CN102694177B - Preparation method for carbon-coated lithium titanate/carbon nanotube composite - Google Patents

Preparation method for carbon-coated lithium titanate/carbon nanotube composite Download PDF

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CN102694177B
CN102694177B CN201210163712.6A CN201210163712A CN102694177B CN 102694177 B CN102694177 B CN 102694177B CN 201210163712 A CN201210163712 A CN 201210163712A CN 102694177 B CN102694177 B CN 102694177B
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carbon
tube
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lithium titanate
carbon nano
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CN102694177A (en
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王振波
戴凤玲
阙奕鹏
雷龙飞
顾大明
尹鸽平
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention discloses a preparation method for a carbon-coated lithium titanate/carbon nanotube composite, belonging to the field of a lithium-ion battery cathode material. The technical problem that the current Li4Ti5O12 has poor specific capacity and cycle performance. The preparation method comprises the following steps: 1. adding carbon nanotube and titaniferous compound which can be easily hydrolyzed to an alcohol-water solution, stirring the mixture to form an emulsion; diluting, spraying and drying the emulsion; 2. ball-milling the emulsion with soluble lithium salt, sintering the mixture under an inert atmosphere to acquire a precursor; and 3. uniformly mixing the precursor acquired from the second step with a carbon source, and sintering the mixture under the inert atmosphere to acquire the carbon-coated lithium titanate/carbon nanotube composite. With the adoption of the preparation method, the obtained product is used as the lithium-ion battery cathode material.

Description

Carbon is coated the preparation method of lithium titanate/carbon mano-tube composite
Technical field
The invention belongs to lithium ion battery negative material field; Be specifically related to the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon.
Background technology
Now commercial lithium ion battery negative material mainly adopts material with carbon element, although adopt the lithium ion battery of material with carbon element to possess considerable specific capacity, but because carbon negative pole material is very approaching with the discharge platform of lithium sheet after embedding lithium, if overcharged, can on negative pole, separate out lithium metallic dendrite, easily poke barrier film and cause battery short circuit, there is great potential safety problem.Also caused pessimistic on cycle performance of carbon negative pole material.So, seek a kind of have higher-security simultaneously cycle performance again good negative material be a developing direction of lithium rechargeable battery.
Li 4ti 5o 12itself is non-conductive, is stable white powder in air, deposits conveniently.Li 4ti 5o 12belong to spinel structure, its space group is Fd3m, with a Li 4ti 5o 12structure cell is example, the Li of fraction +occupy in the tetrahedral gap of 8a in structure cell most of Li +with all Ti 4+occupy in the octahedral interstice of 16d, and all O 2-in the position of 32e, form FCC dot matrix, when there being Li +during embedding, the Li of embedding +will with the Li of 8a position +migrate to together 16c and form Li 7ti 5o 12, formed Li azury in embedding lithium process 7ti 5o 12conduct electricity, and be spinel structure, so his cell parameter a is substantially constant, can produce the bulk effect of material and cause total variable effect to the cycle performance of battery.
Spinel-type Li 4ti 5o 12there is stable discharge platform, and the embedding of lithium ion and deviate from can be on the larger impact of structure generation itself, so just because of this feature of itself is referred to as " zero strain material ", his this specific character has just caused prepared lithium ion battery to have very good cycle performance.In addition, while contact lower than the negative material of 0.8V due to the organic solvent in electrolyte and relative current potential (with respect to lithium metal), can be reduced formation SEI film, and Li 4ti 5o 12relative current potential be about 1.55V, so Li 4ti 5o 12in the process of first charge-discharge, can not form on surface SEI film.And the carbon negative pole (the relative current potential of graphite is 0.15V) that is all negative material is because he has formed SEI film with contacting of electrolyte in the process of first charge-discharge, therefore just caused the increase of irreversible capacity, also just reduced the specific discharge capacity of carbon negative pole.In view of Li 4ti 5o 12there is the incomparable superior function of other negative materials, so by Li 4ti 5o 12be applied in commercial batteries, realize its industrialization and there is very large commercial promise and huge business potential.
