CN108878845A - A kind of lithium titanate microballoon/carbon nano tube compound material and preparation method thereof - Google Patents
A kind of lithium titanate microballoon/carbon nano tube compound material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of lithium titanate microballoon/carbon nano tube compound materials and preparation method thereof；The method that the present invention prepares lithium titanate/carbon/carbon nano tube is simple, and compound is monodisperse particles, carbon nanotube layer is uniformly adsorbed in lithium titanate particle surface, the carbon nanotube layer has good electric conductivity, be conducive to the quick diffusion of lithium ion during high power charging-discharging, to improve the performance of material；When the composite material that the present invention is prepared is as lithium ion battery negative material, good charge-discharge magnification performance and cyclical stability are shown；Lithium titanate microballoon/carbon mano-tube composite that wherein content of carbon nanotubes is 13% specific discharge capacity under the multiplying power of 1C reaches 172mAh/g, and charge-discharge magnification when being up to 100C capacity still have 121mAh/g, and under 10C multiplying power after charge and discharge cycles 500 times, capacity retention ratio 89%.
Description
Technical field
The present invention relates to lithium ion battery negative material field, specifically a kind of lithium titanate microballoon/carbon nanotube composite
Material and preparation method thereof.
Background technique
Lithium ion battery has been widely used for energy storage device, electric car, electronics field etc..In recent years, environment
Problem get worse and the fast development of electric car, people are to the cycle life of lithium ion battery, high rate performance and peace
More stringent requirements are proposed for full unfailing performance etc..Spinel type lithium titanate is as lithium cell cathode material, and because having, " zero is answered
Become " and the advantages such as have extended cycle life have received widespread attention.
However, the low electronic conductivity of lithium titanate material has seriously affected its high rate capability.Research shows that：Lithium titanate/
Carbon material can effectively improve the electronic conduction characteristic of material, and the preparation method of composite material, carbon materials in carbon composite
Material property and content have larger impact to the chemical property of prepared compound.
The lithium titanate/carbon/carbon nano tube material being prepared using different carbon source and its preparation are successively disclosed in the prior art
Method.
Wherein, in the prior art include one kind under protective atmosphere or vacuum environment, by lithium titanate with it is carbon containing vapor-phase
Object heating is closed, reaction obtains metatitanic acid lithium/carbon composite material.The carbon source is cracked into the carbon of carbonization structure under 1000 DEG C of high temperature
And lithium titanate surface is evenly coated at membranaceous.The material is 148mAh/g in 10C discharge capacity, lives through 200 circulations
Afterwards, capacity retention ratio 98.1%.
It in the prior art include that one kind is uniformly coated under the action of oxidant by gaseous polymerization, obtained polypyrrole
Lithium titanate precursor calcines this presoma under an inert gas, obtains lithium titanate/nitrogen-doped carbon composite material.The material exists
Under 5C multiplying power, specific discharge capacity is up to 130~140mAh/g, and under 10C multiplying power, specific discharge capacity is up to 100~110mAh/g.
In the prior art further include a kind of refinement for realizing lithium titanate using micro emulsion method, and solution is made in carbon source, utilizes
Hydro-thermal reaction realizes the carbon coating of nanoscale lithium titanate, forms uniform, compact conductive carbon network on lithium titanate surface, should
Material is 92% by 5000 circulation volume conservation rates when charging and discharging currents density is 2.5A/g.
But the degree of graphitization of lithium titanate/Carbon composites layer of charcoal prepared by the above method is lower, makes its electric conductivity
Poor, it still needs further improvement for the chemical property of prepared compound.
Summary of the invention
Present invention aim to address problems of the prior art, and it is multiple to provide a kind of lithium titanate microballoon/carbon nanotube
Condensation material and preparation method thereof.
