CN104300133B - A kind of lithium titanate material of CNT cladding and preparation method thereof - Google Patents
A kind of lithium titanate material of CNT cladding and preparation method thereof Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of lithium titanate material of CNT cladding and preparation method thereof, this material includes lithium titanate particle, described one layer of clad with three-dimensional net structure being formed by CNT of lithium titanate particle Surface coating.The lithium titanate material of the CNT cladding of the present invention, one layer of clad with three-dimensional net structure being formed by CNT of lithium titanate particle Surface coating, lithium titanate has excellent lithium storage performance in itself, coat after there is the CNT clad of three-dimensional net structure, its electrical conductivity, gram volume, high rate performance and cyclical stability are greatly improved, and make lithium titanate material can play more excellent effect in lithium ion battery and mixed capacitor.
Description
Technical field
The invention belongs to lithium titanate material technical field is and in particular to a kind of lithium titanate material of CNT cladding, same
When further relate to a kind of CNT cladding lithium titanate material preparation method.
Background technology
Lithium ion battery has running voltage height, energy density is big, have extended cycle life, self discharge is little, memory-less effect, ring
The features such as border is friendly, has become as the optimal portable power source of the equipment such as communication, electric tool, electric vehicle, Aero-Space.
In current lithium ion battery active material, Li4Ti5012There is special embedding lithium performance, its embedding lithium takes off lithium
Reaction be Li4Ti5012With Li7Ti5012Biphase conversion process, Li therebetween4Ti5012Framing structure hardly change,
Lithium ion quickly can be embedded abjection, thus its cycle performance and fast charging and discharging ability are very prominent；Additionally, this is embedding
The current potential of lithium process is about 1.55V (vs Li/Li+), in above-mentioned biphase interconversion processes, electrode potential is very flat, and works as two
When the transformation of phase is basically completed, the hop that electrode potential can rise or fall.Therefore, lithium titanate material has splendid following
Ring performance and the charge and discharge potential of safety, are a kind of remarkable lithium cell cathode materials of performance.
Due to the very low (＜ 10 of the electrical conductivity of lithium titanate-13S/m), lead to the high rate performance of battery of lithium titanate system not
Good.Accordingly, it would be desirable to be combined by the nano-carbon material superior with electric conductivity, improve the electrical conductivity of lithium titanate, just can make metatitanic acid
Lithium material plays excellent performance in lithium ion battery and in mixed capacitor.But, existing prepare CNT cladding/
In the technology of parcel lithium titanate compound, CNT often disperses not uniformly, to need to add dispersant；And preparation process
In also can add the materials such as doping element compound, chelating agent, electrode material introduces excessive impurity, causes lithium titanate
The end-use properties of composite not good it is impossible to meet use requirement.
Content of the invention
It is an object of the invention to provide a kind of lithium titanate material of CNT cladding, solve existing lithium titanate material conductive
Performance and high rate performance not good it is impossible to meet the problem of use requirement.
Second object of the present invention is to provide a kind of preparation method of the lithium titanate material of CNT cladding.
In order to realize object above, the technical solution adopted in the present invention is：A kind of lithium titanate material of CNT cladding
Material, including lithium titanate (Li4Ti5O12) granule, one layer of described lithium titanate particle Surface coating has three by what CNT was formed
The clad of dimension network structure.
The mass percent of each component is：Lithium titanate 70%～99%, CNT 1%～30%.
In described clad, it is chemical bonding between CNT.
A diameter of 1～100nm of described CNT, length is 1～50 μm.
Described CNT is SWCN, double-walled carbon nano-tube, in multi-walled carbon nano-tubes any one or many
Kind.
A kind of preparation method of the above-mentioned lithium titanate material of CNT cladding, comprises the following steps：
1) take the CNT of sense dough, be dispersed in water, obtain mixture A；
2) by step 1) gained mixture A add organic solvent in, mix to obtain mixture B；
3) to step 2) add lithium carbonate, titanium dioxide and sodium chloride in gained mixture B, carry out hydro-thermal after mix homogeneously
Reaction, obtains CNT gel detached with dicyandiamide solution；
4) taking step 3) gained CNT gel carries out roasting under an inert atmosphere, obtains final product.
