CN104600288B - 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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CN104600288B
CN104600288B CN201410835459.3A CN201410835459A CN104600288B CN 104600288 B CN104600288 B CN 104600288B CN 201410835459 A CN201410835459 A CN 201410835459A CN 104600288 B CN104600288 B CN 104600288B
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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 of a kind of lithium ion battery negative material cobalt cladding and synthetic method thereof
Technical field
The present invention relates to the cobalt chromium lithium titanate (Co/Li of a kind of lithium ion battery negative material cobalt cladding3Ti4CoCrO12) 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, during combustion of fossil fuel, not only utilization ratio is low, and can discharge a large amount of greenhouse gases, even harmful gas, thus brings threat greatly to environment.Along with growth economic from now on, the supply of the energy also to increase, but China exists again populous problem, if selecting the energy resource consumption mode as developed country in China, the energy supply problem how solving China just seems most important.For the challenge that more preferable response environment pollutes and lack of energy brings, realizing low-carbon (LC) society and just require that we research and develop efficient, safe and pollution-free and reproducible new forms of energy, one of most important of which research direction is that the mutually conversion between electrochmical power source research and utilization chemical energy and electric energy is developed efficient pollution-free and reproducible high-energy chemistry power supply.
First electrochmical power source " voltaic cell " is after the initial stage in 19th century produces in the world, and via power technology revolution for several times, electrochmical power source is helping mankind's processing environment to pollute and serving extremely important effect in the middle of the process of energy crisis.Novel electrochmical power source serondary lithium battery, owing to its voltage is high, lightweight, volume is little, specific capacity is big, memory-less effect, have extended cycle life, can the advantage of a series of highly significant such as fast charging and discharging and non-environmental-pollution and receive much attention, and obtain and develop sharp.The commercially produced product of 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. now.
At present, the lithium ion battery negative material of commercialization uses various material with carbon element mostly, but material with carbon element also has some to be difficult to the weakness overcome in actual applications as negative pole, such as, the current potential of Carbon anode is about at 0.1V, when the battery is overcharged, carbon electrodes easily separates 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 service life of graphite cathode.In order to solve the safety problem of lithium battery, people have done substantial amounts of research.
Canadian Studies person K.Zaghib proposed selection lithium titanate for the first time and constitutes lithium-ions battery as negative material and high-voltage anode material in 1996, or formed electrochemical mixed capacitor (K. with carbon electrode Zaghib, Solid state lithium ion batteries using carbon or an oxide as negative electrode, Proceedings of Lithium Polymer Batteries (ISBN 1 56677 167 6)).Afterwards, the researcher little bavin letter of Japan is fine et al. has also carried out lithium titanate as the research of ion cathode material lithium.Spinel type lithium titanate has Li+Three-dimensional diffusion passage, high rate charge-discharge can be carried out, and the Stability Analysis of Structures of material is constant in the middle of charge and discharge process, therefore be referred to as " zero strain " material, there is splendid cycle performance and security performance, so spinel type lithium titanate is considered as preferable lithium ion battery negative material.But, cause its chemical property under high magnification poor owing to Li4Ti5O12 electronic conductivity is low.Begin one's study the modification of lithium titanate for a lot of scholar of this situation.
Hany El-Shinawi et al. uses modified sol-gel process to prepare double ion doped titanic acid lithium material (Li3Ti4NiMnO12 and Li3Ti4NiCrO12: 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, has preferable chemical property.It is 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 that uses sol-gel process to prepare is higher, output capacity ratio is relatively low, and production process is complicated, is not suitable for industrialization and produces.
Analyzed by above; there is charge and discharge cycles poor stability in existing lithium titanate anode material; the electronic conductivity of material is low; cost is higher; operating procedure is complicated, be difficult to accomplish scale production, battery exists the problems such as flatulence in charge and discharge process, needs to research and develop Novel Titanium silicate material and meets the demand of battery industry.
