CN104600288A - Lithium ion battery porous negative electrode material cobalt coated cobalt chromium lithium titanate and synthetic method thereof - Google Patents

Lithium ion battery porous negative electrode material cobalt coated cobalt chromium lithium titanate and synthetic method thereof Download PDF

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CN104600288A
CN104600288A CN201410835459.3A CN201410835459A CN104600288A CN 104600288 A CN104600288 A CN 104600288A CN 201410835459 A CN201410835459 A CN 201410835459A CN 104600288 A CN104600288 A CN 104600288A
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cobalt
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常程康
郭倩
邓玲
蔡元元
王永强
陈茜
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Shanghai Institute of Technology
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Abstract

The invention discloses a lithium ion battery porous negative electrode material cobalt coated cobalt chromium lithium titanate and a synthetic method thereof. The raw materials used in the synthetic process are as follows in parts by weight: 82 parts of titanium dioxide, 400 parts of de-ionized water, 17.3-21.1 parts of chromium sesquioxide, 20.4-24.8 parts of cobaltous oxide and 30-36 parts of lithium hydroxide. The synthetic method comprises the following steps: preparing titanium dioxide suspension firstly, adding chromium sesquioxide and cobaltous oxide sequentially into the titanium dioxide suspension to obtain a mixed solution, pouring the obtained mixed solution into a ball mill, and performing ball milling; dissolving lithium hydroxide into de-ionized water to obtain a lithium hydroxide aqueous solution, adding the lithium hydroxide aqueous solution into the ball mill, further performing ball milling so as to obtain a gray slurry, spray-drying, and then roasting in an inert gas atmosphere mixed with a reducing agent, so as to obtain the lithium ion battery porous negative electrode material cobalt coated cobalt chromium lithium titanate with excellent electrochemical properties and circulatory stability.

Description

The cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt is coated and synthetic method thereof
Technical field
The present invention relates to the cobalt chromium lithium titanate (Co/Li that a kind of lithium ion battery negative material cobalt is coated 3ti 4coCrO 12) synthetic method, belong to new energy materials field, in field of lithium ion battery, there is wide application prospect.
Background technology
The survival and development of the mankind all be unable to do without the support of the energy.For a long time, the mankind obtain the important sources of energy is traditional fossil fuel.But not only utilization ratio is low during combustion of fossil fuel, and a large amount of greenhouse gas can be discharged, or even pernicious gas, thus bring great threat to environment.Along with growth economic from now on, the supply of the energy also will increase, but China exists again populous problem, if select the energy resource consumption mode the same with developed country in China, the energy supply problem how solving China just seems most important.In order to the challenge that better response environment pollutes and lack of energy brings, realize low-carbon (LC) society and just require that we research and develop efficient, safe, pollution-free and reproducible new forms of energy, wherein one of most important research direction studies chemical power source---utilize the mutual conversion between chemical energy and electric energy to develop efficient pollution-free and reproducible high-energy chemistry power supply.
First chemical power source in the world---" voltaic cell " is after the initial stage in 19th century produces, and via the revolution of several power technology, chemical power source serves extremely important effect in the middle of the process helping the pollution of mankind's processing environment and energy crisis.Novel chemical power source---serondary lithium battery, because its voltage is high, lightweight, volume is little, specific capacity is large, memory-less effect, have extended cycle life, can a series of highly significant such as fast charging and discharging and non-environmental-pollution advantage and receive much attention, and obtain and develop sharp.The commercially produced product of present serondary lithium battery has been widely used in pure electric vehicle (EV), plug-in electric motor car (PHEV), hybrid-power electric vehicle (HEV), portable electric appts (Portable Electronics), energy storing device (Energy Storage) etc.
At present, commercial lithium ion battery negative material adopts various 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 is greatly about 0.1V, when the battery is overcharged, carbon electrodes is easily separated out Li dendrite and causes safety issue; Graphite cathode is a kind of layer structure, Lithium-ion embeding embedding go out time can deform, reduce the useful life of graphite cathode.In order to solve the safety problem of lithium battery, people have done large quantifier elimination.