Step 1) in, the CNT of described sense dough is that CNT is obtained successively with nitric acid, hydrochloric acid reaction.
The CNT of described sense dough is the CNT with hydroxyl, carboxyl functional group.
The preparation method of the CNT of described sense dough, including following concrete steps：
A) CNT is taken to mix with nitric acid, after heating reflux reaction, stratification, discard the transparent clear liquid in upper strata, obtain black
Color suspension；
B) after taking step a) gained black suspension and mixed in hydrochloric acid, centrifugation, obtain precipitate；
C) after taking centrifugation gained sediment and mixed in hydrochloric acid, centrifugation, obtain precipitate；
D) operation of repeat step c), the supernatant to centrifugation is colourless, collects precipitate, standby；
E) step d) gained sediment is dispersed in water, adjusting pH is 10, filters, obtain filter cake after ultrasonic disperse；
F) take filtration gained filter cake, be dispersed in water, adjusting pH is 10, filters, obtain filter cake after ultrasonic disperse；
G) operation of repeat step f), the filtrate to after filter is colourless, collects filter cake, standby；
H) step g) gained filter cake is taken to add water dispersion, filtering to filtrate is in neutrality, collects filter cake drying, obtains final product functional group
The CNT changed.
In step a), the concentration of described nitric acid is 2.6mol/L；CNT is 1 with the mass ratio of nitric acid:2～10.
In step a), the temperature of described heating reflux reaction is 50～95 DEG C, and the time is 24h.
In step a), the time of described standing is 20min.
Step b), c), d) in, the rotating speed of described centrifugation is 8000rpm, and the time is 20min.
Step b), c), d) in, the concentration of described hydrochloric acid is 1.0mol/L；The amount of addition hydrochloric acid is every time：Black suspension
Volume ratio with hydrochloric acid is 1:2～10.
Step e), f), g) in, time of described ultrasonic disperse is 30min.
Step e), f), g) in, adjust pH method be to be adjusted with NaOH solution, KOH solution or ammonia.
Step e), f), g) in, described filtration is that the film being 0.45 μm with aperture carries out sucking filtration.
In step h), the temperature of described drying is 120 DEG C.
Step 1) in, in gained mixture A, the content of the CNT of sense dough is 0.5～15mg/ml.
Step 2) in, described organic solvent is ethanol, acetone, any one or more in isopropyl acetone.
The addition of described organic solvent is：Mixture A is 1 with the volume ratio of organic solvent:1～5.
Step 3) in, add lithium carbonate, the amount of titanium dioxide and sodium chloride is to make the mol ratio of Li, Ti and NaCl be 0.4:
0.5:1～10.
Step 3) described in hydro-thermal reaction temperature be 120 DEG C～220 DEG C, the time be 6～24h.
Step 3) described in hydro-thermal reaction carry out in hydrothermal reaction kettle, in hydrothermal reaction kettle, the volume of material accounts for water
The 50%～80% of thermal response kettle total measurement (volume).
Step 4) described in roasting temperature be 450 DEG C～1200 DEG C, the time be 0.5～10h.
Step 4) described in inert atmosphere be nitrogen, any one or two kinds in argon.
The lithium titanate material of the CNT cladding of the present invention, one layer of lithium titanate particle Surface coating is formed by CNT
The clad with three-dimensional net structure, lithium titanate has excellent lithium storage performance in itself, coated and had three-dimensional network
After the CNT clad of structure, its electrical conductivity, gram volume, high rate performance and cyclical stability have obtained significantly carrying
High；Under the discharging condition of 0.5C multiplying power, gram volume reaches 160mAh/g, significantly larger than uncoated lithium titanate material
(130mAh/g) lithium titanate material (140mAh/g) with CNT physical doping；Clad Stability Analysis of Structures, carries on the whole
The high chemical property of lithium titanate material, makes lithium titanate material can play in lithium ion battery and mixed capacitor more excellent
Effect.