Existing Li 4ti 5o 12the synthetic high temperature solid-state method that mainly contains, sol-gel processing, spraying is dry, molten salt growth method etc., the many of application is now high temperature solid-state method and sol-gel processing.The high temperature solid-state method Li that is simply easy to get wherein 4ti 5o 12, but if being applied in industry still there are some problems, for example: the temperature requirement of sintering is too high, substantially concentrate between 800 ~ 1000 ℃, and the product purity after sintering is not high, due to the inhomogeneities of its particle, causes its tap density problem on the low side; And although sol-gel processing can obtain the Li that purity is higher 4ti 5o 12product, but its technique is comparatively complicated, is not suitable for large-scale industrial production.
Patent CN201010149910.8 directly by solubility lithium salt solution the carbon nano-tube after ultrasonic dispersion mix with anatase titania and dry sintering and both obtained lithium titanate, the bad assurance of control due to its carbon nano-tube amount, cause the prepared lithium titanate/carbon/carbon nano tube network structure of this method to exist the carbon nano-tube distribution between lithium titanate particle disorderly and unsystematic, cannot play good connection bridging action.
Summary of the invention
The present invention will solve existing Li 4ti 5o 12the technical problem that specific capacity and cycle performance are poor; And provide carbon to be coated the preparation method of lithium titanate/carbon mano-tube composite.
In the present invention, the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon carries out in the steps below: the preparation method that carbon is coated lithium titanate/carbon mano-tube composite carries out in the steps below:
Step 1, in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis, be that 0.5 ~ 1:1 ratio adds the titanium-containing compound of carbon nano-tube and facile hydrolysis in alcohol solution, the weight ratio of the titanium-containing compound of described carbon nano-tube and facile hydrolysis is 0.005 ~ 0.05:1, then under 40 ~ 60 ℃ of conditions, with 100 ~ 300 r/min speed, be stirred to formation emulsion, then dilute 5 ~ 10 times, the drier bead type amorphous titania/carbon nano-tube that obtains of spraying;
Step 2, by Li/Ti mol ratio, be (3.9 ~ 4.3): 5 take bead type amorphous titania/carbon nano-tube and the solubility lithium salts that step 1 obtains is placed in ball mill, press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h, then sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions, be warming up to again 650 ~ 1000 ℃, heat preservation sintering 3 ~ 8h, obtains presoma;
Step 3, presoma and carbon source that step 2 is obtained mix, then sintering 2 ~ 6 hours at inert atmosphere, 500 ~ 650 ℃; Obtain the coated lithium titanate/carbon mano-tube composite of carbon.
The preparation method of the coated lithium titanate/carbon mano-tube composite of carbon of the present invention also can carry out in the steps below: step 1, in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis, be that 0.5 ~ 1:1 ratio is by carbon nano-tube, the titanium-containing compound of doped chemical and facile hydrolysis adds in alcohol solution, the weight ratio of the titanium-containing compound of described carbon nano-tube and facile hydrolysis is 0.005 ~ 0.05:1, then under 40 ~ 60 ℃ of conditions, with 100 ~ 300 r/min speed, be stirred to formation emulsion, then dilute 5 ~ 10 times, spraying is dried and obtains bead type amorphous titania/carbon nano-tube again,
Step 2, by Li/Ti mol ratio, be (3.9 ~ 4.3): 5 take bead type amorphous titania/carbon nano-tube and the solubility lithium salts that step 1 obtains is placed in ball mill, press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h, then sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions, be warming up to again 650 ~ 1000 ℃, heat preservation sintering 3 ~ 8h, obtains presoma;
Step 3, presoma and carbon source that step 2 is obtained mix, then sintering 2 ~ 6 hours at inert atmosphere, 500 ~ 650 ℃; Obtain the coated lithium titanate/carbon mano-tube composite of carbon, wherein described in step 1, doped chemical is one or both in Mg, Al, Co, V, W, F, and doped chemical is 0.005 ~ 0.08:1 with the molal weight ratio of titanium elements.
The present invention adopts the titanium-containing compound and the carbon nano-tube that are easy to hydrolysis to take the lead in preparing bead type structure, be conducive to follow-up synthetic lithium titanate material be carried out to better modification and coated, the presoma that prepare bead type structure (sugarcoated haws structure) early stage can not exert an influence to the lattice of synthetic negative material lithium titanate, strengthens later stage Ti 3+and Ti 4+conduction between electronics, specific capacity and the high rate performance of raising negative material.
Adopt appropriate carbon source to carry out low temperature to synthetic material and be coated, prevent that the agglomeration of particle from occurring, better form the sugarcoated haws type special construction of the lithium titanate of strip simultaneously.