Canadian Studies person K.Zaghib proposes first time in 1996 and selects lithium titanate to form lithium-ions battery as negative material and high-voltage anode material, or form electrochemical mixed capacitor (K. Zaghib with carbon electrode, Solid state lithium ion batteries using carbon or an oxide as negative electrode, Proceedings of Lithium Polymer Batteries (ISBN 1 56,677 167 6)).Afterwards, researcher's little bavin letter of Japan is fine waits people also to carry out the research of lithium titanate as ion cathode material lithium.Spinel type lithium titanate has Li +three-dimensional diffusion passage, can carry out high rate charge-discharge, and the Stability Analysis of Structures of material is constant in the middle of charge and discharge process, is therefore called as " zero strain " material, there is splendid cycle performance and security performance, so spinel type lithium titanate is considered to desirable lithium ion battery negative material.But, cause its chemical property under high magnification poor because Li4Ti5O12 electronic conductivity is low.Begin one's study for a lot of scholar of this situation the modification of lithium titanate.
The people such as Hany El-Shinawi adopt the sol-gel process of modification 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 0.2C multiplying power is 156mAh/g, close to theoretical specific capacity, there is 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 cost compare adopting sol-gel process to prepare is high, output capacity is lower, and production process is complicated, is not suitable for industrialization and produces.
By above analysis; there is charge and discharge cycles poor stability in existing lithium titanate anode material; the electronic conductivity of material is low; cost compare is high; operating procedure is complicated, not easily accomplish scale production, battery exists the problems such as flatulence in charge and discharge process, needs to research and develop the demand that Novel Titanium silicate material meets battery industry.
Summary of the invention
An object of the present invention there is charge and discharge cycles poor stability to solve above-mentioned lithium titanate anode material; the electronic conductivity of material is low; cost compare is high, and operating procedure is complicated, not easily accomplish scale production, cobalt chromium lithium titanate (Co/Li that battery exists the technical problems such as flatulence and provides a kind of Novel cathode material for lithium ion battery cobalt coated in charge and discharge process 3ti 4coCrO 12) and synthetic method.Namely replace lithium, titanium ion with cobalt, chromium ion, after replacing, the structure of crystal is still spinel structure, and the conductive metal simple substance cobalt of cobalt chromium lithium titanate mask simultaneously prepared by one-step calcination is coated, i.e. Co/Li 3ti 4coCrO 12.This material is tested under 0.5C, and its averaged discharge specific capacity is 151.2 mAh/g, and electric discharge mean voltage is 1.50V.Capability retention 99.5% after 20 circulations.This Co/Li 3ti 4coCrO 12negative material has good chemical property.
Technical scheme of the present invention
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 17.3-21.1 part
Cobalt black 20.4-24.8 part
Lithium hydroxide 30-36 part
Its synthetic method specifically comprises the steps:
(1), by titanium dioxide join in the deionized water of 1/2 total amount, obtain tio_2 suspension;
Chrome green and cobalt black are joined in tio_2 suspension successively and mixes, obtain mixed liquor, then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 200-350nm, obtain slurry;
(2), by lithium hydroxide be dissolved in remaining deionized water and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 700-900 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1-5%, and inert gas is argon gas, nitrogen or helium.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated and Co/Li 3ti 4coCrO 12, main ball milling and the atomizing granulating technology of adopting controls the particle diameter of presoma and the pattern of material, and obtain the coated cobalt chromium lithium titanate of lithium ion battery negative material cobalt by carrying out high-temperature calcination under reducing atmosphere, its initial specific capacities is high, good cycle.
Cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained is assembled into button battery, under 0.5C multiplying power, the charge-discharge performance of this button cell is tested, test result shows, its averaged discharge specific capacity is 151.2mAh/g, its first discharge specific capacity is 151.3-156.1mAh/g, initial charge specific capacity is 148.3-150.1mAh/g, coulombic efficiency is 95.8-98.3% first, electric discharge mean voltage is 1.48-1.53V, after 20 times charge and discharge cycles terminates, capability retention is 99.5%.
Beneficial effect of the present invention
The cobalt chromium lithium titanate (Co/Li that a kind of lithium ion battery negative material cobalt of the present invention is coated 3ti 4coCrO 12), owing to adopting nano ball grinding and atomizing granulating technology to control the particle diameter of presoma and the pattern of material in building-up process, and obtain the coated cobalt chromium lithium titanate of the cobalt of nano-scale by the high-temperature calcination under reducing atmosphere.Namely the particle diameter of the cobalt chromium lithium titanate that the cobalt of gained is coated is little and even, reduces Li +migration path, diffusional resistance reduces, can removal lithium embedded better; Certain space is there is, the embedding existing for lithium ion in these spaces and embeddingly go out to provide favourable condition between the particle of the cobalt chromium lithium titanate that cobalt is coated; Simultaneously because the surface of cobalt chromium lithium titanate has cobalt coated, the surperficial steric hindrance of material is reduced, and conductivity strengthens, and cyclical stability improves.
