CN107221647A - A kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material - Google Patents
A kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material Download PDFInfo
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- CN107221647A CN107221647A CN201710585876.0A CN201710585876A CN107221647A CN 107221647 A CN107221647 A CN 107221647A CN 201710585876 A CN201710585876 A CN 201710585876A CN 107221647 A CN107221647 A CN 107221647A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material, a certain amount of titanium source is weighed first and is dispersed in absolute ethyl alcohol and adjusts pH value with glacial acetic acid, add deionized water and stir titanium hydroxide colloidal sol is obtained after a period of time；Appropriate graphene oxide is weighed, graphene oxide colloidal sol is obtained after ultrasonic disperse in deionized water；Titanium hydroxide colloidal sol and graphene oxide colloidal sol are mixed；Appropriate lithium source dissolving is weighed again in deionized water, is added chitosan and is adjusted pH to acidity with watery hydrochloric acid, mixed liquor is obtained after stirring；Resulting titanium hydroxide/graphene oxide mixed sols system is added in mixed liquor, and adds in whipping process appropriate crosslinking agent, it is freeze-dried after obtain solid；The nano composite material of nitrogen-doped titanic acid lithium/graphene is obtained after solid is calcined in inert gas atmosphere.The above method prepare composite there is high conductivity and high rate capability, can as lithium-ion capacitor negative material.
Description
Technical field
The present invention relates to electrode material technical field, more particularly to a kind of nitrogen-doped titanic acid lithium/graphene nano composite wood
The preparation method of material.
Background technology
Lithium-ion capacitor is a kind of energy storage device based on lithium ion battery and the dual energy storage mechanism of ultracapacitor, because
This possesses the double grading of battery and electric capacity, higher than lithium ion battery power density with bigger than conventional capacitor energy density
Advantage.Lithium-ion capacitor is had extended cycle life due to high with energy density, is received people the advantages of safe and got over
The research emphasis of energy storage of new generation and dynamic field to pay close attention to more, be included in portable electric appts, electric automobile,
There is vast potential for future development in terms of aeronautical and space technology.
As the negative material of lithium-ion capacitor, lithium titanate material is because with " zero strain " structure, in Li+It is embedded or
The deformation quantity of material structure is very small during abjection, so as to there is good cyclical stability.It has higher electric discharge
Voltage platform (1.55V vs.Li/Li+), oxidation Decomposition hardly occurs for electrolyte under this discharge platform and reduction decomposition is anti-
Should, SEI films will not be formed, are difficult to cause lithium metal to separate out, with very superior security performance, with very big researching value
And commercial application prospect.But lithium titanate is a kind of insulator in itself, electric conductivity is very poor, with relatively low electronic conductivity (10-13S/cm).Make its under the conditions of heavy-current discharge capacity attenuation quickly, high rate performance is poor.The theoretical specific volume of lithium titanate material
Amount is also than relatively low, only 175mAh g-1, drawbacks described above seriously limits its large-scale application in energy storage field.
The content of the invention
It is an object of the invention to provide a kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material, the party
Method prepare composite there is high conductivity and high rate capability, can as lithium-ion capacitor negative material.
A kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material, methods described includes：
Step 1, weigh a certain amount of titanium source be dispersed in absolute ethyl alcohol and with glacial acetic acid adjust pH value, add deionization
Water, which is stirred, obtains titanium hydroxide colloidal sol after a period of time；
Step 2, appropriate graphene oxide is weighed, obtain graphene oxide after ultrasonic disperse in deionized water molten
Glue；
Step 3, resulting titanium hydroxide colloidal sol and graphene oxide colloidal sol mixed, it is sonicated after obtain hydrogen-oxygen
Change titanium/graphene oxide mixed sols system；
Step 4, appropriate lithium source dissolving is weighed again in deionized water, add a certain amount of chitosan and simultaneously adjusted with watery hydrochloric acid
PH is saved to acidity, mixed liquor is obtained after stirring；
Step 5, the titanium hydroxide obtained by step 3/graphene oxide mixed sols system is added to obtained by step 4
Mixed liquor in, and add in whipping process appropriate crosslinking agent, it is freeze-dried after obtain solid；
Step 6, the solid obtained by step 5 is calcined in inert gas atmosphere after obtain nitrogen-doped titanic acid lithium/stone
The nano composite material of black alkene.
In the step 1, selected titanium source is butyl titanate, tetraethyl titanate, titanium tetrachloride, Titanium Nitrate and metatitanic acid
One or more in isopropyl ester；
And the pH value range adjusted with glacial acetic acid is 5-7；Mixing time is 30-240min.
In the step 2, the concentration of resulting graphene oxide colloidal sol is 1g/L-15g/L；The time of ultrasonic disperse
For 1-6h.
In the step 3, the ultrasonically treated time is 15-180min.
