CN102694177A - 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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CN102694177A
CN102694177A CN2012101637126A CN201210163712A CN102694177A CN 102694177 A CN102694177 A CN 102694177A CN 2012101637126 A CN2012101637126 A CN 2012101637126A CN 201210163712 A CN201210163712 A CN 201210163712A CN 102694177 A CN102694177 A CN 102694177A
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carbon
preparation
lithium titanate
lithium
cnt
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CN102694177B (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 coats the preparation method of lithium titanate/carbon mano-tube composite
Technical field
The invention belongs to the lithium ion battery negative material field; Be specifically related to the preparation method of carbon coating lithium titanate/carbon mano-tube composite.
Background technology
Commercial at present lithium ion battery negative material mainly adopts material with carbon element; Though 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 behind the embedding lithium; Can on negative pole, separate out the lithium metallic dendrite if overcharge, poke barrier film easily and cause battery short circuit, have great potential safety problem.Also caused carbon negative pole material pessimistic on cycle performance.So, seek a kind of have higher-security simultaneously the good again negative material of cycle performance 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 an example, the Li of fraction +Occupy in the tetrahedral gap of 8a in the structure cell most of Li +With all Ti 4+Then occupy in the octahedral interstice of 16d, and all O 2-Then constitute the FCC dot matrix, as Li in the position of 32e +During embedding, the Li of embedding +Will with the Li of 8a position +Migrate to 16c together and form Li 7Ti 5O 12, formed Li azury in embedding lithium process 7Ti 5O 12Conduct electricity, and be spinel structure,, can not produce the bulk effect of material and cause the cycle performance of total variable effect to battery so his cell parameter a is constant basically.
Spinel-type Li 4Ti 5O 12Has the stable discharge platform; And the embedding of lithium ion and deviate from can not produce bigger influence to the structure of itself; So just because of these characteristics of itself are referred to as " zero strain material ", his this specific character has very excellent cycle performance with regard to having caused the prepared lithium ion battery that goes out.In addition,, the organic solvent in the electrolyte and relative current potential (with respect to lithium metal) can be reduced formation SEI film because being lower than when the negative material of 0.8V contacts, 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 the SEI film on the surface.And be all the carbon negative pole (the relative current potential of graphite is 0.15V) of negative material because he has formed the SEI film with contacting of electrolyte in the process of first charge-discharge, and 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 12Has the incomparable superior function of other negative materials, so with Li 4Ti 5O 12Be applied in the commodity battery, realize that its industrialization has 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, spray drying, molten salt growth method or the like, use now many be high temperature solid-state method and sol-gel processing.The high temperature solid-state method Li that simply is easy to get wherein 4Ti 5O 12, but if being applied in industry still exists some problems, and for example: the temperature requirement of sintering is too high; Basically concentrate between 800 ~ 1000 ℃; And the product purity after the sintering is not high, because the inhomogeneities of its particle causes its tap density problem of lower; Though and sol-gel processing can obtain the higher Li of purity 4Ti 5O 12Product, but its technology is comparatively complicated, is not suitable for large-scale commercial production.
Patent CN201010149910.8 directly mixes the oven dry sintering with the solubility lithium salt solution in ultrasonic dispersed carbon nanotubes and had both obtained lithium titanate with anatase titania; Because the bad assurance of control of its CNT amount; Cause the prepared lithium titanate/carbon/carbon nano tube network structure of this method to exist the CNT distribution between the lithium titanate particle disorderly and unsystematic, can't play good connection bridging action.
Summary of the invention
The present invention will solve existing Li 4Ti 5O 12The technical problem of specific capacity and cycle performance difference; And provide carbon to coat the preparation method of lithium titanate/carbon mano-tube composite.