The preparation method of the lithium titanate material of CNT cladding of the present invention, is by the CNT dispersion of sense dough
In water/organic solvent, add the presoma (lithium carbonate, titanium dioxide) preparing lithium titanate and sodium chloride carries out hydro-thermal reaction
Roasting generates Li afterwards4Ti5O12, repair the conductive capability of CNT simultaneously；On the CNT of sense dough carry carboxyl and
Hydroxyl, polycondensation in hydro-thermal reaction forms three-dimensional netted stereochemical structure, chemically bonded to one another between CNT, is coated on metatitanic acid
On lithium granule, improve the electric conductivity of lithium titanate material；The CNT of sense dough has good hydrophilic and electrification
Learn performance, not only facilitate the dispersion of CNT, also can improve the chemical property that CNT coats lithium titanate material；Profit
With hydro-thermal reaction so that mixture can be under conditions of without dispersant and other impurity, by CNT and reaction
Persursor material mix homogeneously, make CNT formed three-dimensional network structure, be coated in lithium titanate particle；It is added without point
The materials such as powder, doping element compound, complex, will not introduce excessive impurity in the electrodes it is ensured that the quality of battery；Work
Skill is simple, easy to operate, suitable large-scale industrial production.
In the preparation method of lithium titanate material of CNT cladding of the present invention, the CNT of sense dough can dissolve
In water, CNT contains substantial amounts of hydroxyl and carboxyl, in hydro-thermal reaction, the hydroxyl on CNT and carboxyl occur
Reaction, formation CNT gel detached with dicyandiamide solution, to obtain CNT cladding lithium titanate material by sintering；NaCl is
Water soluble salt, it, is stayed in dicyandiamide solution after hydro-thermal reaction terminates as hydro-thermal reaction auxiliary agent, thus coagulating with CNT
Glue separates.CNT gel includes hydrone and the NaCl of CNT, lithium titanate material and denier.
Brief description
Fig. 1 is the scanning electron microscope (SEM) photograph of the lithium titanate material of embodiment 1 gained CNT cladding；
Fig. 2 is the electrochemical property test result schematic diagram of the lithium titanate material of embodiment 1 gained CNT cladding；
Fig. 3 is the discharge curve of the lithium titanate material of embodiment 2 gained CNT cladding；
Fig. 4 is the discharge curve of comparative example 1 (uncoated lithium titanate material)；
Fig. 5 is the discharge curve of comparative example 2 (lithium titanate material of CNT physical doping).
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
The lithium titanate material of the CNT cladding of the present embodiment, including lithium titanate particle, described lithium titanate particle surface
One layer of clad with three-dimensional net structure being formed by CNT of cladding；The mass percent of each component is：Lithium titanate
99%th, CNT 1%；In described clad, it is chemical bonding between CNT.
Described CNT is SWCN；A diameter of 1～100nm of CNT, length is 1～50 μm.
The preparation method of the lithium titanate material of CNT cladding of the present embodiment, comprises the following steps：
1) take the CNT of sense dough, be added to the water, ultrasonic make it dispersed, obtain mixture A, in mixture A
The content of the CNT of sense dough is 0.5mg/ml；
2) by step 1) gained mixture A adds in ethanol, and the volume ratio of mixture A and ethanol is 1:1, ultrasonic make it equal
Even dispersion, obtains mixture B；
3) to step 2) add lithium carbonate, titanium dioxide and sodium chloride in gained mixture B, make rubbing of Li, Ti and NaCl
That ratio is 0.4:0.5:5, add in hydrothermal reaction kettle after mix homogeneously and carry out hydro-thermal reaction, the volume of material in hydrothermal reaction kettle
Account for the 50% of hydrothermal reaction kettle total measurement (volume), hydrothermal temperature is 120 DEG C, the response time is 24h, obtains detached with dicyandiamide solution
CNT gel；
4) taking step 3) gained CNT gel carries out roasting under an inert atmosphere (nitrogen), and sintering temperature is 1200
DEG C, the time is 0.5h, obtains final product the lithium titanate material of described CNT cladding.