In the step 4, selected lithium source is lithium acetate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride and lemon
One or more in lemon acid lithium；
And be Li according to lithium source and titanium source atomic ratio：Ti=0.8-0.86：1 ratio weighs lithium source；
The pH range adjusted with watery hydrochloric acid is 2-6；The concentration of the chitosan is 0.5g/L-5g/L.
In the step 5, the crosslinking agent added is the one or more in cyanamide, silane, glutaraldehyde and citric acid；
The concentration of added crosslinking agent is 0g/L-1g/L；
And the time of freeze-drying is 24-120h.
In the step 6, the inert gas used is the one or more in nitrogen, argon gas, helium；
And calcining heat is 500-1200 DEG C, calcination time is 6-18h, and heating rate is 2-10 DEG C/min.
As seen from the above technical solution provided by the invention, the composite that prepared by the above method has high conductivity
And high rate capability, can as lithium-ion capacitor negative material.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, being used required in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is provided the preparation method schematic flow sheet of nano composite material by the embodiment of the present invention；
Fig. 2 be example of the present invention in prepared by nitrogen-doped titanic acid lithium/graphene nanocomposite material XRD；
Fig. 3 is the cyclic voltammogram of button cell progress electro-chemical test in example of the present invention；
Fig. 4 is the constant current charge-discharge diagram of button cell progress electro-chemical test in example of the present invention.
Embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
The embodiment of invention, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to protection scope of the present invention.
Methods described of the embodiment of the present invention is gathered by adding nitrogenous shell in titanium hydroxide/graphene oxide sol system
Sugar juice, has good hydrogen bond into key, while shell is poly- using the hydroxyl of hydroxyl in chitosan molecule and titanium hydroxide surface
Amino can be condensed bonding with surface of graphene oxide carboxyl in glycan molecule, and titanium hydroxide colloidal sol is fixed on into graphene oxide
On, titanium hydroxide and graphene oxide are realized in the compound of molecular level, with regard to that can obtain nitrogen-doped titanic acid lithium/graphite after heat treatment
Alkene nano composite material.The embodiment of the present invention is described in further detail below in conjunction with accompanying drawing, is as shown in Figure 1 this hair
Bright embodiment provides the preparation method schematic flow sheet of nano composite material, and methods described includes：
Step 1, weigh a certain amount of titanium source be dispersed in absolute ethyl alcohol and with glacial acetic acid adjust pH value, add deionization
Water, which is stirred, obtains titanium hydroxide colloidal sol after a period of time；
In the step 1, selected titanium source is butyl titanate, tetraethyl titanate, titanium tetrachloride, Titanium Nitrate and metatitanic acid
One or more in isopropyl ester；
And the pH value range adjusted with glacial acetic acid is 5-7；Mixing time is 30-240min.
Step 2, appropriate graphene oxide is weighed, obtain graphene oxide after ultrasonic disperse in deionized water molten
Glue；
In the step 2, the concentration of resulting graphene oxide colloidal sol is 1g/L-15g/L；The time of ultrasonic disperse
For 1-6h.
Here, graphene is that a kind of electric conductivity is excellent, the two-dimensional material of thermal performance and satisfactory mechanical property, if will
Lithium titanate is combined with graphene, can be improved the electric conductivity of lithium titanate material, be improved its high rate performance.
Step 3, resulting titanium hydroxide colloidal sol and graphene oxide colloidal sol mixed, it is sonicated after obtain hydrogen-oxygen
Change titanium/graphene oxide mixed sols system；
In the step 3, the ultrasonically treated time is 15-180min.
Step 4, appropriate lithium source dissolving is weighed again in deionized water, add a certain amount of chitosan and simultaneously adjusted with watery hydrochloric acid
PH is saved to acidity, mixed liquor is obtained after stirring；
In the step 4, selected lithium source is lithium acetate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride and lemon
One or more in lemon acid lithium；
And be Li according to lithium source and titanium source atomic ratio：Ti=0.8-0.86：1 ratio weighs lithium source；
The pH range adjusted with watery hydrochloric acid is 2-6；The concentration of the chitosan is 0.5g/L-5g/L.
Here, chitosan is a kind of alkaline polysaccharide, is product of the chitin after chemical Treatment deacetylation, chitosan
With cheap, easy to process, the non-toxic and good biodegradation character of tool, in food, environmental protection, medicine and functional material
It is widely applied very much Deng having in field, has substantial amounts of hydroxyl and amino in chitosan molecule, this causes chitosan to have good hydrogen
Key is into key.
Step 5, the titanium hydroxide obtained by step 3/graphene oxide mixed sols system is added to obtained by step 4
Mixed liquor in, and add in whipping process appropriate crosslinking agent, it is freeze-dried after obtain solid；
In the step 5, the crosslinking agent added is the one or more in cyanamide, silane, glutaraldehyde and citric acid；
The concentration of added crosslinking agent is 0g/L-1g/L；Here, if being added without crosslinking agent, it is 0 to take its concentration；
And the time of freeze-drying is 24-120h.