Summary of the invention
An object of the present invention is to there is charge and discharge cycles poor stability to solve above-mentioned lithium titanate anode material; the electronic conductivity of material is low; cost is higher, and operating procedure is complicated, be difficult to the cobalt chromium lithium titanate (Co/Li that accomplishes scale production, battery exists the technical problems such as flatulence in charge and discharge process and provides a kind of Novel cathode material for lithium ion battery cobalt to be coated with3Ti4CoCrO12) and synthetic method.I.e. replacing lithium, titanium ion with cobalt, chromium ion, after replacement, the structure of crystal is still spinel structure, and the cobalt chromium conductive metal simple substance cobalt of lithium titanate mask simultaneously prepared by one-step calcination is coated with, i.e. Co/Li3Ti4CoCrO12.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/Li3Ti4CoCrO12Negative material has good chemical property.
Technical scheme
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 17.3-21.1 part
Cobalt black 20.4-24.8 part
Lithium hydrate 30-36 part
Its synthetic method specifically includes following steps:
(1), by titanium dioxide join in the deionized water of 1/2 total amount, obtain tio_2 suspension；
It is added sequentially in tio_2 suspension mix by chromic oxide and cobalt black, obtains mixed liquor, then the mixed liquor obtained is poured in ball mill ball milling while stirring, control granule D50 a size of 200-350nm, obtain slurry；
(2), by Lithium hydrate it is dissolved in remaining deionized water and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1-5%, and noble gas is argon, nitrogen or helium.
The cobalt i.e. Co/Li of chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained3Ti4CoCrO12, the main particle diameter and the pattern of material that use ball milling and atomizing granulating technology to control presoma, the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding is obtained by carrying out high-temperature calcination under reducing atmosphere, its initial specific capacities is high, good cycle.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with 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 effects of the present invention
A kind of cobalt chromium lithium titanate (Co/Li of the lithium ion battery negative material cobalt cladding of the present invention3Ti4CoCrO12), owing to building-up process using nano ball grinding and atomizing granulating technology control particle diameter and the pattern of material of presoma, and obtained the cobalt chromium lithium titanate of the cobalt cladding of nano-scale by the high-temperature calcination under reducing atmosphere.The i.e. particle diameter of the cobalt chromium lithium titanate of the cobalt cladding of gained is little and uniform, reduces Li+Migration path, diffusional resistance reduce, it is possible to preferably removal lithium embedded；There is certain space between the granule of the cobalt chromium lithium titanate of cobalt cladding, the embedding of lithium ion that exist in these spaces goes out to provide favourable condition with embedding；Simultaneously because the surface of cobalt chromium lithium titanate has cobalt to be coated with, making the surface steric hindrance of material reduce, electric conductivity strengthens, and cyclical stability improves.
Further, the cobalt chromium lithium titanate pattern of a kind of lithium ion battery negative material cobalt cladding of the present invention is unified for 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 nanorize of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding decreases the distance of lithium ion mobility；The existence of nanoaperture provides diffusion and the exchange of the capillary channel that lithium ion exchanged needs, beneficially lithium ion.Such architectural feature makes the specific capacity of the cobalt chromium lithium titanate that a kind of lithium ion battery negative material cobalt of the present invention is coated with increase, and cyclical stability improves.Testing under 0.5C multiplying power, first discharge specific capacity can reach 152.1mAh/g, and averaged discharge specific capacity is 151.2 mAh/g.Having 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 of a kind of lithium ion battery negative material cobalt cladding of the present invention, its technique is simple, with low cost, is suitable for industrialized production.