To realize the present invention purpose and the technical solution adopted is that such, a kind of lithium titanate microballoon/carbon nanotube is compound
The preparation method of material, which is characterized in that include the following steps：
1) pretreatment of carbon nanotube
1.1) carbon nanotube is added in nitric acid solution, after ultrasonic disperse, obtains mixture A；
The concentration of the nitric acid solution is 10%~68%；
The w/v (g ︰ mL) of the carbon nanotube and nitric acid solution is (0.5~5) ︰ (50~500)；
1.2) mixture A obtained in step 1.1) is subjected to constant temperature processing, obtains mixture B；
In the constant temperature treatment process：Temperature is 60~118 DEG C, and the time is 2~12h；
1.3) after mixture B obtained in step 1.2) is cooled to room temperature, mixture B is filtered using distilled water,
Until obtained filtrate is in neutrality, then after obtained filter cake is dried, pretreated carbon nanotube is obtained；
In the drying process process：Temperature be 60~80 DEG C, the time be 12~for 24 hours；
2) preparation of lithium titanate precursor
2.1) under stirring, cetyl trimethylammonium bromide is added in ethylene glycol, is heated to cetyl
Trimethylammonium bromide is completely dissolved, and obtains mixture C；
The temperature of the heating process is 40~60 DEG C；
The concentration of the cetyl trimethylammonium bromide is 0.1~0.3g/mL；
2.2) butyl titanate is added in the mixture C obtained in step 2.1), obtains mixture D；
The volume ratio of ethylene glycol in the butyl titanate and step 2.1) is 3.4 ︰ (20~30)；
2.3) lithium hydroxide is soluble in water, obtain lithium hydroxide solution；
The molar ratio of butyl titanate used in the lithium hydroxide and step 2.2) is 10 ︰ (8.8~9)；
The volume ratio of the water in ethylene glycol and this step in the step 2.1) is 0.6 ︰ 1.5；
2.4) while stirring, lithium hydroxide solution obtained in step 2.3) is added drop-wise in step 2.2) and is obtained
Mixture D in, after being added dropwise to complete, obtain product A；
The rate of addition is 0.5~5ml/min；
2.5) product A obtained in step 2.4) is subjected to hydro-thermal reaction, to after reaction, by obtained product B into
Row is dried, and obtains lithium titanate precursor；
In the hydrothermal reaction process：Temperature is 130~180 DEG C, and the time is 6~72h；
In the drying process process：Temperature is 60~80 DEG C, and the time is 24~48h；
3) preparation of lithium titanate microballoon
Lithium titanate precursor obtained in step 2.5) is calcined in air atmosphere, obtains lithium titanate microballoon；
In the calcination process：Temperature is 500~700 DEG C, and the time is 2~10h；
4) lithium titanate microballoon/carbon nano tube compound material preparation
It is 4.1) pretreated carbon nanotube and cetyl trimethylammonium bromide obtained in step 1.3) is soluble in water,
After ultrasonic disperse, mixture E is obtained；
The pretreated carbon nanotube and the weight ratio of cetyl trimethylammonium bromide are 1.25 ︰, 1~2.8 ︰ 1；
The w/v (g ︰ mL) of the pretreated carbon nanotube and water is (0.01~0.1) ︰ 100；
4.2) lithium titanate microballoon obtained in step 3) is added to the water, after ultrasonic disperse, obtains white suspension；
The w/v (g ︰ mL) of the lithium titanate and water is (0.4~2) ︰ 10；
4.3) white suspension obtained in step 4.2) is added drop-wise in mixture E obtained in step 4.1), is added dropwise
After, obtain product C；
5~the 10ml/min of rate of addition；
4.4) it stands after being vibrated product C obtained in step 4.3), after standing, is filtered, will be filtered
After cake is dried, product D is obtained；
In the oscillatory process：Frequency is 100~200r/min, and the time is 10~30min；
The time of repose is 0.5~2h；
In the drying process：Temperature be 60~80 DEG C, the time be 12~for 24 hours；
4.5) product D obtained in step 4.4) is calcined, obtains lithium titanate microballoon/carbon nano tube compound material；
In the calcination process：Temperature is 290~350 DEG C, and the time is 10~120min.
Further, in the ultrasonic procedure in the step 1.1)：Ultrasonic power be 100~200w, ultrasonic time be 0.5~
1h。
Further, in the ultrasonic procedure in the step 4.1)：Ultrasonic power be 100~200w, ultrasonic time be 0.5~
5h。
Further, in the ultrasonic procedure in the step 4.2)：Ultrasonic power be 100~200w, ultrasonic time be 5~
15min。
One kind is micro- by the described in any item preparation methods of Claims 1 to 4 carbon nanotube cladding lithium titanate obtained
Ball composite material.
