architectural feature makes the specific capacity of material increase, 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.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates that the lithium ion battery negative material of embodiment 1 gained has the chromium nickel lithium titanate of nickel coated;
Fig. 2 is the SEM figure that the lithium ion battery negative material of embodiment 1 gained has the chromium nickel lithium titanate of nickel coated;
Fig. 3 is the chemical property collection of illustrative plates that the lithium ion battery negative material of embodiment 1 gained has the chromium nickel lithium titanate of nickel coated.
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 of acquisition, conductive carbon powder, organic binder bond are gathered inclined tetrafluoroethene (PVDF) and calculate according to mass ratio, i.e. lithium ion battery negative material chromium nickel lithium titanate: conductive carbon powder: it is that the ratio of 80:10:10 mixes that organic binder bond gathers inclined tetrafluoroethene, slurry is formed after abundant stirring, be coated on aluminium foil surface, after oven dry, repeatedly rolling, obtains battery cathode sheet;
(2), battery assembling and performance test
2016 type half-cell assessments are used to obtain the chemical property of chromium nickel lithium titanate.The battery pole piece that rolling is good is stamped into the disk of diameter 12 millimeters, after its quality of precise, the quality of the lithium titanate in pole piece is calculated according to formula composition, use the barrier film of diameter 19 millimeters, use the metal lithium sheet of diameter 15 millimeters as positive pole, being assembled in German Braun glove box can test battery.
The specific capacity test of battery uses Wuhan Lan electricity company cell tester (Land2000) to carry out.Repeatedly loop test is carried out under 0.5C condition.
embodiment 1
A preparation method for the chromium nickel lithium titanate of lithium ion battery negative material nickel coated, raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 160 parts
Deionized water 1500 parts
Chrome green 36 parts
Nickel acetate 137 parts
Lithium hydroxide 63 parts
Its synthetic method specifically comprises the steps:
(1), take 160 parts of titanium dioxide to add 200 parts of deionized waters and be configured to tio_2 suspension, taking 36 parts of chrome greens again joins in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, obtain the slurry of nano-scale, be of a size of 330nm;
(2), by 63 parts of lithium hydroxides be 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), by 137 parts of nickel acetates be dissolved in 800 parts of deionized waters and be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2), ball milling discharging in 0.5 hour;
(4), by the green slurry of step (3) gained under stirring, carry out spraying dry, obtain presoma powder;
(5), last 700 DEG C of calcinings under the inert gas atmosphere being mixed with 1% concentration reducibility gas, namely obtain the chromium nickel lithium titanate (Ni/Li with nickel coated 3ti 4niCrO 12).
The chromium nickel lithium titanate that the lithium ion battery negative material of above-mentioned gained has nickel coated is detected by X-ray diffractometer (XRD, Rigaku Rigaku), and Discriminating materials result is as Fig. 1.Can find out in Fig. 1 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, namely 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 the final material of synthetic method gained that nickel chromium triangle double ion that above-mentioned lithium ion battery negative material has a nickel coated replaces lithium titanate is the chromium nickel lithium titanate with nickel coated.
The lithium ion battery negative material of above-mentioned gained has the chromium nickel lithium titanate of nickel coated, and use ESEM (SEM, NEC 6700F) to carry out Shape measure, the SEM observed result of gained is as Fig. 2.As can be seen from Figure 2, the chromium nickel lithium titanate that the lithium ion battery negative material of gained has a nickel coated presents the shape characteristic of 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, improves the chemical property of material.