The preparation method of carbon coating lithium titanate/carbon mano-tube composite is undertaken by following step among the present invention: the preparation method that carbon coats lithium titanate/carbon mano-tube composite is undertaken by following step:
Step 1, to be 0.5 ~ 1:1 ratio in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis add the titanium-containing compound of CNT and facile hydrolysis in the alcohol solution; The weight ratio of the titanium-containing compound of said CNT and facile hydrolysis is 0.005 ~ 0.05:1; Under 40 ~ 60 ℃ of conditions, be stirred to formation emulsion then with 100 ~ 300 r/min speed; Dilute 5 ~ 10 times then, spray drying obtains bead type amorphous titania/CNT again;
Step 2, be (3.9 ~ 4.3) by the Li/Ti mol ratio: 5 take by weighing bead type amorphous titania/CNT and the solubility lithium salts that step 1 obtains is placed in the ball mill; Press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h; Sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions then; Be warming up to 650 ~ 1000 ℃ again, heat preservation sintering 3 ~ 8h obtains presoma;
Step 3, presoma and carbon source mixing that step 2 is obtained are then inert atmosphere, 500 ~ 650 ℃ of following sintering 2 ~ 6 hours; Promptly obtain carbon and coat lithium titanate/carbon mano-tube composite.
Carbon of the present invention coats that the preparation method of lithium titanate/carbon mano-tube composite also can carry out in following step: step 1, be in the titanium-containing compound adding alcohol solution of 0.5 ~ 1:1 ratio with CNT, doped chemical and facile hydrolysis in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis; The weight ratio of the titanium-containing compound of said CNT and facile hydrolysis is 0.005 ~ 0.05:1; Under 40 ~ 60 ℃ of conditions, be stirred to formation emulsion then with 100 ~ 300 r/min speed; Dilute 5 ~ 10 times then, spray drying obtains bead type amorphous titania/CNT again;
Step 2, be (3.9 ~ 4.3) by the Li/Ti mol ratio: 5 take by weighing bead type amorphous titania/CNT and the solubility lithium salts that step 1 obtains is placed in the ball mill; Press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h; Sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions then; Be warming up to 650 ~ 1000 ℃ again, heat preservation sintering 3 ~ 8h obtains presoma;
Step 3, presoma and carbon source mixing that step 2 is obtained are then inert atmosphere, 500 ~ 650 ℃ of following sintering 2 ~ 6 hours; Promptly obtain carbon and coat lithium titanate/carbon mano-tube composite, wherein the said doped chemical of step 1 is one or both among Mg, Al, Co, V, W, the 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 CNT that are easy to hydrolysis to take the lead in preparing the bead type structure; Help follow-up synthetic lithium titanate material being carried out better modification and coating; The presoma of preparing 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 the electronics, the specific capacity and the high rate performance of raising negative material.
Adopt an amount of carbon source that synthetic material is carried out low temperature and coat, prevent that the agglomeration of particle from taking place, better form the sugarcoated haws type special construction of the lithium titanate of strip simultaneously.
The present invention adopts to possess certain intensity with very high absorption property CNT initiatively adsorbs the solubility titanium-containing compound, and its adsorption mechanism is, because the zeta potential of CNT is a negative potential, adsorbs the Ti after solvable through electrostatic adsorption 4+And under the condition of acidity; The absorption property of CNT is best, so will control its pH 4.5 ~ 5.0 in the process that forms colloidal sol, forms the particle of titanium-containing compound at its body; Then can form the compound of the CNT of titaniferous after the spray drying, thus for back preferably and modified lithium titanate lay the foundation.
Lithium titanate anode material that the present invention synthesized and the prepared lithium titanate of existing existing technology compare to possess has better high magnification cycle performance; And its technology is simple, is easy to realize industrialization.
Description of drawings
Fig. 1 is embodiment 20 resulting XRD figures; The CV figure that Fig. 2 obtains for embodiment 20; Fig. 3 is embodiment 20 resulting EIS figure; Fig. 4 is embodiment 20 resulting Specific Capacitity-Cycle Number figure; 1 is illustrated in Specific Capacitity under the 1C multiplying power-Cycle Numbe figure among the figure, and 2 are illustrated in the Specific Capacitity-Cycle Numbe figure under the 2C multiplying power; Fig. 5 is the resulting Li of embodiment 20 methods 4Ti 5O 12Theoretical microstructure sketch map.