Wherein, the preparation method of the CNT of described sense dough, including following concrete steps：
A) CNT is taken to mix with nitric acid, the concentration of described nitric acid is 2.6mol/L, the quality of CNT and nitric acid
Than for 1:After 2,95 DEG C of heating reflux reaction 24h, it is cooled to room temperature, stand 20min AUTOMATIC ZONING, discard upper strata brownish red transparent
Clear liquid, obtains black suspension；The tail gas concentrated NaOH solution that heating reflux reaction produces absorbs；
B) step a) gained black suspension is taken to mix with hydrochloric acid stirring, the concentration of hydrochloric acid is 1.0mol/L, black suspension
Liquid is 1 with the volume ratio of hydrochloric acid:2, with the rotating speed centrifugation 20min of 8000rpm, abandon upper strata acid solution, obtain precipitate；
C) centrifugation gained sediment is taken to mix with hydrochloric acid stirring, the concentration of hydrochloric acid is 1.0mol/L, adds hydrochloric acid
The same step b) of volume, with the rotating speed centrifugation 20min of 8000rpm, abandons supernatant, obtains precipitate；
D) operation of repeat step c), colourless (the no free Ni of the supernatant to centrifugation2+), collect precipitate, standby
With；
E) step d) gained sediment is disperseed in deionized water, adjusting pH with NaOH solution is 10, ultrasonic disperse
After 30min, the filter membrane sucking filtration being 0.45 μm with aperture, obtain filter cake；
F) take gained filter cake, in deionized water, adjusting pH with NaOH solution is 10 for dispersion, after ultrasonic disperse 30min, uses
Aperture is 0.45 μm of filter membrane sucking filtration, obtains filter cake；
G) operation of repeat step f), the filtrate to sucking filtration is colourless, collects filter cake, standby；
H) take step g) gained filter cake, plus deionized water dispersion washing, sucking filtration to filtrate is neutrality, collects filter cake, 120
It is dried under the conditions of DEG C, obtain final product the CNT of sense dough.
The scanning electron microscope (SEM) photograph of the lithium titanate material of the present embodiment gained CNT cladding is as shown in Figure 1.Can from Fig. 1
Go out：By hydro-thermal reaction, CNT is coated on lithium titanate particle surface, defines and coats metatitanic acid than more uniform CNT
Lithium material.
Embodiment 2
The lithium titanate material of the CNT cladding of the present embodiment, including lithium titanate particle, described lithium titanate particle surface
One layer of clad with three-dimensional net structure being formed by CNT of cladding；The mass percent of each component is：Lithium titanate
90%th, CNT 10%；In described clad, it is chemical bonding between CNT.
Described CNT is double-walled carbon nano-tube；A diameter of 1～100nm of CNT, length is 1～50 μm.
The preparation method of the lithium titanate material of CNT cladding of the present embodiment, comprises the following steps：
1) take the CNT of sense dough, be added to the water, ball milling makes it dispersed, obtain mixture A, in mixture A
The content of the CNT of sense dough is 5mg/ml；
2) by step 1) gained mixture A adds in acetone, and the volume ratio of mixture A and ethanol is 1:5, ball milling makes it equal
Even dispersion, obtains mixture B；
3) to step 2) add lithium carbonate, titanium dioxide and sodium chloride in gained mixture B, make rubbing of Li, Ti and NaCl
That ratio is 0.4:0.5:1, add in hydrothermal reaction kettle after mix homogeneously and carry out hydro-thermal reaction, the volume of material in hydrothermal reaction kettle
Account for the 70% of hydrothermal reaction kettle total measurement (volume), hydrothermal temperature is 220 DEG C, the response time is 6h, obtains detached with dicyandiamide solution
CNT gel；
4) taking step 3) gained CNT gel carries out roasting under an inert atmosphere (nitrogen), and sintering temperature is 450 DEG C,
Time is 10h, obtains final product the lithium titanate material of described CNT cladding.