The present invention adopts to possess certain intensity and very high absorption property carbon nano-tube is initiatively adsorbed solubility titanium-containing compound, and its adsorption mechanism is, because the zeta potential of carbon nano-tube is negative potential, by electrostatic adsorption, adsorbs the Ti after solvable 4+and under acid condition, the absorption property of carbon nano-tube is best, so will control its pH 4.5 ~ 5.0 in the process that forms colloidal sol, at its body, form the particle of titanium-containing compound, after spraying is dry, can form the compound of the carbon nano-tube of titaniferous, thus for below preferably and modified lithium titanate lay the foundation.
The prepared lithium titanate of the lithium titanate anode material of synthesized of the present invention and existing existing technology compares to possess better high rate cyclic performance; And its technique is simple, be easy to realize industrialization.
Accompanying drawing explanation
Fig. 1 is the resulting XRD figure of embodiment 20; Fig. 2 is the CV figure that embodiment 20 obtains; Fig. 3 is the resulting EIS figure of embodiment 20; Fig. 4 is the resulting Specific Capacitity-Cycle of embodiment 20 Number figure, the 1 Specific Capacitity-Cycle Numbe figure being illustrated under 1C multiplying power in figure, 2 are illustrated in the Specific Capacitity-Cycle Numbe figure under 2C multiplying power; Fig. 5 is the resulting Li of embodiment 20 method 4ti 5o 12theoretical microstructure schematic diagram.
Embodiment
Embodiment one: in present embodiment, the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon carries out in the steps below:
Step 1, in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis, be that 0.5 ~ 1:1 ratio adds the titanium-containing compound of carbon nano-tube and facile hydrolysis in alcohol solution, the weight ratio of the titanium-containing compound of described carbon nano-tube and facile hydrolysis is 0.005 ~ 0.05:1, then under 40 ~ 60 ℃ of conditions, with 100 ~ 300 r/min speed, be stirred to formation emulsion, then dilute 5 ~ 10 times, the drier bead type amorphous titania/carbon nano-tube that obtains of spraying;
Step 2, by Li/Ti mol ratio, be (3.9 ~ 4.3): 5 take bead type amorphous titania/carbon nano-tube and the solubility lithium salts that step 1 obtains is placed in ball mill, press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h, then sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions, be warming up to again 650 ~ 1000 ℃, heat preservation sintering 3 ~ 8h, obtains presoma;
Step 3, presoma and carbon source that step 2 is obtained mix, then sintering 2 ~ 6 hours at inert atmosphere, 500 ~ 650 ℃; Obtain the coated lithium titanate/carbon mano-tube composite of carbon.
Embodiment two: present embodiment is different from embodiment one: described in step 1, the titanium-containing compound of facile hydrolysis is metatitanic acid methyl esters, tetrabutyl titanate, tetraethyl titanate or isopropyl titanate.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: described in step 1 alcohol solution be by alcohol and deionized water by (0.5 ~ 1): 1 volume ratio preparation.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: spraying dry described in step 1 is to be 180 ~ 250 ℃ in temperature, and flow velocity is to carry out under 1 ~ 33 mL/min condition.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: described in step 1, carbon nano-tube is the multi-walled carbon nano-tubes after double-walled carbon nano-tube, multi-walled carbon nano-tubes, graphitized carbon nano pipe or vacuum high-temperature are processed.Other step and parameter are identical with one of embodiment one to four.
Multi-walled carbon nano-tubes after described vacuum high-temperature is processed is that the effective high-temperature vacuum furnace of multi-wall carbon nano-tube after vacuum high-temperature is processed has carried out 1500 ~ 2150 ℃ to the multi-walled carbon nano-tubes of preparing with catalystic pyrolysis in nanometer agglomerate fluid bed.