Embodiment
Embodiment one: the preparation method of carbon coating lithium titanate/carbon mano-tube composite is undertaken by following step in this execution mode:
Step 1, to be 0.5 ~ 1:1 ratio in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis add the titanium-containing compound of CNT and facile hydrolysis in the alcohol solution; The weight ratio of the titanium-containing compound of said CNT and facile hydrolysis is 0.005 ~ 0.05:1; Under 40 ~ 60 ℃ of conditions, be stirred to formation emulsion then with 100 ~ 300 r/min speed; Dilute 5 ~ 10 times then, spray drying obtains bead type amorphous titania/CNT again;
Step 2, be (3.9 ~ 4.3) by the Li/Ti mol ratio: 5 take by weighing bead type amorphous titania/CNT and the solubility lithium salts that step 1 obtains is placed in the ball mill; Press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h; Sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions then; Be warming up to 650 ~ 1000 ℃ again, heat preservation sintering 3 ~ 8h obtains presoma;
Step 3, presoma and carbon source mixing that step 2 is obtained are then inert atmosphere, 500 ~ 650 ℃ of following sintering 2 ~ 6 hours; Promptly obtain carbon and coat lithium titanate/carbon mano-tube composite.
Embodiment two: what this execution mode and embodiment one were different is: the titanium-containing compound of the said facile hydrolysis of step 1 is metatitanic acid methyl esters, tetrabutyl titanate, tetraethyl titanate or isopropyl titanate.Other step is identical with embodiment one with parameter.
Embodiment three: what this execution mode was different with embodiment one or two is: the said alcohol solution of step 1 be by pure and mild deionized water by (0.5 ~ 1): 1 volume ratio preparation.Other step is identical with embodiment one or two with parameter.
Embodiment four: what this execution mode was different with one of embodiment one to three is: the said spray drying of step 1 is to be 180 ~ 250 ℃ in temperature, and flow velocity is to carry out under 1 ~ 33 mL/min condition.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what this execution mode was different with one of embodiment one to four is: the said CNT of step 1 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 handled.Other step is identical with one of embodiment one to four with parameter.
Multi-walled carbon nano-tubes after said vacuum high-temperature is handled is that the effective high-temperature vacuum furnace of multi-wall carbon nano-tube after vacuum high-temperature is handled has carried out 1500 ~ 2150 ℃ to gather the multi-walled carbon nano-tubes for preparing with catalystic pyrolysis in the fluid bed in nanometer.
Embodiment six: what this execution mode was different with one of embodiment one to five is: alcohol is a kind of wherein several kinds the mixing in absolute ethyl alcohol, acetone, isopropyl alcohol, ethylene glycol, glycerine, butanediol, tetramethylenthanediol and the butantriol in the said alcohol solution of step 1.Other step is identical with one of embodiment one to five with parameter.
Embodiment seven: what this execution mode was different with one of embodiment one to six is: the described solubility lithium salts of step 2 is lithium hydroxide, lithium acetate, lithium carbonate or lithium fluoride.Other step is identical with one of embodiment one to six with parameter.
Embodiment eight: what this execution mode was different with one of embodiment one to seven is: the said inert atmosphere of step 2 is nitrogen or argon gas, and the said inert atmosphere of step 3 is nitrogen or argon gas.Other step is identical with one of embodiment one to seven with parameter.
Embodiment nine: what this execution mode was different with one of embodiment one to eight is: the content of the said carbon coated of step 2 is that 0.5% ~ 5% presoma with the step 2 acquisition mixes with carbon source, and carbon source is sucrose, glucose, pitch, glycogen, phenolic resins or epoxy resin.Other step is identical with one of embodiment one to eight with parameter.
Embodiment ten: the preparation method of carbon coating lithium titanate/carbon mano-tube composite is undertaken by following step in this execution mode:
Step 1, to be 0.5 ~ 1:1 ratio in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis add the titanium-containing compound of CNT, doped chemical and facile hydrolysis in the alcohol solution; The weight ratio of the titanium-containing compound of said CNT and facile hydrolysis is 0.005 ~ 0.05:1; Under 40 ~ 60 ℃ of conditions, be stirred to formation emulsion then with 100 ~ 300 r/min speed; Dilute 5 ~ 10 times then, spray drying obtains bead type amorphous titania/CNT again;
Step 2, be (3.9 ~ 4.3) by the Li/Ti mol ratio: 5 take by weighing bead type amorphous titania/CNT and the solubility lithium salts that step 1 obtains is placed in the ball mill; Press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h; Sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions then; Be warming up to 650 ~ 1000 ℃ again, heat preservation sintering 3 ~ 8h obtains presoma;
Step 3, presoma and carbon source mixing that step 2 is obtained are then inert atmosphere, 500 ~ 650 ℃ of following sintering 2 ~ 6 hours; Promptly obtain carbon and coat lithium titanate/carbon mano-tube composite, wherein the said doped chemical of step 1 is one or both among Mg, Al, Co, V, W, the F, and doped chemical is 0.005 ~ 0.08:1 with the molal weight ratio of titanium elements.