Further, the coated cobalt chromium lithium titanate pattern of a kind of lithium ion battery negative material cobalt of the present invention is unified is spherical second particle, particle diameter is at 10-20 micron, second particle is made up of less nano particle (i.e. primary particle), at 100-200nm, between nano particle, there is certain nanoaperture in the size of this nano particle.The nanometer of the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated decreases the distance of lithium ion mobility; The existence of nanoaperture provides the capillary channel of lithium ion exchanged needs, is conducive to diffusion and the exchange of lithium ion.The specific capacity of the cobalt chromium lithium titanate that such architectural feature makes a kind of lithium ion battery negative material cobalt of the present invention coated increases, and cyclical stability improves.Test under 0.5C multiplying power, first discharge specific capacity can reach 152.1mAh/g, and averaged discharge specific capacity is 151.2 mAh/g.Have good cyclical stability, after 20 times charge and discharge cycles terminates, capability retention is 99.5% simultaneously.
Further, the synthetic method of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt of the present invention is coated, its technique is simple, with low cost, is applicable to suitability for industrialized production.
Accompanying drawing explanation
The XRD collection of illustrative plates of the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of Fig. 1, embodiment 1 gained is coated;
The SEM figure of cobalt chromium lithium titanate gained under 3.00K multiplying power that the lithium ion battery negative material cobalt of Fig. 2 a, embodiment 1 gained is coated;
The SEM figure of cobalt chromium lithium titanate gained under 30.0K multiplying power that the lithium ion battery negative material cobalt of Fig. 2 b, embodiment 1 gained is coated;
The chemical property collection of illustrative plates of the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of Fig. 3, embodiment 1 gained is 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
Cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt 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 cobalt chromium 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 the coated cobalt chromium lithium titanate of lithium ion battery negative material cobalt;
The disk of diameter 12 millimeters is stamped into by the battery cathode sheet that rolling is good, after its quality of precise, the quality of the coated cobalt chromium lithium titanate of the cobalt calculated in pole piece is formed according to formula, use the poly-micropore propylene barrier film of diameter 19mm, use the metal lithium sheet of diameter 15mm as positive pole, in German Braun glove box, be assembled into testable button cell;
After assembling, the specific capacity test of the button cell of gained uses Wuhan Lan electricity company cell tester (Land2000) to carry out.Repeatedly loop test is carried out under 0.5C condition.
embodiment 1
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 19.2 parts
Cobalt black 22.8 parts
Lithium hydroxide 33 parts;
Its synthetic method specifically comprises the steps:
(1), by 82 parts of titanium dioxide join in the 1/2 total amount i.e. deionized water of 200 parts, obtain tio_2 suspension;
19.2 parts of chrome greens and 22.8 parts of cobalt blacks are joined in the tio_2 suspension of above-mentioned gained successively and mixes, obtain mixed liquor;
Then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 300nm, obtain slurry;
(2), by 33 parts of lithium hydroxides be dissolved in the deionized water of remaining 200 parts and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 700-900 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, i.e. Co/Li 3ti 4coCrO 12;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 5%, and inert gas is argon gas.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained as shown in Figure 1, as can be seen from Figure 1 in this XRD figure, all diffraction maximums can be demarcated as the diffraction maximum of cobalt chromium lithium titanate and metallic cobalt, namely the peak position of other materials is not had to occur, the diffraction maximum of cobalt chromium lithium titanate and the similar (Li of diffraction maximum of nickel chromium triangle lithium titanate in document 3ti 4niMnO 12and Li 3ti 4niCrO 12: New substituted lithium titanium oxides, Solid State Sciences, 22 (2013) 65-70), show that the final material of above-mentioned gained is the coated cobalt chromium lithium titanate of cobalt thus.