Wherein, the preparation method of the CNT of described sense dough, including following concrete steps：
A) CNT is taken to mix with nitric acid, the concentration of described nitric acid is 2.6mol/L, the quality of CNT and nitric acid
Than for 1:After 10,50 DEG C of heating reflux reaction 24h, it is cooled to room temperature, stand 20min AUTOMATIC ZONING, discard upper strata brownish red saturating
Ming and Qing liquid, obtains black suspension；The tail gas concentrated NaOH solution that heating reflux reaction produces absorbs；
B) step a) gained black suspension is taken to mix with hydrochloric acid stirring, the concentration of hydrochloric acid is 1.0mol/L, black suspension
Liquid is 1 with the volume ratio of hydrochloric acid:5, with the rotating speed centrifugation 20min of 8000rpm, abandon upper strata acid solution, obtain precipitate；
C) centrifugation gained sediment is taken to mix with hydrochloric acid stirring, the concentration of hydrochloric acid is 1.0mol/L, adds hydrochloric acid
The same step b) of volume, with the rotating speed centrifugation 20min of 8000rpm, abandons supernatant, obtains precipitate；
D) operation of repeat step c), colourless (the no free Ni of the supernatant to centrifugation2+), collect precipitate, standby
With；
E) step d) gained sediment is disperseed in deionized water, adjusting pH with KOH solution is 10, ultrasonic disperse
After 30min, the filter membrane sucking filtration being 0.45 μm with aperture, obtain filter cake；
F) take gained filter cake, in deionized water, adjusting pH with KOH solution is 10 for dispersion, after ultrasonic disperse 30min, uses
Aperture is 0.45 μm of filter membrane sucking filtration, obtains filter cake；
G) operation of repeat step f), the filtrate to sucking filtration is colourless, collects filter cake, standby；
H) take step g) gained filter cake, plus deionized water dispersion washing, sucking filtration to filtrate is neutrality, collects filter cake, 120
It is dried under the conditions of DEG C, obtain final product the CNT of sense dough.
Embodiment 3
The lithium titanate material of the CNT cladding of the present embodiment, including lithium titanate particle, described lithium titanate particle surface
One layer of clad with three-dimensional net structure being formed by CNT of cladding；The mass percent of each component is：Lithium titanate
80%th, CNT 20%；In described clad, it is chemical bonding between CNT.
Described CNT is multi-walled carbon nano-tubes；A diameter of 1～100nm of CNT, length is 1～50 μm.
The preparation method of the lithium titanate material of CNT cladding of the present embodiment, comprises the following steps：
1) take the CNT of sense dough, be added to the water, mechanical agitation makes it dispersed, obtain mixture A, mixture
In A, the content of the CNT of sense dough is 15mg/ml；
2) by step 1) gained mixture A adds in isopropanol, and the volume ratio of mixture A and ethanol is 1:2, mechanical agitation
Make it dispersed, obtain mixture B；
3) to step 2) add lithium carbonate, titanium dioxide and sodium chloride in gained mixture B, make rubbing of Li, Ti and NaCl
That ratio is 0.4:0.5:10, add in hydrothermal reaction kettle after mix homogeneously and carry out hydro-thermal reaction, the body of material in hydrothermal reaction kettle
Amass and account for the 60% of hydrothermal reaction kettle total measurement (volume), hydrothermal temperature is 150 DEG C, the response time is 17h, obtains and separates with dicyandiamide solution
CNT gel；
4) taking step 3) gained CNT gel carries out roasting under inert atmosphere (argon), and sintering temperature is 700 DEG C,
Time is 7h, obtains final product the lithium titanate material of described CNT cladding.