When doped chemical is two kinds in this execution mode, press between each doped chemical arbitrarily than mixing.
Embodiment 11: what this execution mode and embodiment ten were different is: the titanium-containing compound of the said facile hydrolysis of step 1 is metatitanic acid methyl esters, tetrabutyl titanate, tetraethyl titanate or isopropyl titanate.Other step is identical with embodiment ten with parameter.
Embodiment 12: what this execution mode was different with embodiment ten or 11 is: the said alcohol solution of step 1 be by pure and mild deionized water by (0.5 ~ 1): 1 volume ratio preparation.Other step is identical with embodiment ten or 11 with parameter.
Embodiment 13: what this execution mode was different with one of embodiment ten to 12 is: the said spray drying of step 1 is to be 180 ~ 250 ℃ in temperature, and flow velocity is to carry out under 1 ~ 33 mL/min condition.Other step is identical with one of embodiment ten to 12 with parameter.
Embodiment 14: what this execution mode was different with one of embodiment ten to 13 is: the said CNT of step 1 is the 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 is identical with one of embodiment ten to 13 with parameter.
Multi-walled carbon nano-tubes after said vacuum high-temperature is handled is that the effective high-temperature vacuum furnace of multi-wall carbon nano-tube after vacuum high-temperature is handled has carried out 1500 ~ 2150 ℃ to gather the multi-walled carbon nano-tubes for preparing with catalystic pyrolysis in the fluid bed in nanometer.
Embodiment 15: what this execution mode was different with one of embodiment ten to 14 is: alcohol is a kind of wherein several kinds the mixing in absolute ethyl alcohol, acetone, isopropyl alcohol, ethylene glycol, glycerine, butanediol, tetramethylenthanediol and the butantriol in the said alcohol solution of step 1.Other step is identical with one of embodiment ten to 14 with parameter.
Embodiment 16: what this execution mode was different with one of embodiment ten to 15 is: the described solubility lithium salts of step 2 is lithium hydroxide, lithium acetate, lithium carbonate or lithium fluoride.Other step is identical with one of embodiment ten to 15 with parameter.
Embodiment 17: what this execution mode was different with one of embodiment ten to 16 is: the said inert atmosphere of step 2 is nitrogen or argon gas, and the said inert atmosphere of step 3 is nitrogen or argon gas.Other step is identical with one of embodiment ten to 16 with parameter.
Embodiment 18: what this execution mode was different with one of embodiment ten to 17 is: the content of the said carbon coated of step 2 is that 0.5% ~ 5% presoma with the step 2 acquisition mixes with carbon source, and carbon source is sucrose, glucose, pitch, glycogen, phenolic resins or epoxy resin.Other step is identical with one of embodiment ten to 17 with parameter.
Embodiment 19: the preparation method of carbon coating lithium titanate/carbon mano-tube composite is undertaken by following step in this execution mode:
Step 1, with 0.0085g CNT (CNT) CNT and 0.1mol tetrabutyl titanate (C 16H 36O 4Ti) add in the 500mL alcohol solution (wherein absolute ethyl alcohol and deionized water are the ratio row configuration of 0.8:1 according to volume ratio); Under 50 ℃ of conditions, be stirred to formation emulsion then with 200r/min speed; Dilute 2 times then; Spray drying (200 ℃ of baking temperatures, material flow are 25ml/min) obtains bead type amorphous titania/CNT again;
Step 2,1.974g bead type amorphous titania/CNT and 0.7886g Li 2CO 3Be placed in the ball mill, press rotating speed 300 ~ 350r/min ball milling 10 ~ 12h, (heating rate is 5 ℃/min) sintering 8h under the condition, is warming up to 850 ℃ again, and heat preservation sintering 4h cools to room temperature with the furnace, obtains presoma nitrogen atmosphere, 600 ℃ then;
Step 3, presoma and 1.1143g citric acid (C that the 9g step 2 is obtained 6H 8O 7H 2O) mixing is then nitrogen atmosphere, 400 ℃ of following sintering 2 hours; Promptly obtain carbon and coat lithium titanate/carbon mano-tube composite.