Accompanying drawing explanation
The XRD figure spectrum of the cobalt chromium lithium titanate that Fig. 1, the lithium ion battery negative material cobalt of embodiment 1 gained are coated with；
The SEM figure of cobalt chromium lithium titanate gained under 3.00K multiplying power that Fig. 2 a, the lithium ion battery negative material cobalt of embodiment 1 gained are coated with；
The SEM figure of cobalt chromium lithium titanate gained under 30.0K multiplying power that Fig. 2 b, the lithium ion battery negative material cobalt of embodiment 1 gained are coated with；
The chemical property collection of illustrative plates of the cobalt chromium lithium titanate that Fig. 3, the lithium ion battery negative material cobalt of embodiment 1 gained are coated with.
Detailed description of the invention
Below by specific embodiment and combine accompanying drawing the present invention is described in detail, but it is not limiting as the present invention.
The preparation of battery and the method for testing of chemical property
(1), the preparation of battery cathode sheet
The cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding 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: organic binder bond gathers the ratio that inclined tetrafluoroethene is 80:10:10 and mixes, slurry is formed after being sufficiently stirred for, it is coated on aluminium foil surface, after drying, repeatedly roll, it is thus achieved that battery cathode sheet；
(2), battery assembles and performance test
2016 type half-cell assessments are used to obtain the chemical property of the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated with；
The battery cathode sheet that will roll is stamped into the disk of diameter 12 millimeters, after its quality of precise, the quality of the cobalt chromium lithium titanate that the cobalt in pole piece is coated with is calculated according to formula composition, use the poly-micropore propylene barrier film of diameter 19mm, use the metal lithium sheet of diameter 15mm as positive pole, in Germany's 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 the conditions of 0.5C.
Embodiment 1
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 19.2 parts
Cobalt black 22.8 parts
Lithium hydrate 33 parts；
Its synthetic method specifically includes following steps:
(1), by 82 parts of titanium dioxide join in the deionized water of 1/2 total amount that is 200 part, obtain tio_2 suspension；
It is added sequentially in the tio_2 suspension of above-mentioned gained mix by 19.2 parts of chromic oxides and 22.8 parts of cobalt blacks, obtains mixed liquor；
Then the mixed liquor obtained is poured in ball mill ball milling while stirring, controls granule D50 a size of 300nm, obtain slurry；
(2), by 33 parts of Lithium hydrates it is dissolved in the deionized water of remaining 200 parts and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding, i.e. Co/Li3Ti4CoCrO12；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 5%, and noble gas is argon.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is as shown in Figure 1, as can be seen from Figure 1 in this XRD figure, all of diffraction maximum can be demarcated as cobalt chromium lithium titanate and the diffraction maximum of metallic cobalt, the peak position i.e. not having other materials occurs, the diffraction maximum of cobalt chromium lithium titanate and the similar (Li of the diffraction maximum of nickel chromium triangle lithium titanate in document3Ti4NiMnO12 and Li3Ti4NiCrO12: New substituted lithium titanium oxides, Solid State Sciences, 22 (2013) 65-70), it is indicated above the cobalt chromium lithium titanate that final material is cobalt cladding of above-mentioned gained.