Embodiment six: present embodiment is different from one of embodiment one to five: described in step 1, in alcohol solution, alcohol is a kind of wherein several mixing in absolute ethyl alcohol, acetone, isopropyl alcohol, ethylene glycol, glycerol, butanediol, tetramethylenthanediol and butantriol.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: the solubility lithium salts described in step 2 is lithium hydroxide, lithium acetate, lithium carbonate or lithium fluoride.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: described in step 2, inert atmosphere is nitrogen or argon gas, inert atmosphere is nitrogen or argon gas described in step 3.Other step and parameter are identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: described in step 2, the content of carbon coated is that 0.5% ~ 5% presoma that step 2 is obtained mixes with carbon source, and carbon source is sucrose, glucose, pitch, glycogen, phenolic resins or epoxy resin.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: in present embodiment, the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon carries out in the steps below:
Step 1, in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis, be that 0.5 ~ 1:1 ratio adds the titanium-containing compound of carbon nano-tube, doped chemical and facile hydrolysis in alcohol solution, the weight ratio of the titanium-containing compound of described carbon nano-tube and facile hydrolysis is 0.005 ~ 0.05:1, then under 40 ~ 60 ℃ of conditions, with 100 ~ 300 r/min speed, be stirred to formation emulsion, then dilute 5 ~ 10 times, the drier bead type amorphous titania/carbon nano-tube that obtains of spraying;
Step 2, by Li/Ti mol ratio, be (3.9 ~ 4.3): 5 take bead type amorphous titania/carbon nano-tube and the solubility lithium salts that step 1 obtains is placed in ball mill, press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h, then sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions, be warming up to again 650 ~ 1000 ℃, heat preservation sintering 3 ~ 8h, obtains presoma;
Step 3, presoma and carbon source that step 2 is obtained mix, then sintering 2 ~ 6 hours at inert atmosphere, 500 ~ 650 ℃; Obtain the coated lithium titanate/carbon mano-tube composite of carbon, wherein described in step 1, doped chemical is one or both in Mg, Al, Co, V, W, F, and doped chemical is 0.005 ~ 0.08:1 with the molal weight ratio of titanium elements.
When in present embodiment, doped chemical is two kinds, between each doped chemical, be mixed by any ratio.
Embodiment 11: present embodiment is different from embodiment ten: described in step 1, the titanium-containing compound of facile hydrolysis is metatitanic acid methyl esters, tetrabutyl titanate, tetraethyl titanate or isopropyl titanate.Other step and parameter are identical with embodiment ten.
Embodiment 12: present embodiment is different from embodiment ten or 11: described in step 1 alcohol solution be by alcohol and deionized water by (0.5 ~ 1): 1 volume ratio preparation.Other step and parameter are identical with embodiment ten or 11.
Embodiment 13: present embodiment is different from one of embodiment ten to 12: spraying dry described in step 1 is to be 180 ~ 250 ℃ in temperature, and flow velocity is to carry out under 1 ~ 33 mL/min condition.Other step and parameter are identical with one of embodiment ten to 12.
Embodiment 14: present embodiment is different from one of embodiment ten to 13: described in step 1, carbon nano-tube is multi-walled carbon nano-tubes or the graphitized carbon nano pipe of double-walled carbon nano-tube, multi-walled carbon nano-tubes, vacuum high-temperature processing.Other step and parameter are identical with one of embodiment ten to 13.
Multi-walled carbon nano-tubes after described vacuum high-temperature is processed is that the effective high-temperature vacuum furnace of multi-wall carbon nano-tube after vacuum high-temperature is processed has carried out 1500 ~ 2150 ℃ to the multi-walled carbon nano-tubes of preparing with catalystic pyrolysis in nanometer agglomerate fluid bed.
Embodiment 15: present embodiment is different from one of embodiment ten to 14: described in step 1, in alcohol solution, alcohol is a kind of wherein several mixing in absolute ethyl alcohol, acetone, isopropyl alcohol, ethylene glycol, glycerol, butanediol, tetramethylenthanediol and butantriol.Other step and parameter are identical with one of embodiment ten to 14.
Embodiment 16: present embodiment is different from one of embodiment ten to 15: the solubility lithium salts described in step 2 is lithium hydroxide, lithium acetate, lithium carbonate or lithium fluoride.Other step and parameter are identical with one of embodiment ten to 15.
Embodiment 17: present embodiment is different from one of embodiment ten to 16: described in step 2, inert atmosphere is nitrogen or argon gas, inert atmosphere is nitrogen or argon gas described in step 3.Other step and parameter are identical with one of embodiment ten to 16.
Embodiment 18: present embodiment is different from one of embodiment ten to 17: described in step 2, the content of carbon coated is that 0.5% ~ 5% presoma that step 2 is obtained mixes with carbon source, and carbon source is sucrose, glucose, pitch, glycogen, phenolic resins or epoxy resin.Other step and parameter are identical with one of embodiment ten to 17.