Use ESEM (SEM, NEC 6700F) the cobalt chromium lithium titanate coated to the lithium ion battery negative material cobalt of above-mentioned gained scan respectively under 3.00K and 30.0k multiplying power, the SEM figure of gained respectively as shown in Figure 2 a and 2 b, the overall pattern of the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated can be found out from Fig. 2 a, be rendered as spherical second particle, particle diameter is at 10-20 micron.Can find out that from Fig. 2 b the second particle of the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated is made up of less nano particle (i.e. primary particle), the size of this nano particle is at 100-200nm.Certain space is there is between spheric granules, nanovoids is as the capillary channel of electrolyte and material exchange lithium ion, be conducive to the embedding of lithium ion and deviate from, thus the nanometer indicating the coated cobalt chromium lithium titanate particle size of lithium ion battery negative material cobalt can improve the chemical property of the coated cobalt chromium lithium titanate of this lithium ion battery negative material cobalt.
By cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, the chemical property figure of gained as shown in Figure 3, as can be seen from Figure 3 its averaged discharge specific capacity is 151.2 mAh/g, close to the theoretical capacity (155.3mAh/g) of material, its first discharge specific capacity is 151.9mAh/g, initial charge specific capacity is 149.1mAh/g, coulombic efficiency is 98.2% first, and electric discharge mean voltage is 1.50V.After 20 circulations, charge specific capacity is 148.4mAh/g, and performance degradation is faint.
The above results shows, the cobalt chromium lithium titanate material that the lithium ion battery negative material cobalt of gained of the present invention is coated has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
embodiment 2
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 21.1 parts
Cobalt black 20.4 parts
Lithium hydroxide 33 parts;
Its synthetic method specifically comprises the steps:
(1), by 82 parts of titanium dioxide join in the 1/2 total amount i.e. deionized water of 200 parts, obtain tio_2 suspension;
21.1 parts of chrome greens and 20.4 parts of cobalt blacks are joined in tio_2 suspension successively and mixes, obtain mixed liquor, then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 320nm, obtain slurry;
(2), by 33 parts of lithium hydroxides be dissolved in 200 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control the speed of stirring be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 700 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, i.e. Co/Li 3ti 4coCrO 12;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 3%, and inert gas is argon gas.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, diffraction maximums all in XRD figure can be demarcated as the diffraction maximum of cobalt chromium lithium titanate and metallic cobalt, namely do not have the peak position of other materials to occur, show that the final thing of above-mentioned gained is the coated cobalt chromium lithium titanate of cobalt thus.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, use ESEM (SEM, NEC 6700F) carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result, namely the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of gained is coated is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheric granules (second particle) are made up of less nano particle (primary particle), and the size of this nano particle is at 100-200nm.There is certain space between spheric granules, nanoaperture as the capillary channel of electrolyte and material exchange lithium ion, be conducive to lithium ion embedding and embedding go out, improve the chemical property of the coated cobalt chromium lithium titanate material of lithium ion battery negative material cobalt.
By cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, its averaged discharge specific capacity is 151.2mAh/g, close to the theoretical capacity (155.3mAh/g) of material, its first discharge specific capacity is 151.3mAh/g, and initial charge specific capacity is 148.3mAh/g, coulombic efficiency is 98.0% first, and electric discharge mean voltage is 1.51V.After 20 circulations, charge specific capacity is 147.6 mAh/g, and performance degradation is faint.Test result shows, the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned synthetic method gained is coated has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
embodiment 3
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 17.3 parts
Cobalt black 24.8 parts
Lithium hydroxide 33 parts;
Its synthetic method specifically comprises the steps:
(1), by 82 parts of titanium dioxide join in the 1/2 total amount i.e. deionized water of 200 parts, obtain tio_2 suspension;
17.3 parts of chrome greens and 24.8 parts of cobalt blacks are joined in tio_2 suspension successively and mixes, obtain mixed liquor;
Then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 340nm, obtain slurry;
(2), by 33 parts of lithium hydroxides be dissolved in 200 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 900 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1%, and inert gas is argon gas.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, diffraction maximums all in XRD figure can be demarcated as the diffraction maximum of cobalt chromium lithium titanate and metallic cobalt, namely do not have the peak position of other materials to occur, show that the final thing of above-mentioned gained is the coated cobalt chromium lithium titanate of cobalt thus.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, use ESEM (SEM, NEC 6700F) carry out Shape measure, SEM observed result and Fig. 2 result of gained are similar, namely the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of gained is coated is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheric granules (second particle) are made up of less nano particle (primary particle), and the size of this nano particle is at 100-200nm.There is certain space between spheric granules, nanoaperture as the capillary channel of electrolyte and material exchange lithium ion, be conducive to lithium ion embedding and embedding go out, improve the chemical property that lithium ion battery negative material is the coated cobalt chromium lithium titanate material of cobalt.
By cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, its averaged discharge specific capacity is 151.2 mAh/g, close to the theoretical capacity (155.3mAh/g) of material, its first discharge specific capacity is 152.1mAh/g, and initial charge specific capacity is 148.9mAh/g, coulombic efficiency is 97.9% first, and electric discharge mean voltage is 1.53V.After 20 circulations, charge specific capacity is 148.2mAh/g, and performance degradation is faint.Test result shows, the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned synthetic method gained is coated has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
embodiment 4
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 19.2 parts
Cobalt black 22.8 parts
Lithium hydroxide 36 parts;
Its synthetic method specifically comprises the steps:
(1), by 82 parts of titanium dioxide join in the 1/2 total amount i.e. deionized water of 200 parts, obtain tio_2 suspension;
19.2 parts of chrome greens and 22.8 parts of cobalt blacks are joined in the tio_2 suspension of above-mentioned gained successively and mixes, obtain mixed liquor;
Then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 290nm, obtain slurry;
(2), by 36 parts of lithium hydroxides be dissolved in the deionized water of remaining 200 parts and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 700 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, i.e. Co/Li 3ti 4coCrO 12;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 5%, and inert gas is argon gas.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, diffraction maximums all in XRD figure can be demarcated as the diffraction maximum of cobalt chromium lithium titanate and metallic cobalt, namely do not have the peak position of other materials to occur, show that the final thing of above-mentioned gained is the coated cobalt chromium lithium titanate of cobalt thus.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, use ESEM (SEM, NEC 6700F) carry out Shape measure, SEM observed result and Fig. 2 result of gained are similar, namely the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of gained is coated is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheric granules (second particle) are made up of less nano particle (primary particle), and the size of this nano particle is at 100-200nm.There is certain space between spheric granules, nanoaperture as the capillary channel of electrolyte and material exchange lithium ion, be conducive to lithium ion embedding and embedding go out, improve the chemical property that lithium ion battery negative material is the coated cobalt chromium lithium titanate material of cobalt.
By cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, its averaged discharge specific capacity is 151.2mAh/g, close to the theoretical capacity (155.3mAh/g) of material, its first discharge specific capacity is 153.5mAh/g, and initial charge specific capacity is 149.4mAh/g, coulombic efficiency is 97.3% first, and electric discharge mean voltage is 1.48V.After 20 circulations, charge specific capacity is 148.7mAh/g, and performance degradation is faint.Test result shows, the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned synthetic method gained is coated has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
embodiment 5
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 21.1 parts
Cobalt black 20.4 parts
Lithium hydroxide 36 parts;
Its synthetic method specifically comprises the steps:
(1), by 82 parts of titanium dioxide join in the 1/2 total amount i.e. deionized water of 200 parts, obtain tio_2 suspension;
21.1 parts of chrome greens and 20.4 parts of cobalt blacks are joined in the tio_2 suspension of above-mentioned gained successively and mixes, obtain mixed liquor;
Then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 270nm, obtain slurry;
(2), by 36 parts of lithium hydroxides be dissolved in the deionized water of remaining 200 parts and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 900 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, i.e. Co/Li 3ti 4coCrO 12;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 3%, and inert gas is argon gas.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, diffraction maximums all in XRD figure can be demarcated as the diffraction maximum of cobalt chromium lithium titanate and metallic cobalt, namely do not have the peak position of other materials to occur, show that the final thing of above-mentioned gained is the coated cobalt chromium lithium titanate of cobalt thus.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, use ESEM (SEM, NEC 6700F) carry out Shape measure, SEM observed result and Fig. 2 result of gained are similar, namely the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of gained is coated is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheric granules (second particle) are made up of less nano particle (primary particle), and the size of this nano particle is at 100-200nm.There is certain space between spheric granules, nanoaperture as the capillary channel of electrolyte and material exchange lithium ion, be conducive to lithium ion embedding and embedding go out, improve the chemical property that lithium ion battery negative material is the coated cobalt chromium lithium titanate material of cobalt.
By cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, its averaged discharge specific capacity is 151.2mAh/g, close to the theoretical capacity (155.3mAh/g) of material, its first discharge specific capacity is 154.1mAh/g, and initial charge specific capacity is 150.0mAh/g, coulombic efficiency is 97.3% first, and electric discharge mean voltage is 1.50V.After 20 circulations, charge specific capacity is 149.3mAh/g, and performance degradation is faint.Test result shows, the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned synthetic method gained is coated has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
embodiment 6
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 17.3 parts
Cobalt black 24.8 parts
Lithium hydroxide 36 parts;
Its synthetic method specifically comprises the steps:
(1), by 82 parts of titanium dioxide join in the 1/2 total amount i.e. deionized water of 200 parts, obtain tio_2 suspension;
17.3 parts of chrome greens and 24.8 parts of cobalt blacks are joined in the tio_2 suspension of above-mentioned gained successively and mixes, obtain mixed liquor;
Then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 350nm, obtain slurry;
(2), by 36 parts of lithium hydroxides be dissolved in the deionized water of remaining 200 parts and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 800 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, i.e. Co/Li 3ti 4coCrO 12;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1%, and inert gas is argon gas.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, diffraction maximums all in XRD figure can be demarcated as the diffraction maximum of cobalt chromium lithium titanate and metallic cobalt, namely do not have the peak position of other materials to occur, show that the final thing of above-mentioned gained is the coated cobalt chromium lithium titanate of cobalt thus.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, use ESEM (SEM, NEC 6700F) carry out Shape measure, SEM observed result and Fig. 2 result of gained are similar, namely the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of gained is coated is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheric granules (second particle) are made up of less nano particle (primary particle), and the size of this nano particle is at 100-200nm.There is certain space between spheric granules, nanoaperture as the capillary channel of electrolyte and material exchange lithium ion, be conducive to lithium ion embedding and embedding go out, improve the chemical property that lithium ion battery negative material is the coated cobalt chromium lithium titanate material of cobalt.
By cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, its averaged discharge specific capacity is 151.2mAh/g, close to the theoretical capacity (155.3mAh/g) of material, its first discharge specific capacity is 155.4mAh/g, and initial charge specific capacity is 150.1mAh/g, coulombic efficiency is 96.6% first, and electric discharge mean voltage is 1.49V.After 20 circulations, charge specific capacity is 149.3mAh/g, and performance degradation is faint.Test result shows, the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned synthetic method gained is coated has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
embodiment 7
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 19.2 parts
Cobalt black 22.8 parts
Lithium hydroxide 30 parts;
Its synthetic method specifically comprises the steps:
(1), by 82 parts of titanium dioxide join in the 1/2 total amount i.e. deionized water of 200 parts, obtain tio_2 suspension;
19.2 parts of chrome greens and 22.8 parts of cobalt blacks are joined in the tio_2 suspension of above-mentioned gained successively and mixes, obtain mixed liquor;
Then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 320nm, obtain slurry;
(2), by 30 parts of lithium hydroxides be dissolved in the deionized water of remaining 200 parts and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 900 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, i.e. Co/Li 3ti 4coCrO 12;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 5%, and inert gas is argon gas.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, diffraction maximums all in XRD figure can be demarcated as the diffraction maximum of cobalt chromium lithium titanate and metallic cobalt, namely do not have the peak position of other materials to occur, show that the final thing of above-mentioned gained is the coated cobalt chromium lithium titanate of cobalt thus.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, use ESEM (SEM, NEC 6700F) carry out Shape measure, SEM observed result and Fig. 2 result of gained are similar, namely the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of gained is coated is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheric granules (second particle) are made up of less nano particle (primary particle), and the size of this nano particle is at 100-200nm.There is certain space between spheric granules, nanoaperture as the capillary channel of electrolyte and material exchange lithium ion, be conducive to lithium ion embedding and embedding go out, improve the chemical property that lithium ion battery negative material is the coated cobalt chromium lithium titanate material of cobalt.
By cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, its averaged discharge specific capacity is 151.2mAh/g, close to the theoretical capacity (155.3mAh/g) of material, its first discharge specific capacity is 156.1mAh/g, and initial charge specific capacity is 149.8mAh/g, coulombic efficiency is 96.0% first, and electric discharge mean voltage is 1.50V.After 20 circulations, charge specific capacity is 149.0mAh/g, and performance degradation is faint.Test result shows, the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned synthetic method gained is coated has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
embodiment 8
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 21.1 parts
Cobalt black 20.4 parts
Lithium hydroxide 30 parts;
Its synthetic method specifically comprises the steps:
(1), by 82 parts of titanium dioxide join in the 1/2 total amount i.e. deionized water of 200 parts, obtain tio_2 suspension;
21.1 parts of chrome greens and 20.4 parts of cobalt blacks are joined in the tio_2 suspension of above-mentioned gained successively and mixes, obtain mixed liquor;
Then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 260nm, obtain slurry;
(2), by 30 parts of lithium hydroxides be dissolved in the deionized water of remaining 200 parts and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 800 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, i.e. Co/Li 3ti 4coCrO 12;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 3%, and inert gas is argon gas.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, diffraction maximums all in XRD figure can be demarcated as the diffraction maximum of cobalt chromium lithium titanate and metallic cobalt, namely do not have the peak position of other materials to occur, show that the final thing of above-mentioned gained is the coated cobalt chromium lithium titanate of cobalt thus.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, use ESEM (SEM, NEC 6700F) carry out Shape measure, SEM observed result and Fig. 2 result of gained are similar, namely the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of gained is coated is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheric granules (second particle) are made up of less nano particle (primary particle), and the size of this nano particle is at 100-200nm.There is certain space between spheric granules, nanoaperture as the capillary channel of electrolyte and material exchange lithium ion, be conducive to lithium ion embedding and embedding go out, improve the chemical property that lithium ion battery negative material is the coated cobalt chromium lithium titanate material of cobalt.
By cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, its averaged discharge specific capacity is 151.2mAh/g, close to the theoretical capacity (155.3mAh/g) of material, its first discharge specific capacity is 155.8mAh/g, and initial charge specific capacity is 149.2mAh/g, coulombic efficiency is 95.8% first, and electric discharge mean voltage is 1.51V.After 20 circulations, charge specific capacity is 148.5mAh/g, and performance degradation is faint.Test result shows, the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned synthetic method gained is coated has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
embodiment 9
A synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 17.3 parts
Cobalt black 24.8 parts
Lithium hydroxide 30 parts;
Its synthetic method specifically comprises the steps:
(1), by 82 parts of titanium dioxide join in the 1/2 total amount i.e. deionized water of 200 parts, obtain tio_2 suspension;
17.3 parts of chrome greens and 24.8 parts of cobalt blacks are joined in the tio_2 suspension of above-mentioned gained successively and mixes, obtain mixed liquor;
Then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 310nm, obtain slurry;
(2), by 30 parts of lithium hydroxides be dissolved in the deionized water of remaining 200 parts and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry of the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 700 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, i.e. Co/Li 3ti 4coCrO 12;
Described is mixed with in the inert gas of reducibility gas, and reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1%, and inert gas is argon gas.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, diffraction maximums all in XRD figure can be demarcated as the diffraction maximum of cobalt chromium lithium titanate and metallic cobalt, namely do not have the peak position of other materials to occur, show that the final thing of above-mentioned gained is the coated cobalt chromium lithium titanate of cobalt thus.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated, use ESEM (SEM, NEC 6700F) carry out Shape measure, SEM observed result and Fig. 2 result of gained are similar, namely the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of gained is coated is rendered as spherical second particle, particle diameter is at 10-20 micron, and these spheric granules (second particle) are made up of less nano particle (primary particle), and the size of this nano particle is at 100-200nm.There is certain space between spheric granules, nanoaperture as the capillary channel of electrolyte and material exchange lithium ion, be conducive to lithium ion embedding and embedding go out, improve the chemical property of the coated cobalt chromium lithium titanate material of lithium ion battery negative material cobalt.
By cobalt chromium lithium titanate coated for the lithium ion battery negative material cobalt of above-mentioned gained, half-cell method is used to be assembled into button-shaped 2016 batteries, test under 0.5C multiplying power, its averaged discharge specific capacity is 151.2mAh/g, close to the theoretical capacity (155.3mAh/g) of material, its first discharge specific capacity is 151.3mAh/g, and initial charge specific capacity is 148.7mAh/g, coulombic efficiency is 98.3% first, and electric discharge mean voltage is 1.50V.After 20 circulations, charge specific capacity is 148.0mAh/g, and performance degradation is faint.
The above results shows, the cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of gained of the present invention is coated has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement, these improvement also should be considered as protection scope of the present invention.