It is beading structure that the present invention obtains carbon coating lithium titanate/carbon mano-tube composite.
Embodiment 20: the preparation method of carbon coating lithium titanate/carbon mano-tube composite is undertaken by following step in this execution mode:
Step 1, with 1.1942g basic magnesium carbonate [(MgCO 3) 4Mg (OH) 26H 2O], 0.0085g CNT (CNT) CNT and 0.1mol tetrabutyl titanate (C 16H 36O 4Ti) wherein absolute ethyl alcohol and deionized water are during the ratio row of 0.8:1 dispose according to volume ratio to add the 500mL alcohol solution; Under 50 ℃ of conditions, be stirred to formation emulsion then with 200 r/min speed; Dilute 2 times then; Spray drying (200 ℃ of baking temperatures, material flow are 25 ml/min) obtains bead type amorphous titania/CNT again;
Step 2,1.974g bead type amorphous titania/CNT and 0.7886g Li 2CO 3Be placed in the ball mill, press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h, (heating rate is 5 ℃/min) sintering 8h under the condition, is warming up to 850 ℃ again, and heat preservation sintering 4h cools to room temperature with the furnace, obtains presoma nitrogen atmosphere, 600 ℃ then;
Step 3, presoma and 1.1143g citric acid (C that the 9g step 2 is obtained 6H 8O 7H 2O) mixing is then nitrogen atmosphere, 400 ℃ of following sintering 2 hours; Promptly obtain carbon and coat lithium titanate/carbon mano-tube composite.
It is beading structure (as shown in Figure 5) that the present invention obtains carbon coating lithium titanate/carbon mano-tube composite.
The surface area of making specimen is 10mm * 10mm, and sample thickness is 0.08mm, 70 ° of scanning angles during test (2 θ), sweep speed 10 o/ min; Result such as Fig. 1; Reference standard card (PDF49-0207) can know that product is the Li of pure phase 4Ti 5O 12, do not have the generation of impurity phase.Be illustrated under this synthesis condition synthetic Li 4Ti 5O 12Not influence 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 12The cyclic voltammetry curve of material is as shown in Figure 2, occurs tangible redox peak among Fig. 2, corresponding Li +Embedding and deviate from process, have only one group of redox peak, Li is described 4Ti 5O 12In the middle of having, the doff lithium course of reaction do not generate mutually.And oxidation peak and reduction peak spacing difference are less in the way, and this is with regard to the good reversibility of illustrative material, and electrochemical polarization is little, and 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.
Can know that by downward semicircle of high frequency region and the real axis intercept of Z ' internal resistance of cell is about 80 Ω.
Fig. 4 is preceding 100 cycle graphs under the different multiplying, and experiment is set, discharge cut-off voltage 1V, and charging cut-ff voltage 3V, the discharging current of 1C multiplying power is set at 0.21mA, and cycle-index sets 100; The discharging current of 2C multiplying power is set at the 0.392mA cycle-index and sets 100.

Claims (10)

1. carbon coats the preparation method of lithium titanate/carbon mano-tube composite, it is characterized in that the preparation method of carbon coating lithium titanate/carbon mano-tube composite is undertaken by following step:
Step 1, to be 0.5 ~ 1:1 ratio in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis add the titanium-containing compound of CNT and facile hydrolysis in the alcohol solution; The weight ratio of the titanium-containing compound of said CNT and facile hydrolysis is 0.005 ~ 0.05:1; Under 40 ~ 60 ℃ of conditions, be stirred to formation emulsion then with 100 ~ 300 r/min speed; Dilute 5 ~ 10 times then, spray drying obtains bead type amorphous titania/CNT again;
Step 2, be (3.9 ~ 4.3) by the Li/Ti mol ratio: 5 take by weighing bead type amorphous titania/CNT and the solubility lithium salts that step 1 obtains is placed in the ball mill; Press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h; Sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions then; Be warming up to 650 ~ 1000 ℃ again, heat preservation sintering 3 ~ 8h obtains presoma;
Step 3, presoma and carbon source mixing that step 2 is obtained are then inert atmosphere, 500 ~ 650 ℃ of following sintering 2 ~ 6 hours; Promptly obtain carbon and coat lithium titanate/carbon mano-tube composite.