It is worth noting that：The method that the present invention uses self assembly, has for one layer in lithium titanate microsphere surface uniform adsorption
The carbon nanotube of high conductivity, to effectively improve the electric conductivity and chemical property of lithium titanate.
The solution have the advantages that unquestionable, the present invention has the following advantages that：
1) it is simple to prepare lithium titanate microballoon/carbon nanotube method by the present invention, and compound is monodisperse particles, lithium titanate
Microsphere surface has uniformly adsorbed carbon nanotube layer, which has good electric conductivity, is conducive to fill in high magnification
The quick diffusion of lithium ion in discharge process, to improve the performance of material；
2) when the composite material that the present invention is prepared is as lithium ion battery negative material, good charge and discharge are shown
High rate performance and cyclical stability；
Lithium titanate microballoon/carbon mano-tube composite that wherein content of carbon nanotubes is 13% in compound is under the multiplying power of 1C
Specific discharge capacity reaches 172mAh/g, and capacity still has 121mAh/g when charge-discharge magnification is up to 100C, and under 10C multiplying power
After charge and discharge cycles 500 times, capacity retention ratio 89%.
Detailed description of the invention
Fig. 1 is lithium titanate microballoon/carbon nanotube composite materials scanning electron microscope (SEM) photograph that embodiment 1 provides；
Fig. 2 is that lithium titanate microballoon/carbon nanotube composite materials assembled battery high rate performance that embodiment 2 provides is bent
Line chart；
Fig. 3 is that lithium titanate microballoon/carbon nanotube composite materials assembled battery cycle performance that embodiment 2 provides is bent
Line chart.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention only
It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used
With means, various replacements and change are made, should all include within the scope of the present invention.
Embodiment 1：
A kind of preparation method of lithium titanate microballoon/carbon nano tube compound material, which is characterized in that include the following steps：
1) pretreatment of carbon nanotube
1.1) 2g carbon nanotube is added in 200mL nitric acid solution, after ultrasonic disperse, obtains mixture A；
The concentration of the nitric acid solution is 68%；
1.2) mixture A obtained in step 1.1) is pre-processed, obtains mixture B；
In the preprocessing process：Temperature is 118 DEG C, time 2h；
1.3) after mixture B obtained in step 1.2) is cooled to room temperature, mixture B is filtered using distilled water,
Until obtained filtrate is in neutrality, then after obtained filter cake is dried, pretreated carbon nanotube is obtained；
In the drying process process：Temperature is 60 DEG C, and the time is for 24 hours；
2) preparation of lithium titanate precursor
2.1) 1g cetyl trimethylammonium bromide (CTAB) is added in 20mL ethylene glycol, being heated to 40 DEG C makes 16
Alkyl trimethyl ammonium bromide is completely dissolved, and obtains mixture C；
2.2) 3.4mL butyl titanate is added in the mixture C obtained in step 2.1), obtains mixture D；
2.3) 0.3559g lithium hydroxide is dissolved in 30mL water, obtains lithium hydroxide solution；
2.4) while stirring, lithium hydroxide solution obtained in step 2.3) is added drop-wise in step 2.2) and is obtained
Mixture D in, after being added dropwise to complete, obtain product A；
The rate of addition is 1ml/min；
2.5) product A obtained in step 2.4) is subjected to hydro-thermal reaction, to after reaction, by obtained product B into
Row is dried, and obtains lithium titanate precursor；
In the hydrothermal reaction process：Temperature is 170 DEG C, and the time is for 24 hours；
In the drying process process：Temperature is 80 DEG C, and the time is for 24 hours；
3) preparation of lithium titanate
Lithium titanate precursor obtained in step 2.5) is calcined in air atmosphere, obtains lithium titanate；
In the calcination process：Temperature is 500 DEG C, time 5h；
4) lithium titanate microballoon/carbon nano tube compound material preparation
4.1) by the pretreated carbon nanotube of 0.1g obtained in step 1.3) (CNT) and 80mg cetyl trimethyl bromine
Change ammonium to be dissolved in 100mL water, after ultrasonic disperse 2h, obtains mixture E；
4.2) 0.75g lithium titanate (LTO) obtained in step 3) is added in 10mL water, after ultrasonic disperse 5min, is obtained
To white suspension；
4.3) white suspension obtained in step 4.2) is added drop-wise in mixture E obtained in step 4.1), is added dropwise
After, obtain product C；
The rate of addition is 10ml/min；
4.4) it stands after being vibrated product C obtained in step 4.3), after standing, is filtered, will be filtered
After cake is dried, product D is obtained；
In the oscillatory process：Speed is 200r/min, time 30min；
The time of repose is 2h；
In the drying process：Temperature is 60 DEG C, time 12h；
4.5) product D obtained in step 4.4) is calcined, obtains lithium titanate microballoon/carbon nano tube compound material；
In the calcination process：Temperature is 350 DEG C, time 2h.