Wherein, the preparation method of the CNT of described sense dough, including following concrete steps：
A) CNT is taken to mix with nitric acid, the concentration of described nitric acid is 2.6mol/L, the quality of CNT and nitric acid
Than for 1:After 6,70 DEG C of heating reflux reaction 24h, it is cooled to room temperature, stand 20min AUTOMATIC ZONING, discard upper strata brownish red transparent
Clear liquid, obtains black suspension；The tail gas concentrated NaOH solution that heating reflux reaction produces absorbs；
B) step a) gained black suspension is taken to mix with hydrochloric acid stirring, the concentration of hydrochloric acid is 1.0mol/L, black suspension
Liquid is 1 with the volume ratio of hydrochloric acid:10, with the rotating speed centrifugation 20min of 8000rpm, abandon upper strata acid solution, obtain precipitate；
C) centrifugation gained sediment is taken to mix with hydrochloric acid stirring, the concentration of hydrochloric acid is 1.0mol/L, adds hydrochloric acid
The same step b) of volume, with the rotating speed centrifugation 20min of 8000rpm, abandons supernatant, obtains precipitate；
D) operation of repeat step c), colourless (the no free Ni of the supernatant to centrifugation2+), collect precipitate, standby
With；
E) step d) gained sediment is disperseed in deionized water, adjusting pH with ammonia is 10, ultrasonic disperse 30min
Afterwards, the filter membrane sucking filtration being 0.45 μm with aperture, obtains filter cake；
F) take gained filter cake, in deionized water, adjusting pH with ammonia is 10, after ultrasonic disperse 30min, uses aperture for dispersion
Filter membrane sucking filtration for 0.45 μm, obtains filter cake；
G) operation of repeat step f), the filtrate to sucking filtration is colourless, collects filter cake, standby；
H) take step g) gained filter cake, plus deionized water dispersion washing, sucking filtration to filtrate is neutrality, collects filter cake, 120
It is dried under the conditions of DEG C, obtain final product the CNT of sense dough.
Embodiment 4
The lithium titanate material of the CNT cladding of the present embodiment, including lithium titanate particle, described lithium titanate particle surface
One layer of clad with three-dimensional net structure being formed by CNT of cladding；The mass percent of each component is：Lithium titanate
70%th, CNT 30%；In described clad, it is chemical bonding between CNT.
Described CNT is the mixture of SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes；Carbon nanometer
A diameter of 1～100nm of pipe, length is 1～50 μm.
The preparation method of the lithium titanate material of CNT cladding of the present embodiment, comprises the following steps：
1) take the CNT of sense dough, be added to the water, ultrasonic make it dispersed, obtain mixture A, in mixture A
The content of the CNT of sense dough is 10mg/ml；
2) by step 1) gained mixture A adds the mixed liquor of ethanol and propanol (ethanol is 1 with the volume ratio of propanol:1)
) in, mixture A is 1 with the volume ratio of ethanol/propanol mixed liquor:4, ultrasonic make it dispersed, obtain mixture B；
3) to step 2) add lithium carbonate, titanium dioxide and sodium chloride in gained mixture B, make rubbing of Li, Ti and NaCl
That ratio is 0.4:0.5:7, add in hydrothermal reaction kettle after mix homogeneously and carry out hydro-thermal reaction, the volume of material in hydrothermal reaction kettle
Account for the 80% of hydrothermal reaction kettle total measurement (volume), hydrothermal temperature is 180 DEG C, the response time is 12h, obtains detached with dicyandiamide solution
CNT gel；
4) taking step 3) gained CNT gel carries out roasting under inert atmosphere (argon), and sintering temperature is 1000
DEG C, the time is 3h, obtains final product the lithium titanate material of described CNT cladding.