Use scanning electron microscope (SEM, NEC 6700F) the cobalt chromium lithium titanate that is coated with the lithium ion battery negative material cobalt of above-mentioned gained is scanned under 3.00K and 30.0k multiplying power respectively, the SEM figure of gained is the most 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 with is can be seen that from Fig. 2 a, being rendered as spherical second particle, particle diameter is at 10-20 micron.Can be seen that from Fig. 2 b the second particle of the cobalt chromium lithium titanate that lithium ion battery negative material cobalt is coated with 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 spheroidal particle, nanovoids is as the capillary channel of electrolyte Yu material exchange lithium ion, be conducive to embedding and the abjection of lithium ion, thus the nanorize indicating the cobalt chromium lithium titanate particle size of lithium ion battery negative material cobalt cladding can improve the chemical property of the cobalt chromium lithium titanate that this lithium ion battery negative material cobalt is coated with.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with, 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 is as shown in Figure 3, as can be seen from Figure 3 its averaged discharge specific capacity is 151.2 mAh/g, theoretical capacity (155.3mAh/g) close to 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 of the lithium ion battery negative material cobalt cladding of gained of the present invention has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
Embodiment 2
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 21.1 parts
Cobalt black 20.4 parts
Lithium hydrate 33 parts；
Its synthetic method specifically includes following steps:
(1), by 82 parts of titanium dioxide join in the deionized water of 1/2 total amount that is 200 part, obtain tio_2 suspension；
It is added sequentially in tio_2 suspension mix by 21.1 parts of chromic oxides and 20.4 parts of cobalt blacks, obtains mixed liquor, then the mixed liquor obtained is poured in ball mill ball milling while stirring, control granule D50 a size of 320nm, obtain slurry；
(2), by 33 parts of Lithium hydrates it is dissolved in 200 parts of deionized waters and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), to control to stir speed by the Lycoperdon polymorphum Vitt slurry of step (2) gained be 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding, i.e. Co/Li3Ti4CoCrO12；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 3%, and noble gas is argon.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, in XRD figure, all of diffraction maximum can be demarcated as cobalt chromium lithium titanate and the diffraction maximum of metallic cobalt, the peak position i.e. not having other materials occurs, is indicated above the cobalt chromium lithium titanate that final thing is cobalt cladding of above-mentioned gained.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, use scanning electron microscope (SEM, NEC 6700F) carry out Shape measure, the SEM observed result of gained is also similar with Fig. 2 result, the i.e. cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of gained is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheroidal particle (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 spheroidal particle, nanoaperture as the capillary channel of electrolyte Yu material exchange lithium ion, beneficially lithium ion embedding and embedding go out, improve the chemical property of cobalt chromium lithium titanate material of lithium ion battery negative material cobalt cladding.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with, 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, performance degradation is faint.Test result shows, the cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
Embodiment 3
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 17.3 parts
Cobalt black 24.8 parts
Lithium hydrate 33 parts；
Its synthetic method specifically includes following steps:
(1), by 82 parts of titanium dioxide join in the deionized water of 1/2 total amount that is 200 part, obtain tio_2 suspension；
It is added sequentially in tio_2 suspension mix by 17.3 parts of chromic oxides and 24.8 parts of cobalt blacks, obtains mixed liquor；
Then the mixed liquor obtained is poured in ball mill ball milling while stirring, controls granule D50 a size of 340nm, obtain slurry；
(2), by 33 parts of Lithium hydrates it is dissolved in 200 parts of deionized waters and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1%, and noble gas is argon.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, in XRD figure, all of diffraction maximum can be demarcated as cobalt chromium lithium titanate and the diffraction maximum of metallic cobalt, the peak position i.e. not having other materials occurs, is indicated above the cobalt chromium lithium titanate that final thing is cobalt cladding of above-mentioned gained.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, use scanning electron microscope (SEM, NEC 6700F) carry out Shape measure, the SEM observed result of gained is similar with Fig. 2 result, the i.e. cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of gained is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheroidal particle (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 spheroidal particle, nanoaperture as the capillary channel of electrolyte Yu material exchange lithium ion, beneficially lithium ion embedding and embedding go out, improve the chemical property of cobalt chromium lithium titanate material that lithium ion battery negative material is cobalt cladding.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with, 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 of the lithium ion battery negative material cobalt cladding of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