The carbon nanotube covering amount for analyzing this compound through TPO is 13%.
As shown in Figure 1, the as obtained lithium titanate microballoon/carbon nano tube compound material scanning electron microscope (SEM) photograph of the present embodiment.
Embodiment 2：
It is followed the steps below using the microballoon of lithium titanate obtained in embodiment 1/carbon nano tube compound material：
1) by lithium titanate microballoon/carbon nano tube compound material respectively with conductive agent acetylene black, binder CMC, according to quality
Than 8:1:1 mixing, is modulated into slurry for this mixture using distilled water as solvent, is coated uniformly on copper foil, 60 DEG C of vacuum drying 8
Hour, obtained experimental cell pole piece；
It 2) is to electrode with lithium piece, electrolyte is 1mol/L (volume ratio 1:1:1) LiPF6/EC+DEC+DMC solution, every
Film is 2400 film of Celgard, is assembled into LIR2430 type button cell in the glove box full of argon atmosphere；
Fig. 2 and Fig. 3 is the multiplying power of lithium titanate microballoon/carbon nanotube composite materials assembled battery provided in this embodiment
Performance curve and cycle performance curve；
After being assembled into battery with the material, specific discharge capacity has reached 172mAh/g, and charge and discharge times under the multiplying power of 1C
Capacity still has 121mAh/g when rate is up to 100C, under 10C multiplying power after charge and discharge cycles 500 times, capacity retention ratio 89%.
Embodiment 3：
A kind of preparation method of lithium titanate microballoon/carbon nano tube compound material, which is characterized in that include the following steps：
1) pretreatment of carbon nanotube
1.1) 0.5g carbon nanotube is added in 100mL nitric acid solution, after ultrasonic disperse, obtains mixture A；
The concentration of the nitric acid solution is 30%；
1.2) mixture A obtained in step 1.1) is pre-processed, obtains mixture B；
In the preprocessing process：Temperature is 80 DEG C, time 12h；
1.3) after mixture B obtained in step 1.2) is cooled to room temperature, mixture B is filtered using distilled water,
Until obtained filtrate is in neutrality, then after obtained filter cake is dried, pretreated carbon nanotube is obtained；
In the drying process process：Temperature is 60 DEG C, time 12h；
2) preparation of lithium titanate precursor
2.1) 2g cetyl trimethylammonium bromide (CTAB) is added in 25mL ethylene glycol, after ultrasonic disperse, is obtained
Mixture C；
2.2) 3.4mL butyl titanate is added in the mixture C obtained in step 2.1), obtains mixture D；
2.3) 0.364g lithium hydroxide is dissolved in 25mL water, obtains lithium hydroxide solution；
2.4) while stirring, lithium hydroxide solution obtained in step 2.3) is added drop-wise in step 2.2) and is obtained
Mixture D in, after being added dropwise to complete, obtain product A；
The rate of addition is 5ml/min；
2.5) product A obtained in step 2.4) is subjected to hydro-thermal reaction, to after reaction, by obtained product B into
Row is dried, and obtains lithium titanate precursor；
In the hydrothermal reaction process：Temperature is 150 DEG C, time 48h；
In the drying process process：Temperature is 80 DEG C, and the time is for 24 hours；
3) preparation of lithium titanate
Lithium titanate precursor obtained in step 2.5) is calcined in air atmosphere, obtains lithium titanate；
In the calcination process：Temperature is 600 DEG C, time 2h；
4) lithium titanate microballoon/carbon nano tube compound material preparation
4.1) by the pretreated carbon nanotube of 0.1g obtained in step 1.3) (CNT) and 50mg cetyl trimethyl bromine
Change ammonium to be dissolved in 100mL water, after ultrasonic disperse 2h, obtains mixture E；
4.2) 0.9g lithium titanate (LTO) obtained in step 3) is added separately in 10mL water, after ultrasonic disperse 5min,