Embodiment 19: in present embodiment, the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon carries out in the steps below:
Step 1, by 0.0085g carbon nano-tube (CNT) carbon nano-tube and 0.1mol tetrabutyl titanate (C 16h 36o 4ti) add in 500mL alcohol solution (the ratio row configuration that wherein absolute ethyl alcohol and deionized water are 0.8:1 according to volume ratio), then under 50 ℃ of conditions, with 200r/min speed, be stirred to formation emulsion, then dilute 2 times, spraying dry (200 ℃ of baking temperatures, material flow is 25ml/min) obtains bead type amorphous titania/carbon nano-tube again;
Step 2,1.974g bead type amorphous titania/carbon nano-tube and 0.7886g Li 2cO 3be placed in ball mill, by rotating speed 300 ~ 350r/min ball milling 10 ~ 12h, sintering 8h under nitrogen atmosphere, 600 ℃ of (heating rate is 5 ℃/min) conditions then, then be warming up to 850 ℃, heat preservation sintering 4h, cools to room temperature with the furnace, obtains presoma;
Step 3, presoma and 1.1143g citric acid (C that 9g step 2 is obtained 6h 8o 7h 2o) mix, then sintering 2 hours at nitrogen atmosphere, 400 ℃; Obtain the coated lithium titanate/carbon mano-tube composite of carbon.
It is bead structure that the present invention obtains the coated lithium titanate/carbon mano-tube composite of carbon.
Embodiment 20: in present embodiment, the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon carries out in the steps below:
Step 1, by 1.1942g basic magnesium carbonate [(MgCO 3) 4mg (OH) 26H 2o], 0.0085g carbon nano-tube (CNT) carbon nano-tube and 0.1mol tetrabutyl titanate (C 16h 36o 4ti) add in the ratio row configuration that wherein absolute ethyl alcohol and deionized water are 0.8:1 according to volume ratio of 500mL alcohol solution, then under 50 ℃ of conditions, with 200 r/min speed, be stirred to formation emulsion, then dilute 2 times, spraying dry (200 ℃ of baking temperatures, material flow is 25 ml/min) obtains bead type amorphous titania/carbon nano-tube again;
Step 2,1.974g bead type amorphous titania/carbon nano-tube and 0.7886g Li 2cO 3be placed in ball mill, by rotating speed 200 ~ 350r/min ball milling 6 ~ 12h, sintering 8h under nitrogen atmosphere, 600 ℃ of (heating rate is 5 ℃/min) conditions then, then be warming up to 850 ℃, heat preservation sintering 4h, cools to room temperature with the furnace, obtains presoma;
Step 3, presoma and 1.1143g citric acid (C that 9g step 2 is obtained 6h 8o 7h 2o) mix, then sintering 2 hours at nitrogen atmosphere, 400 ℃; Obtain the coated lithium titanate/carbon mano-tube composite of carbon.
It is bead structure (as shown in Figure 5) that the present invention obtains the coated lithium titanate/carbon mano-tube composite of carbon.
The surface area of making test sample is 10mm * 10mm, and the thickness of sample is 0.08mm, 70 ° of scanning angles during test (2 θ), sweep speed 10 o/ min; Result is as Fig. 1; The known product of reference standard card (PDF49-0207) is the Li of pure phase 4ti 5o 12, there is no the generation of impurity phase.Show under this synthesis condition synthetic Li 4ti 5o 12not impact of crystal structure.
Fig. 2 experiment condition is set: starting voltage 1V, and ceiling voltage 3V, final voltage 1V, sweep speed is 0.001V/s, sampling interval 0.001V, susceptibility 0.001A/V.Synthetic Li 4ti 5o 12as shown in Figure 2, there is obvious redox peak in the cyclic voltammetry curve of material, corresponding Li in Fig. 2 +embedding and deviate from process, only have one group of redox peak, Li is described 4ti 5o 12doff lithium course of reaction generates mutually without centre.And way in oxidation peak and reduction peak spacing difference less, this is with regard to the good reversibility of illustrative material, electrochemical polarization is little, the diffusion of lithium ion is better.
The experiment condition of Fig. 3: high frequency: 105kHZ, low frequency: 0.08HZ, starting voltage: 1V, amplitude: 0.005V.
The known internal resistance of cell of real axis intercept by the downward semicircle in high frequency region and Z ' is about 80 Ω.
Fig. 4 is front 100 cycle graphs under different multiplying, and experiment is set, discharge cut-off voltage 1V, and charge cutoff voltage 3V, the discharging current of 1C multiplying power is set as 0.21mA, and cycle-index sets 100; The discharging current of 2C multiplying power is set as 0.392mA cycle-index and sets 100.