Embodiment 4
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 19.2 parts
Cobalt black 22.8 parts
Lithium hydrate 36 parts；
Its synthetic method specifically includes following steps:
(1), by 82 parts of titanium dioxide join in the deionized water of 1/2 total amount that is 200 part, obtain tio_2 suspension；
It is added sequentially in the tio_2 suspension of above-mentioned gained mix by 19.2 parts of chromic oxides and 22.8 parts of cobalt blacks, obtains mixed liquor；
Then the mixed liquor obtained is poured in ball mill ball milling while stirring, controls granule D50 a size of 290nm, obtain slurry；
(2), by 36 parts of Lithium hydrates it is dissolved in the deionized water of remaining 200 parts and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding, i.e. Co/Li3Ti4CoCrO12；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 5%, and noble gas is argon.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, in XRD figure, all of diffraction maximum can be demarcated as cobalt chromium lithium titanate and the diffraction maximum of metallic cobalt, the peak position i.e. not having other materials occurs, is indicated above the cobalt chromium lithium titanate that final thing is cobalt cladding of above-mentioned gained.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, use scanning electron microscope (SEM, NEC 6700F) carry out Shape measure, the SEM observed result of gained is similar with Fig. 2 result, the i.e. cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of gained is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheroidal particle (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 spheroidal particle, nanoaperture as the capillary channel of electrolyte Yu material exchange lithium ion, beneficially lithium ion embedding and embedding go out, improve the chemical property of cobalt chromium lithium titanate material that lithium ion battery negative material is cobalt cladding.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with, 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 of the lithium ion battery negative material cobalt cladding of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
Embodiment 5
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 21.1 parts
Cobalt black 20.4 parts
Lithium hydrate 36 parts；
Its synthetic method specifically includes following steps:
(1), by 82 parts of titanium dioxide join in the deionized water of 1/2 total amount that is 200 part, obtain tio_2 suspension；
It is added sequentially in the tio_2 suspension of above-mentioned gained mix by 21.1 parts of chromic oxides and 20.4 parts of cobalt blacks, obtains mixed liquor；
Then the mixed liquor obtained is poured in ball mill ball milling while stirring, controls granule D50 a size of 270nm, obtain slurry；
(2), by 36 parts of Lithium hydrates it is dissolved in the deionized water of remaining 200 parts and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding, i.e. Co/Li3Ti4CoCrO12；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 3%, and noble gas is argon.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, in XRD figure, all of diffraction maximum can be demarcated as cobalt chromium lithium titanate and the diffraction maximum of metallic cobalt, the peak position i.e. not having other materials occurs, is indicated above the cobalt chromium lithium titanate that final thing is cobalt cladding of above-mentioned gained.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, use scanning electron microscope (SEM, NEC 6700F) carry out Shape measure, the SEM observed result of gained is similar with Fig. 2 result, the i.e. cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of gained is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheroidal particle (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 spheroidal particle, nanoaperture as the capillary channel of electrolyte Yu material exchange lithium ion, beneficially lithium ion embedding and embedding go out, improve the chemical property of cobalt chromium lithium titanate material that lithium ion battery negative material is cobalt cladding.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with, 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 of the lithium ion battery negative material cobalt cladding of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
Embodiment 6
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 17.3 parts
Cobalt black 24.8 parts
Lithium hydrate 36 parts；
Its synthetic method specifically includes following steps:
(1), by 82 parts of titanium dioxide join in the deionized water of 1/2 total amount that is 200 part, obtain tio_2 suspension；
It is added sequentially in the tio_2 suspension of above-mentioned gained mix by 17.3 parts of chromic oxides and 24.8 parts of cobalt blacks, obtains mixed liquor；
Then the mixed liquor obtained is poured in ball mill ball milling while stirring, controls granule D50 a size of 350nm, obtain slurry；