Obtain white suspension；
4.3) white suspension obtained in step 4.2) is added drop-wise in mixture E obtained in step 4.1), is added dropwise
After, obtain product C；
The rate of addition is 10ml/min；
4.4) it stands after being vibrated product C obtained in step 4.3), after standing, is filtered, will be filtered
After cake is dried, product D is obtained；
In the oscillatory process：100r/min, time 30min；
The time of repose is 2h；
In the drying process：Temperature is 60 DEG C, time 12h；
4.5) product D obtained in step 4.4) is calcined, obtains lithium titanate microballoon/carbon nano tube compound material；
In the calcination process：Temperature is 290 DEG C, time 1h.
It is 10% through the content of carbon nanotubes in TPO analysis compound.
Embodiment 4：
A kind of preparation method of lithium titanate microballoon/carbon nano tube compound material, which is characterized in that include the following steps：
1) pretreatment of carbon nanotube
1.1) 0.5g carbon nanotube is added in 100mL nitric acid solution, after ultrasonic disperse, obtains mixture A；
The concentration of the nitric acid solution is 30%；
1.2) mixture A obtained in step 1.1) is pre-processed, obtains mixture B；
In the preprocessing process：Temperature is 80 DEG C, time 12h；
1.3) after mixture B obtained in step 1.2) is cooled to room temperature, mixture B is filtered using distilled water,
Until obtained filtrate is in neutrality, then after obtained filter cake is dried, pretreated carbon nanotube is obtained；
In the drying process process：Temperature is 60 DEG C, time 12h；
2) preparation of lithium titanate precursor
2.1) 2g cetyl trimethylammonium bromide (CTAB) is added in 25mL ethylene glycol, after ultrasonic disperse, is obtained
Mixture C；
2.2) 3.4mL butyl titanate is added in the mixture C obtained in step 2.1), obtains mixture D；
2.3) 0.364g lithium hydroxide is dissolved in 25mL water, obtains lithium hydroxide solution；
2.4) while stirring, lithium hydroxide solution obtained in step 2.3) is added drop-wise in step 2.2) and is obtained
Mixture D in, after being added dropwise to complete, obtain product A；
The rate of addition is 5ml/min；
2.5) product A obtained in step 2.4) is subjected to hydro-thermal reaction, to after reaction, by obtained product B into
Row is dried, and obtains lithium titanate precursor；
In the hydrothermal reaction process：Temperature is 150 DEG C, time 48h；
In the drying process process：Temperature is 80 DEG C, and the time is for 24 hours；
3) preparation of lithium titanate
Lithium titanate precursor obtained in step 2.5) is calcined in air atmosphere, obtains lithium titanate；
In the calcination process：Temperature is 600 DEG C, time 2h；
4) lithium titanate microballoon/carbon nano tube compound material preparation
4.1) by the pretreated carbon nanotube of 0.1g obtained in step 1.3) (CNT) and 50mg cetyl trimethyl bromine
Change ammonium to be dissolved in 100mL water, after ultrasonic disperse 2h, obtains mixture E；
4.2) 0.4g lithium titanate (LTO) obtained in step 3) is added separately in 10mL water, after ultrasonic disperse 5min,
Obtain white suspension；
4.3) white suspension obtained in step 4.2) is added drop-wise in mixture E obtained in step 4.1), is added dropwise
After, obtain product C；
The rate of addition is 10ml/min；
4.4) it stands after being vibrated product C obtained in step 4.3), after standing, is filtered, will be filtered
After cake is dried, product D is obtained；
In the oscillatory process：100r/min, time 30min；
The time of repose is 2h；
In the drying process：Temperature is 60 DEG C, time 12h；
4.5) product D obtained in step 4.4) is calcined, obtains lithium titanate microballoon/carbon nano tube compound material；
In the calcination process：Temperature is 290 DEG C, time 1h.