By the chromium nickel lithium titanate material of the nickel coated of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, result as shown in Figure 3.Its averaged discharge specific capacity is 155.3mAh/g, close to the theoretical capacity of material.Its first discharge specific capacity is 163.1mAh/g, and initial charge specific capacity is 155.1mAh/g, and coulombic efficiency is 95.1% first, and electric discharge mean voltage is 1.52V.After 20 circulations, charge specific capacity is 153.4mAh/g, and performance degradation is faint.Test result shows, the chromium nickel lithium titanate material of the nickel coated 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 chromium nickel lithium titanate of lithium ion battery negative material nickel coated, raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 160 parts
Deionized water 1500 parts
Chrome green 40 parts
Nickel acetate 125 parts
Lithium hydroxide 63 parts
Its synthetic method specifically comprises the steps:
(1), take 160 parts of titanium dioxide to add 200 parts of deionized waters and be configured to tio_2 suspension, taking 40 parts of chrome greens again joins in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, obtain the slurry of nano-scale, be of a size of 300nm;
(2), by 63 parts of lithium hydroxides be 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), by 125 parts of nickel acetates be dissolved in 800 parts of deionized waters and be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2), ball milling discharging in 0.5 hour;
(4), by the green slurry of step (3) gained under stirring, carry out spraying dry, obtain presoma powder;
(5), last 800 DEG C of calcinings under the inert gas atmosphere being mixed with 3% concentration reducibility gas, namely obtain the chromium nickel lithium titanate (Ni/Li with nickel coated 3ti 4niCrO 12).
The chromium nickel lithium titanate that the lithium ion battery negative material of above-mentioned gained has nickel coated is detected by X-ray diffractometer (XRD, Rigaku Rigaku), and Discriminating materials result is similar to Fig. 1 result.Diffraction maximums all in diffracting spectrum can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, and namely 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 the final material of synthetic method gained that nickel chromium triangle double ion that above-mentioned lithium ion battery negative material has a nickel coated replaces lithium titanate is the chromium nickel lithium titanate with nickel coated.
The lithium ion battery negative material of above-mentioned gained has the chromium nickel lithium titanate of nickel coated, and use ESEM (SEM, NEC 6700F) to carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result.The chromium nickel lithium titanate that the lithium ion battery negative material of gained has a nickel coated presents the shape characteristic of 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, improves the chemical property of material.
By the chromium nickel lithium titanate material of the nickel coated of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.5C, the charge-discharge performance of this battery is tested.Its averaged discharge specific capacity is 154.6mAh/g, close to the theoretical capacity of material.Its first discharge specific capacity is 156.4mAh/g, and initial charge specific capacity is 148.7mAh/g, and coulombic efficiency is 96.1% first, and electric discharge mean voltage is 1.53V.After 20 circulations, charge specific capacity is 147.4mAh/g, and performance degradation is faint.Test result shows, the chromium nickel lithium titanate material of the nickel coated 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 chromium nickel lithium titanate of lithium ion battery negative material nickel coated, raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 160 parts
Deionized water 1500 parts
Chrome green 44 parts
Nickel acetate 112 parts
Lithium hydroxide 63 parts
Its synthetic method specifically comprises the steps:
(1), take 160 parts of titanium dioxide to add 200 parts of deionized waters and be configured to tio_2 suspension, taking 44 parts of chrome greens again joins in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, obtain the slurry of nano-scale, be of a size of 330nm;
(2), by 63 parts of lithium hydroxides be 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), by 112 parts of nickel acetates be dissolved in 800 parts of deionized waters and be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2), ball milling discharging in 0.5 hour;
(4), by the green slurry of step (3) gained under stirring, carry out spraying dry, obtain presoma powder;
(5), last 900 DEG C of calcinings under the inert gas atmosphere being mixed with 5% concentration reducibility gas, namely obtain the chromium nickel lithium titanate (Ni/Li with nickel coated 3ti 4niCrO 12).
The chromium nickel lithium titanate that the lithium ion battery negative material of above-mentioned gained has nickel coated is detected by X-ray diffractometer (XRD, Rigaku Rigaku), and Discriminating materials result is similar to Fig. 1 result.Diffraction maximums all in diffracting spectrum can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, and namely 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 the final material of synthetic method gained that nickel chromium triangle double ion that above-mentioned lithium ion battery negative material has a nickel coated replaces lithium titanate is the chromium nickel lithium titanate with nickel coated.
The lithium ion battery negative material of above-mentioned gained has the chromium nickel lithium titanate of nickel coated, and use ESEM (SEM, NEC 6700F) to carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result.The chromium nickel lithium titanate that the lithium ion battery negative material of gained has a nickel coated presents the shape characteristic of 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, improves the chemical property of material.