(2), by 36 parts of Lithium hydrates it is dissolved in the deionized water of remaining 200 parts and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding, i.e. Co/Li3Ti4CoCrO12；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1%, and noble gas is argon.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, in XRD figure, all of diffraction maximum can be demarcated as cobalt chromium lithium titanate and the diffraction maximum of metallic cobalt, the peak position i.e. not having other materials occurs, is indicated above the cobalt chromium lithium titanate that final thing is cobalt cladding of above-mentioned gained.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, use scanning electron microscope (SEM, NEC 6700F) carry out Shape measure, the SEM observed result of gained is similar with Fig. 2 result, the i.e. cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of gained is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheroidal particle (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 spheroidal particle, nanoaperture as the capillary channel of electrolyte Yu material exchange lithium ion, beneficially lithium ion embedding and embedding go out, improve the chemical property of cobalt chromium lithium titanate material that lithium ion battery negative material is cobalt cladding.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with, 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 of the lithium ion battery negative material cobalt cladding of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
Embodiment 7
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 19.2 parts
Cobalt black 22.8 parts
Lithium hydrate 30 parts；
Its synthetic method specifically includes following steps:
(1), by 82 parts of titanium dioxide join in the deionized water of 1/2 total amount that is 200 part, obtain tio_2 suspension；
It is added sequentially in the tio_2 suspension of above-mentioned gained mix by 19.2 parts of chromic oxides and 22.8 parts of cobalt blacks, obtains mixed liquor；
Then the mixed liquor obtained is poured in ball mill ball milling while stirring, controls granule D50 a size of 320nm, obtain slurry；
(2), by 30 parts of Lithium hydrates it is dissolved in the deionized water of remaining 200 parts and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding, i.e. Co/Li3Ti4CoCrO12；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 5%, and noble gas is argon.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, in XRD figure, all of diffraction maximum can be demarcated as cobalt chromium lithium titanate and the diffraction maximum of metallic cobalt, the peak position i.e. not having other materials occurs, is indicated above the cobalt chromium lithium titanate that final thing is cobalt cladding of above-mentioned gained.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, use scanning electron microscope (SEM, NEC 6700F) carry out Shape measure, the SEM observed result of gained is similar with Fig. 2 result, the i.e. cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of gained is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheroidal particle (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 spheroidal particle, nanoaperture as the capillary channel of electrolyte Yu material exchange lithium ion, beneficially lithium ion embedding and embedding go out, improve the chemical property of cobalt chromium lithium titanate material that lithium ion battery negative material is cobalt cladding.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with, 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 of the lithium ion battery negative material cobalt cladding of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
Embodiment 8
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 21.1 parts
Cobalt black 20.4 parts
Lithium hydrate 30 parts；
Its synthetic method specifically includes following steps:
(1), by 82 parts of titanium dioxide join in the deionized water of 1/2 total amount that is 200 part, obtain tio_2 suspension；
It is added sequentially in the tio_2 suspension of above-mentioned gained mix by 21.1 parts of chromic oxides and 20.4 parts of cobalt blacks, obtains mixed liquor；
Then the mixed liquor obtained is poured in ball mill ball milling while stirring, controls granule D50 a size of 260nm, obtain slurry；
(2), by 30 parts of Lithium hydrates it is dissolved in the deionized water of remaining 200 parts and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding, i.e. Co/Li3Ti4CoCrO12；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 3%, and noble gas is argon.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, in XRD figure, all of diffraction maximum can be demarcated as cobalt chromium lithium titanate and the diffraction maximum of metallic cobalt, the peak position i.e. not having other materials occurs, is indicated above the cobalt chromium lithium titanate that final thing is cobalt cladding of above-mentioned gained.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, use scanning electron microscope (SEM, NEC 6700F) carry out Shape measure, the SEM observed result of gained is similar with Fig. 2 result, the i.e. cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of gained is rendered as spherical second particle, and particle diameter is at 10-20 micron.These spheroidal particle (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 spheroidal particle, nanoaperture as the capillary channel of electrolyte Yu material exchange lithium ion, beneficially lithium ion embedding and embedding go out, improve the chemical property of cobalt chromium lithium titanate material that lithium ion battery negative material is cobalt cladding.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with, 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 of the lithium ion battery negative material cobalt cladding of above-mentioned synthetic method gained has good electrochemical properties and stable circulation performance, is expected to apply in energy-storage battery field.