It is 20% through the content of carbon nanotubes in TPO analysis compound.
Embodiment 5：
It the use of content of carbon nanotubes obtained in embodiment 3 is below 10% lithium titanate/carbon/carbon nano tube composite material carries out
Step：
1) by lithium titanate microballoon/carbon nano tube compound material respectively with conductive agent acetylene black, binder CMC, according to quality
Than 8:1:1 mixing, is modulated into slurry for this mixture using distilled water as solvent, is coated uniformly on copper foil, 60 DEG C of vacuum drying 8
Hour, obtained experimental cell pole piece；
It 2) is to electrode with lithium piece, electrolyte is 1mol/L (volume ratio 1:1:1) LiPF6/EC+DEC+DMC solution, every
Film is 2400 film of Celgard, is assembled into LIR2430 type button cell in the glove box full of argon atmosphere；
After being assembled into battery with the material, specific discharge capacity has reached 181mAh/g, and charge and discharge times under the multiplying power of 1C
Capacity still has 141mAh/g when rate is up to 100C, under 10C multiplying power after charge and discharge cycles 500 times, capacity retention ratio 92%.
Embodiment 6：
It the use of content of carbon nanotubes obtained in embodiment 4 is below 20% lithium titanate/carbon/carbon nano tube composite material carries out
Step：
1) by lithium titanate microballoon/carbon nano tube compound material respectively with conductive agent acetylene black, binder CMC, according to quality
Than 8:1:1 mixing, is modulated into slurry for this mixture using distilled water as solvent, is coated uniformly on copper foil, 60 DEG C of vacuum drying 8
Hour, obtained experimental cell pole piece；
It 2) is to electrode with lithium piece, electrolyte is 1mol/L (volume ratio 1:1:1) LiPF6/EC+DEC+DMC solution, every
Film is 2400 film of Celgard, is assembled into LIR2430 type button cell in the glove box full of argon atmosphere；
After being assembled into battery with the material, specific discharge capacity has reached 197mAh/g, and charge and discharge times under the multiplying power of 1C
Capacity still has 135mAh/g when rate is up to 100C, under 10C multiplying power after charge and discharge cycles 500 times, capacity retention ratio 94%.
Claims (5)
1. a kind of preparation method of lithium titanate microballoon/carbon nano tube compound material, which is characterized in that include the following steps：
1) pretreatment of carbon nanotube
1.1) carbon nanotube is added in nitric acid solution, after ultrasonic disperse, obtains mixture A；
The concentration of the nitric acid solution is 10%~68%；
The w/v (g ︰ mL) of the carbon nanotube and nitric acid solution is (0.5~5) ︰ (50~500)；
1.2) mixture A obtained in step 1.1) is subjected to constant temperature processing, obtains mixture B；
In the constant temperature treatment process：Temperature is 60~118 DEG C, and the time is 2~12h；
1.3) after mixture B obtained in step 1.2) is cooled to room temperature, mixture B is filtered using distilled water, until
Obtained filtrate is in neutrality, then after obtained filter cake is dried, obtains pretreated carbon nanotube；
In the drying process process：Temperature be 60~80 DEG C, the time be 12~for 24 hours；
2) preparation of lithium titanate precursor
2.1) under stirring, cetyl trimethylammonium bromide is added in ethylene glycol, is heated to cetyl front three
Base ammonium bromide is completely dissolved, and obtains mixture C；
The temperature of the heating process is 40~60 DEG C；
The concentration of the cetyl trimethylammonium bromide is 0.1~0.3g/mL；
2.2) butyl titanate is added in the mixture C obtained in step 2.1), obtains mixture D；
The volume ratio of ethylene glycol in the butyl titanate and step 2.1) is 3.4 ︰ (20~30)；
2.3) lithium hydroxide is soluble in water, obtain lithium hydroxide solution；
The molar ratio of butyl titanate used in the lithium hydroxide and step 2.2) is 10 ︰ (8.8~9)；
The volume ratio of the water in ethylene glycol and this step in the step 2.1) is 0.6 ︰ 1.5；