By the chromium nickel lithium titanate material of the nickel coated of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.5C, the charge-discharge performance of this battery is tested.Its averaged discharge specific capacity is 146.5mAh/g, and its first discharge specific capacity is 153.0mAh/g, and initial charge specific capacity is 145.8mAh/g, and coulombic efficiency is 95.3% first, and electric discharge mean voltage is 1.48V.After 20 circulations, charge specific capacity is 144.3mAh/g, and performance degradation is faint.Test result shows, the chromium nickel lithium titanate material of the nickel coated 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 chromium nickel lithium titanate of lithium ion battery negative material nickel coated, raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 160 parts
Deionized water 1500 parts
Chrome green 36 parts
Nickel acetate 137 parts
Lithium hydroxide 66 parts
Its synthetic method specifically comprises the steps:
(1), take 160 parts of titanium dioxide to add 200 parts of deionized waters and be configured to tio_2 suspension, taking 36 parts of chrome greens again joins in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, obtain the slurry of nano-scale, be of a size of 270nm;
(2), by 66 parts of lithium hydroxides be 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), by 137 parts of nickel acetates be dissolved in 800 parts of deionized waters and be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2), ball milling discharging in 0.5 hour;
(4), by the green slurry of step (3) gained under stirring, carry out spraying dry, obtain presoma powder;
(5), last 800 DEG C of calcinings under the inert gas atmosphere being mixed with 1% concentration reducibility gas, namely obtain the chromium nickel lithium titanate (Ni/Li with nickel coated 3ti 4niCrO 12).
The chromium nickel lithium titanate that the lithium ion battery negative material of above-mentioned gained has nickel coated is detected by X-ray diffractometer (XRD, Rigaku Rigaku), and Discriminating materials result is similar to Fig. 1 result.Diffraction maximums all in diffracting spectrum can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, and namely 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 the final material of synthetic method gained that nickel chromium triangle double ion that above-mentioned lithium ion battery negative material has a nickel coated replaces lithium titanate is the chromium nickel lithium titanate with nickel coated.
The lithium ion battery negative material of above-mentioned gained has the chromium nickel lithium titanate of nickel coated, and use ESEM (SEM, NEC 6700F) to carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result.The chromium nickel lithium titanate that the lithium ion battery negative material of gained has a nickel coated presents the shape characteristic of 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, improves the chemical property of material.
By the chromium nickel lithium titanate material of the nickel coated of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, under 0.5C multiplying power, the charge-discharge performance of this battery is tested, its averaged discharge specific capacity is 146.7mAh/g, its first discharge specific capacity is 154.1mAh/g, initial charge specific capacity is 146.7mAh/g, and coulombic efficiency is 95.2% first, and electric discharge mean voltage is 1.49V.After 20 circulations, charge specific capacity is 146.1mAh/g, and performance degradation is faint.Test result shows, the chromium nickel lithium titanate material of the nickel coated 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 chromium nickel lithium titanate of lithium ion battery negative material nickel coated, raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 160 parts
Deionized water 1500 parts
Chrome green 44 parts
Nickel acetate 112 parts
Lithium hydroxide 66 parts
Its synthetic method specifically comprises the steps:
(1), take 160 parts of titanium dioxide to add 200 parts of deionized waters and be configured to tio_2 suspension, taking 44 parts of chrome greens again joins in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, obtain the slurry of nano-scale, be of a size of 250nm;
(2), by 66 parts of lithium hydroxides be 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), by 112 parts of nickel acetates be dissolved in 800 parts of deionized waters and be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2), ball milling discharging in 0.5 hour;
(4), by the green slurry of step (3) gained under stirring, carry out spraying dry, obtain presoma powder;
(5), last 900 DEG C of calcinings under the inert gas atmosphere being mixed with 3% concentration reducibility gas, namely obtain the chromium nickel lithium titanate (Ni/Li with nickel coated 3ti 4niCrO 12).