Embodiment 9
A kind of synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding, the raw material used in building-up process, to calculate according to the mass fraction, its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 17.3 parts
Cobalt black 24.8 parts
Lithium hydrate 30 parts；
Its synthetic method specifically includes following steps:
(1), by 82 parts of titanium dioxide join in the deionized water of 1/2 total amount that is 200 part, obtain tio_2 suspension；
It is added sequentially in the tio_2 suspension of above-mentioned gained mix by 17.3 parts of chromic oxides and 24.8 parts of cobalt blacks, obtains mixed liquor；
Then the mixed liquor obtained is poured in ball mill ball milling while stirring, controls granule D50 a size of 310nm, obtain slurry；
(2), by 30 parts of Lithium hydrates it is dissolved in the deionized water of remaining 200 parts and obtains lithium hydroxide aqueous solution, in the slurry of the ball mill that gained lithium hydroxide aqueous solution is joined step (1), proceed ball milling 1h, obtain Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of lithium ion battery negative material cobalt cladding, i.e. Co/Li3Ti4CoCrO12；
In the described noble gas being mixed with reducibility gas, reducibility gas is hydrogen, by volume percentage calculation, and its concentration is 1%, and noble gas is argon.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, by X-ray diffractometer (XRD, Rigaku Rigaku) detect, the XRD figure of gained is similar to Fig. 1 result, in XRD figure, all of diffraction maximum can be demarcated as cobalt chromium lithium titanate and the diffraction maximum of metallic cobalt, the peak position i.e. not having other materials occurs, is indicated above the cobalt chromium lithium titanate that final thing is cobalt cladding of above-mentioned gained.
The cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of above-mentioned gained, use scanning electron microscope (SEM, NEC 6700F) carry out Shape measure, the SEM observed result of gained is similar with Fig. 2 result, the i.e. cobalt chromium lithium titanate of the lithium ion battery negative material cobalt cladding of gained is rendered as spherical second particle, particle diameter is made up of less nano-particle (primary particle) at 10-20 micron, these spheroidal particle (second particle), and the size of this nano-particle is at 100 200nm.There is certain space between spheroidal particle, nanoaperture as the capillary channel of electrolyte Yu material exchange lithium ion, beneficially lithium ion embedding and embedding go out, improve the chemical property of cobalt chromium lithium titanate material of lithium ion battery negative material cobalt cladding.
The cobalt chromium lithium titanate that the lithium ion battery negative material cobalt of above-mentioned gained is coated with, 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 of the lithium ion battery negative material cobalt cladding of gained of the present invention 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 is noted that for those skilled in the art, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement, and these improvement also should be regarded as protection scope of the present invention.

Claims (12)

1. the synthetic method of the cobalt chromium lithium titanate of a lithium ion battery negative material cobalt cladding, it is characterised in that the raw material used in building-up process, calculates according to the mass fraction, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 17.3-21.1 part
Cobalt black 20.4-24.8 part
Lithium hydrate 30-36 part
Its synthetic method specifically includes following steps:
(1), by titanium dioxide join in the deionized water of 1/2 total amount, obtain tio_2 suspension；
It is added sequentially in tio_2 suspension mix by chromic oxide and cobalt black, obtains mixed liquor；
Then the mixed liquor obtained is poured in ball mill ball milling while stirring, controls granule D50 a size of 200-350nm, obtain slurry；
(2), by Lithium hydrate it is dissolved in remaining deionized water and obtains 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 Lycoperdon polymorphum Vitt slurry；
(3), by the Lycoperdon polymorphum Vitt slurry of step (2) gained controlling mixing speed is 100r/min, and inlet temperature is to be spray-dried 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 of cobalt cladding.
2. the synthetic method of the cobalt chromium lithium titanate of lithium ion battery negative material cobalt cladding as described in claim 1, it is characterized in that in the noble gas being mixed with reducibility gas described in step (4), reducibility gas is hydrogen, by volume percentage calculation, its concentration is 1-5%, and noble gas is argon, nitrogen or helium.