Claims (12)

1. a synthetic method for the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated, is characterized in that the raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 17.3-21.1 part
Cobalt black 20.4-24.8 part
Lithium hydroxide 30-36 part
Its synthetic method specifically comprises the steps:
(1), by titanium dioxide join in the deionized water of 1/2 total amount, obtain tio_2 suspension;
Chrome green and cobalt black are joined in tio_2 suspension successively and mixes, obtain mixed liquor;
Then the mixed liquor obtained to be poured in ball mill into ball milling while stirring, control particle D50 and be of a size of 200-350nm, obtain slurry;
(2), by lithium hydroxide be dissolved in remaining deionized water and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in the slurry in the ball mill of step (1), proceed ball milling 1h, obtain grey slurry;
(3), by the grey slurry of step (2) gained control mixing speed be 100r/min, inlet temperature is carry out spraying dry at 165 DEG C, obtains presoma powder;
(4), under the inert gas atmosphere being mixed with reducibility gas, the presoma powder control temperature of step (3) gained is 700-900 DEG C and carries out calcining 4h, obtain the cobalt chromium lithium titanate that cobalt is coated.
2. the synthetic method of the cobalt chromium lithium titanate that lithium ion battery negative material cobalt as described in claim 1 is coated, it is characterized in that being mixed with in the inert gas of reducibility gas described in step (4), reducibility gas is hydrogen, by volume percentage calculation, its concentration is 1-5%, and inert gas is argon gas, nitrogen or helium.
3. the synthetic method of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt as described in claim 1 is coated, is characterized in that raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 19.2 parts
Cobalt black 22.8 parts
Lithium hydroxide 33 parts;
Be mixed with in the inert gas of reducibility gas described in the step (4) of its synthetic method, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 5%, and inert gas is argon gas, and calcining heat is 800 DEG C.
4. the synthetic method of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt as described in claim 1 is coated, is characterized in that raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 21.1 parts
Cobalt black 20.4 parts
Lithium hydroxide 33 parts;
Be mixed with in the inert gas of reducibility gas described in the step (4) of its synthetic method, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 3%, and inert gas is argon gas, and calcining heat is 700 DEG C.
5. the synthetic method of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt as described in claim 1 is coated, is characterized in that raw material used in building-up process, calculates according to the mass fraction, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 17.3 parts
Cobalt black 24.8 parts
Lithium hydroxide 33 parts;
Be mixed with in the inert gas of reducibility gas described in the step (4) of its synthetic method, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1%, and inert gas is argon gas, and calcining heat is 900 DEG C.
6. the synthetic method of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt as described in claim 1 is coated, is characterized in that raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 19.2 parts
Cobalt black 22.8 parts
Lithium hydroxide 36 parts;
Be mixed with in the inert gas of reducibility gas described in the step (4) of its synthetic method, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 5%, and inert gas is argon gas, and calcining heat is 700 DEG C.
7. the synthetic method of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt as described in claim 1 is coated, is characterized in that raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 21.1 parts
Cobalt black 20.4 parts
Lithium hydroxide 36 parts;
Be mixed with in the inert gas of reducibility gas described in the step (4) of its synthetic method, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 3%, and inert gas is argon gas, and calcining heat is 900 DEG C.
8. the synthetic method of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt as described in claim 1 is coated, is characterized in that raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 17.3 parts
Cobalt black 24.8 parts
Lithium hydroxide 36 parts;
Be mixed with in the inert gas of reducibility gas described in the step (4) of its synthetic method, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1%, and inert gas is argon gas, and calcining heat is 800 DEG C.
9. the synthetic method of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt as described in claim 1 is coated, is characterized in that raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 19.2 parts
Cobalt black 22.8 parts
Lithium hydroxide 30 parts;
Be mixed with in the inert gas of reducibility gas described in the step (4) of its synthetic method, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 5%, and inert gas is argon gas, and calcining heat is 900 DEG C.
10. the synthetic method of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt as described in claim 1 is coated, is characterized in that raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 21.1 parts
Cobalt black 20.4 parts
Lithium hydroxide 30 parts;
Be mixed with in the inert gas of reducibility gas described in the step (4) of its synthetic method, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 3%, and inert gas is argon gas, and calcining heat is 800 DEG C.
The synthetic method of the cobalt chromium lithium titanate that 11. a kind of lithium ion battery negative material cobalts as described in claim 1 are coated, is characterized in that raw material used in building-up process, by mass fraction calculate, its composition and content as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chrome green 17.3 parts
Cobalt black 24.8 parts
Lithium hydroxide 30 parts;
Be mixed with in the inert gas of reducibility gas described in the step (4) of its synthetic method, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1%, and inert gas is argon gas, and calcining heat is 700 DEG C.
The cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt of 12. preparation method's gained as described in claim 1-11 is coated.
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