The chromium nickel lithium titanate that the lithium ion battery negative material of above-mentioned gained has nickel coated is detected by X-ray diffractometer (XRD, Rigaku Rigaku), and Discriminating materials result is similar to Fig. 1 result.Diffraction maximums all in diffracting spectrum can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, and namely 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 the final material of synthetic method gained that nickel chromium triangle double ion that above-mentioned lithium ion battery negative material has a nickel coated replaces lithium titanate is the chromium nickel lithium titanate with nickel coated.
The lithium ion battery negative material of above-mentioned gained has the chromium nickel lithium titanate of nickel coated, and use ESEM (SEM, NEC 6700F) to carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result.The chromium nickel lithium titanate that the lithium ion battery negative material of gained has a nickel coated presents the shape characteristic of 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, improves the chemical property of material.
By the chromium nickel lithium titanate material of the nickel coated of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, under 0.5C multiplying power, the charge-discharge performance of this battery is tested, its averaged discharge specific capacity is 145.3mAh/g, its first discharge specific capacity is 153.1mAh/g, initial charge specific capacity is 146.8mAh/g, and coulombic efficiency is 95.9% first, and electric discharge mean voltage is 1.51V.After 20 circulations, charge specific capacity is 144.8mAh/g, and performance degradation is faint.Test result shows, the chromium nickel lithium titanate material of the nickel coated 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 chromium nickel lithium titanate of lithium ion battery negative material nickel coated, raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 160 parts
Deionized water 1500 parts
Chrome green 36 parts
Nickel acetate 137 parts
Lithium hydroxide 69 parts
Its synthetic method specifically comprises the steps:
(1), take 160 parts of titanium dioxide to add 200 parts of deionized waters and be configured to tio_2 suspension, taking 36 parts of chrome greens again joins in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, obtain the slurry of nano-scale, be of a size of 350nm;
(2), by 69 parts of lithium hydroxides be 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), by 137 parts of nickel acetates be dissolved in 800 parts of deionized waters and be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2), ball milling discharging in 0.5 hour;
(4), by the green slurry of step (3) gained under stirring, carry out spraying dry, obtain presoma powder;
(5), last 700 DEG C of calcinings under the inert gas atmosphere being mixed with 5% concentration reducibility gas, namely obtain the chromium nickel lithium titanate (Ni/Li with nickel coated 3ti 4niCrO 12).
The chromium nickel lithium titanate that the lithium ion battery negative material of above-mentioned gained has nickel coated is detected by X-ray diffractometer (XRD, Rigaku Rigaku), and Discriminating materials result is similar to Fig. 1 result.Diffraction maximums all in diffracting spectrum can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, and namely 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 the final material of synthetic method gained that nickel chromium triangle double ion that above-mentioned lithium ion battery negative material has a nickel coated replaces lithium titanate is the chromium nickel lithium titanate with nickel coated.
The lithium ion battery negative material of above-mentioned gained has the chromium nickel lithium titanate of nickel coated, and use ESEM (SEM, NEC 6700F) to carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result.The chromium nickel lithium titanate that the lithium ion battery negative material of gained has a nickel coated presents the shape characteristic of 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, improves the chemical property of material.
By the chromium nickel lithium titanate material of the nickel coated of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, under 0.5C multiplying power, the charge-discharge performance of this battery is tested, its averaged discharge specific capacity is 154.4mAh/g, its first discharge specific capacity is 154.3mAh/g, initial charge specific capacity is 151.7mAh/g, and coulombic efficiency is 98.3% first, and electric discharge mean voltage is 1.50V.After 20 circulations, charge specific capacity is 150.2mAh/g, and performance degradation is faint.Test result shows, the chromium nickel lithium titanate material of the nickel coated 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 chromium nickel lithium titanate of lithium ion battery negative material nickel coated, raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 160 parts
Deionized water 1500 parts
Chrome green 40 parts
Nickel acetate 125 parts
Lithium hydroxide 69 parts
Its synthetic method specifically comprises the steps:
(1), take 160 parts of titanium dioxide to add 200 parts of deionized waters and be configured to tio_2 suspension, taking 40 parts of chrome greens again joins in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, obtain the slurry of nano-scale, be of a size of 370nm;
(2), by 69 parts of lithium hydroxides be 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), by 125 parts of nickel acetates be dissolved in 800 parts of deionized waters and be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2), ball milling discharging in 0.5 hour;
(4), by the green slurry of step (3) gained under stirring, carry out spraying dry, obtain presoma powder;
(5), last 900 DEG C of calcinings under the inert gas atmosphere being mixed with 1% concentration reducibility gas, namely obtain the chromium nickel lithium titanate (Ni/Li with nickel coated 3ti 4niCrO 12).