2. carbon according to claim 1 coats the preparation method of lithium titanate/carbon mano-tube composite, and the titanium-containing compound that it is characterized in that the said facile hydrolysis of step 1 is metatitanic acid methyl esters, tetrabutyl titanate, tetraethyl titanate or isopropyl titanate.
3. carbon according to claim 2 coats the preparation method of lithium titanate/carbon mano-tube composite, it is characterized in that the said alcohol solution of step 1 be by pure and mild deionized water by (0.5 ~ 1): 1 volume ratio preparation.
4. carbon according to claim 3 coats the preparation method of lithium titanate/carbon mano-tube composite, it is characterized in that the said spray drying of step 1 is is 180 ~ 250 ℃ in temperature, and flow velocity is to carry out under 1 ~ 33mL/min condition.
5. carbon according to claim 4 coats the preparation method of lithium titanate/carbon mano-tube composite, it is characterized in that the said CNT of step 1 is the 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.
6. carbon according to claim 5 coats the preparation method of lithium titanate/carbon mano-tube composite, it is characterized in that alcohol is a kind of wherein several kinds the mixing in absolute ethyl alcohol, acetone, isopropyl alcohol, ethylene glycol, glycerine, butanediol, tetramethylenthanediol and the butantriol in the said alcohol solution of step 1.
7. carbon according to claim 6 coats the preparation method of lithium titanate/carbon mano-tube composite, it is characterized in that the described solubility lithium salts of step 2 is lithium hydroxide, lithium acetate, lithium carbonate or lithium fluoride.
8. carbon according to claim 7 coats the preparation method of lithium titanate/carbon mano-tube composite, it is characterized in that the said inert atmosphere of step 2 is nitrogen or argon gas, and the said inert atmosphere of step 3 is nitrogen or argon gas.
9. coat the preparation method of lithium titanate/carbon mano-tube composite according to the described carbon of each claim among the claim 1-8; The content that it is characterized in that the said carbon coated of step 2 is that 0.5% ~ 5% presoma with the step 2 acquisition mixes with carbon source, and carbon source is sucrose, glucose, pitch, glycogen, phenolic resins or epoxy resin.
10. carbon coats the preparation method of lithium titanate/carbon mano-tube composite, it is characterized in that the preparation method of carbon coating lithium titanate/carbon mano-tube composite is undertaken by following step:
Step 1, to be 0.5 ~ 1:1 ratio in the mass ratio of the titanium-containing compound of alcohol solution and facile hydrolysis add the titanium-containing compound of CNT, doped chemical and facile hydrolysis in the alcohol solution; The weight ratio of the titanium-containing compound of said CNT and facile hydrolysis is 0.005 ~ 0.05:1; Under 40 ~ 60 ℃ of conditions, be stirred to formation emulsion then with 100 ~ 300 r/min speed; Dilute 5 ~ 10 times then, spray drying obtains bead type amorphous titania/CNT again;
Step 2, be (3.9 ~ 4.3) by the Li/Ti mol ratio: 5 take by weighing bead type amorphous titania/CNT and the solubility lithium salts that step 1 obtains is placed in the ball mill; Press rotating speed 200 ~ 350r/min ball milling 6 ~ 12h; Sintering 5 ~ 12h under inert atmosphere, 500 ~ 650 ℃ of conditions then; Be warming up to 650 ~ 1000 ℃ again, heat preservation sintering 3 ~ 8h obtains presoma;
Step 3, presoma and carbon source mixing that step 2 is obtained are then inert atmosphere, 500 ~ 650 ℃ of following sintering 2 ~ 6 hours; Promptly obtain carbon and coat lithium titanate/carbon mano-tube composite, wherein the said doped chemical of step 1 is one or both among Mg, Al, Co, V, W, the F, and doped chemical is 0.005 ~ 0.08:1 with the molal weight ratio of titanium elements.