Wherein, the preparation method of the CNT of described sense dough, including following concrete steps：
A) CNT is taken to mix with nitric acid, the concentration of described nitric acid is 2.6mol/L, the quality of CNT and nitric acid
Than for 1:After 4,80 DEG C of heating reflux reaction 24h, it is cooled to room temperature, stand 20min AUTOMATIC ZONING, discard upper strata brownish red transparent
Clear liquid, obtains black suspension；The tail gas concentrated NaOH solution that heating reflux reaction produces absorbs；
B) step a) gained black suspension is taken to mix with hydrochloric acid stirring, the concentration of hydrochloric acid is 1.0mol/L, black suspension
Liquid is 1 with the volume ratio of hydrochloric acid:8, with the rotating speed centrifugation 20min of 8000rpm, abandon upper strata acid solution, obtain precipitate；
C) centrifugation gained sediment is taken to mix with hydrochloric acid stirring, the concentration of hydrochloric acid is 1.0mol/L, adds hydrochloric acid
The same step b) of volume, with the rotating speed centrifugation 20min of 8000rpm, abandons supernatant, obtains precipitate；
D) operation of repeat step c), colourless (the no free Ni of the supernatant to centrifugation2+), collect precipitate, standby
With；
E) step d) gained sediment is disperseed in deionized water, adjusting pH with NaOH solution is 10, ultrasonic disperse
After 30min, the filter membrane sucking filtration being 0.45 μm with aperture, obtain filter cake；
F) take gained filter cake, in deionized water, adjusting pH with NaOH solution is 10 for dispersion, after ultrasonic disperse 30min, uses
Aperture is 0.45 μm of filter membrane sucking filtration, obtains filter cake；
G) operation of repeat step f), the filtrate to sucking filtration is colourless, collects filter cake, standby；
H) take step g) gained filter cake, plus deionized water dispersion washing, sucking filtration to filtrate is neutrality, collects filter cake, 120
It is dried under the conditions of DEG C, obtain final product the CNT of sense dough.
Experimental example
This experimental example is tested to the chemical property of the lithium titanate material that embodiment 1-4 gained CNT coats,
Result is as shown in Figure 2-5.
Wherein, the active material that comparative example 1 is adopted is uncoated lithium titanate material；The activity that comparative example 2 is adopted
Material is the lithium titanate material of CNT physical doping.
Fig. 2 shows the gram volume under the conditions of different multiplying for the lithium titanate material of embodiment 1 gained CNT cladding,
And the capacity of electric discharge Posterior circle 20 times keeps situation under the conditions of different multiplying.Figure it is seen that in 0.5C multiplying power discharging
Under conditions of, the gram volume of the lithium titanate material of embodiment 2 is 170mAh/g, and after circulating 20 times, capability retention is 100%；
Under conditions of 1C multiplying power discharging, gram volume is 165mAh/g, and after circulating 20 times, capability retention is 100%；Put in 2C multiplying power
Under conditions of electricity, gram volume is 160mAh/g, and after circulating 20 times, capability retention is 100%；Condition in 3C multiplying power discharging
Under, gram volume is 160mAh/g, and after circulating 20 times, capability retention is 100%；Under conditions of 5C multiplying power discharging, gram volume
For 130mAh/g, after circulating 20 times, capability retention is 100%.The experimental result of embodiment 2-4 is with embodiment 1.Experimental result
Show, the lithium titanate material of the CNT cladding of the present invention has higher gram volume and circulation volume conservation rate, forthright again
Can be excellent.
Fig. 3, Fig. 4, Fig. 5 respectively illustrate embodiment 2 gained CNT cladding lithium titanate material and comparative example 1 (not
Cladding lithium titanate material), the discharge curve of comparative example 2 (lithium titanate material of CNT physical doping).From Fig. 3,4,5
As can be seen that the lithium titanate material of embodiment 2 gained CNT cladding is under the discharging condition of 0.5C multiplying power, gram volume is
160mAh/g, and comparative example 1 (uncoated lithium titanate material) is under conditions of 0.5C multiplying power, gram volume is 130mAh/g；Right
Under conditions of 0.5C multiplying power, gram volume is 140mAh/g to ratio 2 (lithium titanate material of CNT physical doping).Embodiment
1st, 3 and 4 experimental result is with embodiment 2.Test result indicate that, the lithium titanate material of the CNT of present invention cladding with respect to
Uncoated lithium titanate material and the lithium titanate material of CNT physical doping, gram volume is greatly improved.