The chromium nickel lithium titanate that the lithium ion battery negative material of above-mentioned gained has nickel coated is detected by X-ray diffractometer (XRD, Rigaku Rigaku), and Discriminating materials result is similar to Fig. 1 result.Diffraction maximums all in diffracting spectrum can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, and namely 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 the final material of synthetic method gained that nickel chromium triangle double ion that above-mentioned lithium ion battery negative material has a nickel coated replaces lithium titanate is the chromium nickel lithium titanate with nickel coated.
The lithium ion battery negative material of above-mentioned gained has the chromium nickel lithium titanate of nickel coated, and use ESEM (SEM, NEC 6700F) to carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result.The chromium nickel lithium titanate that the lithium ion battery negative material of gained has a nickel coated presents the shape characteristic of 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, improves the chemical property of material.
By the chromium nickel lithium titanate material of the nickel coated of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, under 0.5C multiplying power, the charge-discharge performance of this battery is tested, its averaged discharge specific capacity is 150.4mAh/g, its first discharge specific capacity is 156.7mAh/g, initial charge specific capacity is 149.3mAh/g, and coulombic efficiency is 95.3% first, and electric discharge mean voltage is 1.50V.After 20 circulations, charge specific capacity is 147.6mAh/g, and performance degradation is faint.Test result shows, the chromium nickel lithium titanate material of the nickel coated 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 chromium nickel lithium titanate of lithium ion battery negative material nickel coated, raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 160 parts
Deionized water 1500 parts
Chrome green 44 parts
Nickel acetate 112 parts
Lithium hydroxide 69 parts
Its synthetic method specifically comprises the steps:
(1), take 160 parts of titanium dioxide to add 200 parts of deionized waters and be configured to tio_2 suspension, taking 44 parts of chrome greens again joins in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, obtain the slurry of nano-scale, be of a size of 310nm;
(2), by 69 parts of lithium hydroxides be 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), by 112 parts of nickel acetates be dissolved in 800 parts of deionized waters and be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2), ball milling discharging in 0.5 hour;
(4), by the green slurry of step (3) gained under stirring, carry out spraying dry, obtain presoma powder;
(5), last 700 DEG C of calcinings under the inert gas atmosphere being mixed with 3% concentration reducibility gas, namely obtain the chromium nickel lithium titanate (Ni/Li with nickel coated 3ti 4niCrO 12).
The chromium nickel lithium titanate that the lithium ion battery negative material of above-mentioned gained has nickel coated is detected by X-ray diffractometer (XRD, Rigaku Rigaku), and Discriminating materials result is similar to Fig. 1 result.Diffraction maximums all in diffracting spectrum can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, and namely 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 the final material of synthetic method gained that nickel chromium triangle double ion that above-mentioned lithium ion battery negative material has a nickel coated replaces lithium titanate is the chromium nickel lithium titanate with nickel coated.
The lithium ion battery negative material of above-mentioned gained has the chromium nickel lithium titanate of nickel coated, and use ESEM (SEM, NEC 6700F) to carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result.The chromium nickel lithium titanate that the lithium ion battery negative material of gained has a nickel coated presents the shape characteristic of 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, improves the chemical property of material.