Claims (9)

1. the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon, is characterized in that the preparation method that carbon is coated lithium titanate/carbon mano-tube composite carries out in the steps below:
Step 1, in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis, be that 0.5 ~ 1:1 ratio adds the titanium-containing compound of carbon nano-tube and facile hydrolysis in alcohol solution, the weight ratio of the titanium-containing compound of described carbon nano-tube and facile hydrolysis is 0.005 ~ 0.05:1, then under 40 ~ 60 ℃ of conditions, with 100 ~ 300 r/min speed, be stirred to formation emulsion, then dilute 5 ~ 10 times, the drier bead type amorphous titania/carbon nano-tube that obtains of spraying;
Step 2, by Li/Ti mol ratio, be (3.9 ~ 4.3): 5 take bead type amorphous titania/carbon nano-tube and the solubility lithium salts that step 1 obtains is placed in ball mill, press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h, then sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions, be warming up to again 650 ~ 1000 ℃, heat preservation sintering 3 ~ 8h, obtains presoma;
Step 3, presoma and carbon source that step 2 is obtained mix, then sintering 2 ~ 6 hours at inert atmosphere, 500 ~ 650 ℃; Obtain the coated lithium titanate/carbon mano-tube composite of carbon.
2. the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon according to claim 1, is characterized in that the titanium-containing compound of facile hydrolysis is metatitanic acid methyl esters, tetrabutyl titanate, tetraethyl titanate or isopropyl titanate described in step 1.
3. the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon according to claim 2, it is characterized in that described in step 1 alcohol solution be by alcohol and deionized water by (0.5 ~ 1): 1 volume ratio preparation.
4. the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon according to claim 3, it is characterized in that described in step 1 spraying dry be to be 180 ~ 250 ℃ in temperature, flow velocity is to carry out under 1 ~ 33mL/min condition.
5. the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon according to claim 4, is characterized in that carbon nano-tube described in step 1 is multi-walled carbon nano-tubes or the graphitized carbon nano pipe that double-walled carbon nano-tube, multi-walled carbon nano-tubes, vacuum high-temperature are processed.
6. the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon according to claim 5, is characterized in that described in step 1 that alcohol in alcohol solution is one or more the mixing in absolute ethyl alcohol, acetone, isopropyl alcohol, ethylene glycol, glycerol, butanediol, tetramethylenthanediol and butantriol.
7. the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon according to claim 6, is characterized in that the solubility lithium salts described in step 2 is lithium hydroxide, lithium acetate, lithium carbonate or lithium fluoride.
8. the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon according to claim 7, is characterized in that described in step 2 that inert atmosphere is nitrogen or argon gas, and inert atmosphere is nitrogen or argon gas described in step 3.
9. the preparation method of the coated lithium titanate/carbon mano-tube composite of carbon, is characterized in that the preparation method that carbon is coated lithium titanate/carbon mano-tube composite carries out in the steps below:
Step 1, in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis, be that 0.5 ~ 1:1 ratio adds the titanium-containing compound of carbon nano-tube, doped chemical and facile hydrolysis in alcohol solution, the weight ratio of the titanium-containing compound of described carbon nano-tube and facile hydrolysis is 0.005 ~ 0.05:1, then under 40 ~ 60 ℃ of conditions, with 100 ~ 300 r/min speed, be stirred to formation emulsion, then dilute 5 ~ 10 times, the drier bead type that obtains of spraying is containing the amorphous titania/carbon nano-tube of doped chemical;
Step 2, by Li/Ti mol ratio, be (3.9 ~ 4.3): 5 take bead type amorphous titania/carbon nano-tube and the solubility lithium salts that step 1 obtains is placed in ball mill, press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h, then sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions, be warming up to again 650 ~ 1000 ℃, heat preservation sintering 3 ~ 8h, obtains presoma;
Step 3, presoma and carbon source that step 2 is obtained mix, then sintering 2 ~ 6 hours at inert atmosphere, 500 ~ 650 ℃; Obtain the coated lithium titanate/carbon/carbon nano tube compound containing doped chemical of carbon, wherein described in step 1, doped chemical is one or both in Mg, Al, Co, V, W, F, and doped chemical is 0.005 ~ 0.08:1 with the molal weight ratio of titanium elements.
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