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Cited By (10)

* Cited by examiner, † Cited by third party
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CN103107324A (en) * 2013-03-04 2013-05-15 江苏大学 Preparation methods of fluorine-containing lithium ion battery cathode material lithium titanate (Li4Ti5O12)
CN103647065A (en) * 2013-12-20 2014-03-19 安康学院 Preparation method of sulfur/multi-wall carbon nanotube in core-shell structure
CN103682278A (en) * 2013-12-26 2014-03-26 山东精工电子科技有限公司 Preparation method of nanocarbon coated lithium titanate cathode material
CN105514397A (en) * 2016-03-02 2016-04-20 桂林理工大学 Method for preparing nitrogen-doped carbon nanotube
CN106058179A (en) * 2016-07-06 2016-10-26 湖南大学 Preparation method of carbon nanotube/silica/carbon composite cathode material
WO2016188130A1 (en) * 2015-05-22 2016-12-01 田东 Preparation method for porous graphite-doped and carbon-coated lithium titanate negative electrode material
CN107572600A (en) * 2017-09-28 2018-01-12 湖北大学 A kind of preparation method of lithiumation spherical cobaltic-cobaltous oxide particle
CN108417785A (en) * 2018-01-11 2018-08-17 茆胜 Fluorine nitrogen-doped graphene coats lithium titanate composite material and preparation method thereof
CN109786705A (en) * 2019-01-17 2019-05-21 禹城贝尔新材料有限公司 A kind of lithium titanate anode material and its preparation method and application with multistage carbon coating network structure
CN112736234A (en) * 2021-01-15 2021-04-30 辽宁大学 Novel lithium ion battery cathode material based on biomass/carbon nanotube composite modified lithium titanate and application thereof

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CN103107324B (en) * 2013-03-04 2016-03-02 江苏大学 A kind of preparation method of fluorine-containing lithium ionic cell cathode material lithium titanate
CN103107324A (en) * 2013-03-04 2013-05-15 江苏大学 Preparation methods of fluorine-containing lithium ion battery cathode material lithium titanate (Li4Ti5O12)
CN103647065A (en) * 2013-12-20 2014-03-19 安康学院 Preparation method of sulfur/multi-wall carbon nanotube in core-shell structure
CN103682278A (en) * 2013-12-26 2014-03-26 山东精工电子科技有限公司 Preparation method of nanocarbon coated lithium titanate cathode material
CN103682278B (en) * 2013-12-26 2016-05-11 山东精工电子科技有限公司 The preparation method of the coated lithium titanate anode material of a kind of nanometer carbon
WO2016188130A1 (en) * 2015-05-22 2016-12-01 田东 Preparation method for porous graphite-doped and carbon-coated lithium titanate negative electrode material
CN105514397A (en) * 2016-03-02 2016-04-20 桂林理工大学 Method for preparing nitrogen-doped carbon nanotube
CN106058179A (en) * 2016-07-06 2016-10-26 湖南大学 Preparation method of carbon nanotube/silica/carbon composite cathode material
CN107572600A (en) * 2017-09-28 2018-01-12 湖北大学 A kind of preparation method of lithiumation spherical cobaltic-cobaltous oxide particle
CN108417785A (en) * 2018-01-11 2018-08-17 茆胜 Fluorine nitrogen-doped graphene coats lithium titanate composite material and preparation method thereof
CN108417785B (en) * 2018-01-11 2020-11-17 茆胜 Fluorine-nitrogen doped graphene coated lithium titanate composite material and preparation method thereof
CN109786705A (en) * 2019-01-17 2019-05-21 禹城贝尔新材料有限公司 A kind of lithium titanate anode material and its preparation method and application with multistage carbon coating network structure
CN112736234A (en) * 2021-01-15 2021-04-30 辽宁大学 Novel lithium ion battery cathode material based on biomass/carbon nanotube composite modified lithium titanate and application thereof
CN112736234B (en) * 2021-01-15 2024-02-20 辽宁大学 Novel lithium ion battery anode material based on biomass/carbon nanotube composite modified lithium titanate and application thereof

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