By the chromium nickel lithium titanate material of the nickel coated of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test the charge-discharge performance of this battery under 0.5C multiplying power, its averaged discharge specific capacity is 153.4mAh/g, close to the theoretical capacity of material.Its first discharge specific capacity is 160.2mAh/g, and initial charge specific capacity is 152.8mAh/g, and coulombic efficiency is 95.2% first, and electric discharge mean voltage is 1.50V.After 20 circulations, charge specific capacity is 149.7mAh/g, and performance degradation is faint.Test result shows, the chromium nickel lithium titanate material of the nickel coated 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, calculates by mass fraction, its composition and content as follows:
Titanium dioxide 160 parts
Deionized water 1500 parts
Chrome green 40 parts
Nickel acetate 125 parts
Lithium hydroxide 66 parts
Its synthetic method specifically comprises the steps:
(1), take 160 parts of titanium dioxide to add 200 parts of deionized waters and be configured to tio_2 suspension, taking 40 parts of chrome greens again joins in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, obtain the slurry of nano-scale, be of a size of 300nm;
(2), by 66 parts of lithium hydroxides be 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), by 125 parts of nickel acetates be dissolved in 800 parts of deionized waters and be configured to nickel acetate aqueous solution, the nickel acetate aqueous solution of gained is joined in the ball mill of step (2), ball milling discharging in 0.5 hour;
(4), by the green slurry of step (3) gained under stirring, carry out spraying dry, obtain presoma powder;
(5), last 800 DEG C of calcinings under the inert gas atmosphere being mixed with 5% concentration reducibility gas, namely obtain the chromium nickel lithium titanate (Ni/Li with nickel coated 3ti 4niCrO 12).
The chromium nickel lithium titanate that the lithium ion battery negative material of above-mentioned gained has nickel coated is detected by X-ray diffractometer (XRD, Rigaku Rigaku).Discriminating materials result is similar to Fig. 1 result.Diffraction maximums all in diffracting spectrum can be demarcated as the diffraction maximum of chromium nickel lithium titanate and metallic nickel, and namely 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 the final material of synthetic method gained that nickel chromium triangle double ion that above-mentioned lithium ion battery negative material has a nickel coated replaces lithium titanate is the chromium nickel lithium titanate with nickel coated.
The lithium ion battery negative material of above-mentioned gained has the chromium nickel lithium titanate of nickel coated, and use ESEM (SEM, NEC 6700F) to carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result.The chromium nickel lithium titanate that the lithium ion battery negative material of gained has a nickel coated presents the shape characteristic of 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, improves the chemical property of material.
By the chromium nickel lithium titanate material of the nickel coated of above-mentioned gained, use half-cell method to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.5C, the charge-discharge performance of this battery is tested.Its averaged discharge specific capacity is 156mAh/g, close to the theoretical capacity of material.Its first discharge specific capacity is 162.4mAh/g, and initial charge specific capacity is 155.6mAh/g, and coulombic efficiency is 95.8% first, and electric discharge mean voltage is 1.50V.After 20 circulations, charge specific capacity is 153.2mAh/g, and performance degradation is faint.Test result shows, the chromium nickel lithium titanate material of the nickel coated 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 chromium nickel lithium titanate of lithium ion battery negative material nickel coated, is characterized in that comprising 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 and be configured to tio_2 suspension, chrome green is joined in tio_2 suspension, suspension to be poured in ball mill into ball milling while stirring, 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 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) green slurry of step (4) gained is carried out spraying dry under stirring, obtain presoma powder;
(6) by 700 DEG C-900 DEG C calcinings under the inert gas atmosphere being mixed with reducibility gas of presoma powder, namely the chromium nickel lithium titanate of nickel coated is obtained, described chromium nickel lithium titanate presents spherical porous structure, and the size of described chromium nickel lithium titanate particle is between 200-300 nanometers.
2. the preparation method of the chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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 chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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 chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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 chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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 chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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 chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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 chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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 chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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 chromium nickel lithium titanate of a kind of lithium ion battery negative material nickel coated 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.
The preparation method of the chromium nickel lithium titanate of 11. a kind of lithium ion battery negative material nickel coated 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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