The synthetic method of the cobalt chromium lithium titanate of a kind of lithium ion battery negative material cobalt the most as described in claim 1 cladding, it is characterised in that raw material used in building-up process, calculates according to the mass fraction, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 19.2 parts
Cobalt black 22.8 parts
Lithium hydrate 33 parts；
In the noble gas being mixed with 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 noble gas is argon, and calcining heat is 800 DEG C.
The synthetic method of the cobalt chromium lithium titanate of a kind of lithium ion battery negative material cobalt the most as described in claim 1 cladding, it is characterised in that raw material used in building-up process, calculates according to the mass fraction, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 21.1 parts
Cobalt black 20.4 parts
Lithium hydrate 33 parts；
In the noble gas being mixed with 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 noble gas is argon, and calcining heat is 700 DEG C.
The synthetic method of the cobalt chromium lithium titanate of a kind of lithium ion battery negative material cobalt the most as described in claim 1 cladding, it is characterised in that raw material used in building-up process, calculates according to the mass fraction, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 17.3 parts
Cobalt black 24.8 parts
Lithium hydrate 33 parts；
In the noble gas being mixed with 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 noble gas is argon, and calcining heat is 900 DEG C.
The synthetic method of the cobalt chromium lithium titanate of a kind of lithium ion battery negative material cobalt the most as described in claim 1 cladding, it is characterised in that raw material used in building-up process, calculates in parts by weight, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 19.2 parts
Cobalt black 22.8 parts
Lithium hydrate 36 parts；
In the noble gas being mixed with 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 noble gas is argon, and calcining heat is 700 DEG C.
The synthetic method of the cobalt chromium lithium titanate of a kind of lithium ion battery negative material cobalt the most as described in claim 1 cladding, it is characterised in that raw material used in building-up process, calculates in parts by weight, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 21.1 parts
Cobalt black 20.4 parts
Lithium hydrate 36 parts；
In the noble gas being mixed with 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 noble gas is argon, and calcining heat is 900 DEG C.
The synthetic method of the cobalt chromium lithium titanate of a kind of lithium ion battery negative material cobalt the most as described in claim 1 cladding, it is characterised in that raw material used in building-up process, calculates in parts by weight, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 17.3 parts
Cobalt black 24.8 parts
Lithium hydrate 36 parts；
In the noble gas being mixed with 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 noble gas is argon, and calcining heat is 800 DEG C.
The synthetic method of the cobalt chromium lithium titanate of a kind of lithium ion battery negative material cobalt the most as described in claim 1 cladding, it is characterised in that raw material used in building-up process, calculates in parts by weight, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 19.2 parts
Cobalt black 22.8 parts
Lithium hydrate 30 parts；
In the noble gas being mixed with 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 noble gas is argon, and calcining heat is 900 DEG C.
The synthetic method of the cobalt chromium lithium titanate of a kind of lithium ion battery negative material cobalt the most as described in claim 1 cladding, it is characterised in that raw material used in building-up process, calculates in parts by weight, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 21.1 parts
Cobalt black 20.4 parts
Lithium hydrate 30 parts；
In the noble gas being mixed with 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 noble gas is argon, and calcining heat is 800 DEG C.
The synthetic method of the cobalt chromium lithium titanate of 11. a kind of lithium ion battery negative material cobalt as described in claim 1 claddings, it is characterised in that raw material used in building-up process, calculates in parts by weight, and its composition and content are as follows:
Titanium dioxide 82 parts
Deionized water 400 parts
Chromic oxide 17.3 parts
Cobalt black 24.8 parts
Lithium hydrate 30 parts；
In the noble gas being mixed with 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 noble gas is argon, and calcining heat is 700 DEG C.
The cobalt chromium lithium titanate of a kind of lithium ion battery negative material cobalt cladding obtained by 12. synthetic methods as described in one of claim 1-11.
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