Claims (8)
1. a kind of CNT cladding lithium titanate material it is characterised in that：Including lithium titanate particle, described lithium titanate particle table
Bread covers one layer of clad with three-dimensional net structure being formed by CNT；
Described lithium titanate material is obtained by the method comprising the following steps：
1）Take the CNT of sense dough, be dispersed in water, obtain mixture A；
2）By step 1）Gained mixture A adds in organic solvent, mixes to obtain mixture B；
3）To step 2）Add lithium carbonate, titanium dioxide and sodium chloride in gained mixture B, carry out hydro-thermal after mix homogeneously anti-
Should, obtain CNT gel detached with dicyandiamide solution；
4）Take step 3）Gained CNT gel carries out roasting under an inert atmosphere, obtains final product；
Step 3）In, add lithium carbonate, the amount of titanium dioxide and sodium chloride is to make the mol ratio of Li, Ti and NaCl be 0.4:
0.5:1～10；
Step 4）Described in roasting temperature be 450 DEG C～1200 DEG C, the time be 0.5～10h.
2. according to claim 1 CNT cladding lithium titanate material it is characterised in that：The quality hundred of each component
Point ratio is：Lithium titanate 70%～99%, CNT 1%～30%.
3. according to claim 1 or 2 CNT cladding lithium titanate material it is characterised in that：Described clad
In, it is chemical bonding between CNT.
4. according to claim 1 or 2 CNT cladding lithium titanate material it is characterised in that：Described carbon nanometer
A diameter of 1～100nm of pipe, length is 1～50 μm.
5. a kind of as described in claim 1 CNT cladding lithium titanate material preparation method it is characterised in that：Bag
Include the following step：
1）Take the CNT of sense dough, be dispersed in water, obtain mixture A；
2）By step 1）Gained mixture A adds in organic solvent, mixes to obtain mixture B；
3）To step 2）Add lithium carbonate, titanium dioxide and sodium chloride in gained mixture B, carry out hydro-thermal after mix homogeneously anti-
Should, obtain CNT gel detached with dicyandiamide solution；
4）Take step 3）Gained CNT gel carries out roasting under an inert atmosphere, obtains final product；
Step 3）In, add lithium carbonate, the amount of titanium dioxide and sodium chloride is to make the mol ratio of Li, Ti and NaCl be 0.4:
0.5:1～10；
Step 4）Described in roasting temperature be 450 DEG C～1200 DEG C, the time be 0.5～10h.
6. according to claim 5 CNT cladding lithium titanate material preparation method it is characterised in that：Step
1）In, the CNT of described sense dough is that CNT is obtained successively with nitric acid, hydrochloric acid reaction.
7. according to claim 5 CNT cladding lithium titanate material preparation method it is characterised in that：Step
2）In, described organic solvent is ethanol, acetone, any one or more in isopropyl acetone.
8. according to claim 5 CNT cladding lithium titanate material preparation method it is characterised in that：Step
3）Described in hydro-thermal reaction temperature be 120 DEG C～220 DEG C, the time be 6～24h.
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| CN106207132B (en) * | 2016-08-31 | 2019-06-14 | 深圳博磊达新能源科技有限公司 | A kind of preparation method of lithium titanate/carbon fiber/carbon nanotube/graphene quaternary composite material |
| CN106384819A (en) * | 2016-11-07 | 2017-02-08 | 珠海格力电器股份有限公司 | Carbon-coated lithium titanate material and preparation method thereof as well as lithium-ion battery |
| CN107742710B (en) * | 2017-10-18 | 2020-05-19 | 安徽工业大学 | Preparation method of chromium-based lithium ion battery composite negative electrode material |
| CN107732207B (en) * | 2017-10-18 | 2020-05-26 | 安徽工业大学 | Preparation method of chromium titanium-based lithium ion battery multi-stage structure cathode material |
| CN110620213B (en) * | 2018-06-20 | 2022-03-25 | 贝特瑞新材料集团股份有限公司 | Composite material of lithium tetrachloroaluminate and carbon nanotube coated lithium titanate, preparation method and application thereof |
| CN108878845A (en) * | 2018-07-03 | 2018-11-23 | 重庆大学 | A kind of lithium titanate microballoon/carbon nano tube compound material and preparation method thereof |
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