2.4) while stirring, lithium hydroxide solution obtained in step 2.3) is added drop-wise to obtained in step 2.2) and is mixed
It closes in object D, after being added dropwise to complete, obtains product A；
The rate of addition is 0.5~5ml/min；
2.5) product A obtained in step 2.4) is subjected to hydro-thermal reaction, to which after reaction, obtained product B is done
Dry processing, obtains lithium titanate precursor；
In the hydrothermal reaction process：Temperature is 130~180 DEG C, and the time is 6~72h；
In the drying process process：Temperature is 60~80 DEG C, and the time is 24~48h；
3) preparation of lithium titanate microballoon
Lithium titanate precursor obtained in step 2.5) is calcined in air atmosphere, obtains lithium titanate microballoon；
In the calcination process：Temperature is 500~700 DEG C, and the time is 2~10h；
4) lithium titanate microballoon/carbon nano tube compound material preparation
4.1) pretreated carbon nanotube and cetyl trimethylammonium bromide obtained in step 1.3) is soluble in water, ultrasound
After dispersion, mixture E is obtained；
The pretreated carbon nanotube and the weight ratio of cetyl trimethylammonium bromide are 1.25 ︰, 1~2.8 ︰ 1；
The w/v (g ︰ mL) of the pretreated carbon nanotube and water is (0.01~0.1) ︰ 100；
4.2) lithium titanate microballoon obtained in step 3) is added to the water, after ultrasonic disperse, obtains white suspension；
The w/v (g ︰ mL) of the lithium titanate and water is (0.4~2) ︰ 10；
4.3) white suspension obtained in step 4.2) is added drop-wise in mixture E obtained in step 4.1), completion of dropwise addition
Afterwards, product C is obtained；
5~the 10ml/min of rate of addition；
4.4) stand after being vibrated product C obtained in step 4.3), after standing, filtered, by filter cake into
After row is dried, product D is obtained；
In the oscillatory process：Frequency is 100~200r/min, and the time is 10~30min；
The time of repose is 0.5~2h；
In the drying process：Temperature be 60~80 DEG C, the time be 12~for 24 hours；
4.5) product D obtained in step 4.4) is calcined, obtains lithium titanate microballoon/carbon nano tube compound material；
In the calcination process：Temperature is 290~350 DEG C, and the time is 10~120min.
2. a kind of preparation method of lithium titanate microballoon/carbon nano tube compound material according to claim 1, feature exist
In：In ultrasonic procedure in the step 1.1)：Ultrasonic power is 100~200w, and ultrasonic time is 0.5~1h.
3. a kind of preparation method of lithium titanate microballoon/carbon nano tube compound material according to claim 1, feature exist
In：In ultrasonic procedure in the step 4.1)：Ultrasonic power is 100~200w, and ultrasonic time is 0.5~5h.
4. a kind of preparation method of lithium titanate microballoon/carbon nano tube compound material according to claim 1, feature exist
In：In ultrasonic procedure in the step 4.2)：Ultrasonic power is 100~200w, and ultrasonic time is 5~15min.
5. one kind is compound by the described in any item preparation methods of Claims 1 to 4 lithium titanate microballoon/carbon nanotube obtained
Material.
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| CN115799486A (en) * | 2023-02-03 | 2023-03-14 | 中国华能集团清洁能源技术研究院有限公司 | Micron-sized lithium titanate and multi-walled carbon nanotube composite material and preparation method and application thereof |
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| CN109904435A (en) * | 2019-04-08 | 2019-06-18 | 深圳大学 | A kind of preparation method and combination electrode material of combination electrode material |
| CN109904435B (en) * | 2019-04-08 | 2021-11-30 | 深圳大学 | Preparation method of composite electrode material and composite electrode material |
| CN115799486A (en) * | 2023-02-03 | 2023-03-14 | 中国华能集团清洁能源技术研究院有限公司 | Micron-sized lithium titanate and multi-walled carbon nanotube composite material and preparation method and application thereof |
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