Step 6, the solid obtained by step 5 is calcined in inert gas atmosphere after obtain nitrogen-doped titanic acid lithium/stone
The nano composite material of black alkene.
In the step 6, the inert gas used is the one or more in nitrogen, argon gas, helium；
And calcining heat is 500-1200 DEG C, calcination time is 6-18h, and heating rate is 2-10 DEG C/min.
The technical process of above-mentioned preparation method is described in detail with specific example below：
Embodiment 1, the primary variables of the embodiment 1 are graphene oxide solubility and chitosan solubility.
A certain amount of butyl titanate is weighed first to be dispersed in absolute ethyl alcohol and adjust pH=5 with glacial acetic acid, is added few
Titanium hydroxide colloidal sol is obtained after the deionized water of amount, stirring 3h；Appropriate graphene oxide is weighed, in deionized water ultrasound point
Dissipate 5h and obtain 10g/L graphene oxide colloidal sols；Finally obtained titanium hydroxide colloidal sol and graphene oxide colloidal sol are mixed, ultrasound
After obtain titanium hydroxide/graphene oxide sol system A.
Then titanium source lithium source is Li by atomic ratio：Ti=0.86：1 ratio weighs appropriate lithium hydroxide and dissolved
In deionized water；PH=5 is adjusted with watery hydrochloric acid and 3g/L chitosan solution is prepared, and lithium source liquid is mixed with chitosan solution
Mixed liquid B is obtained after stirring.
Titanium hydroxide/graphene oxide sol system A is added in mixed liquid B again, the penta of 0.5g/L is added in stirring
Solid C is obtained after dialdehyde, freeze-drying 72h；By solid C in nitrogen atmosphere 800 DEG C calcining 8h after obtain nitrogen-doped titanic acid lithium/
Graphene nanocomposite material.
The XRD of prepared nitrogen-doped titanic acid lithium/graphene nanocomposite material in example of the present invention as shown in Figure 2
Figure, XRD tests are carried out by composite, and the crystallinity of lithium titanate is good in the composite obtained according to the judgement of peak spectrogram, and
For face-centred cubic spinel type lithium titanate, then pole piece is made in obtained nitrogen-doped titanic acid lithium/graphene nanocomposite material,
Button cell is assembled into together with lithium piece and carries out electro-chemical test.
The cyclic voltammogram that button cell in example of the present invention carries out electro-chemical test is illustrated in figure 3, in current potential
Window is 1-3V, and it is 0.1mV s to sweep speed-1Lower carry out cyclic voltammetry, redox peaks are sharp and high degree of symmetry, illustrate material
Removal lithium embedded is functional.
The constant current charge-discharge diagram that button cell in example of the present invention carries out electro-chemical test is illustrated in figure 4, in electricity
Position window is 1-3V, and constant current charge-discharge test is carried out under 1C and results in 172.8mAh g-1Specific capacity, charge and discharge cycles 100 times
Specific capacity also has 167.5mAh g afterwards-1, capability retention is up to 96.9%.Good electrochemistry can be shown that the N doping of preparation
Lithium titanate/graphene nanocomposite material can be used for lithium-ion capacitor negative material.
Further, from the transmission electron microscope picture of prepared nitrogen-doped titanic acid lithium/graphene nanocomposite material：Grain
Footpath is uniformly distributed on graphene film for 100-200nm lithium titanate particle.
Primary variables in embodiment 2, the embodiment 2 is titanium source species and type of crosslinking agent.
A certain amount of isopropyl titanate is weighed first to be dispersed in absolute ethyl alcohol and adjust pH=5 with glacial acetic acid, is added a small amount of
Deionized water, stirring 3h after obtain titanium hydroxide colloidal sol；Appropriate graphene oxide is weighed, in deionized water ultrasonic disperse
5h obtains 5g/L graphene oxide colloidal sols；Finally obtained titanium hydroxide colloidal sol and graphene oxide colloidal sol are mixed, after ultrasound
Obtain titanium hydroxide/graphene oxide sol system A.
Then titanium source lithium source is Li by atomic ratio：Ti=0.86：1 ratio weighs appropriate lithium hydroxide and dissolved
In deionized water；PH=5 is adjusted with watery hydrochloric acid and 2g/L chitosan solution is prepared, and lithium source liquid is mixed with chitosan solution
Mixed liquid B is obtained after stirring.
Titanium hydroxide/graphene oxide sol system A is added in mixed liquid B again, 0.5g/L cyanogen is added in stirring
Solid C is obtained after amine, freeze-drying 72h；Solid C is obtained into nitrogen-doped titanic acid lithium/stone in nitrogen atmosphere after 800 DEG C of calcining 8h
Black alkene nano composite material.
Primary variables in embodiment 3, the embodiment 3 is lithium source and sublimation drying.
Weigh a certain amount of butyl titanate to be dispersed in absolute ethyl alcohol and adjust pH=5 with glacial acetic acid, add on a small quantity
Titanium hydroxide colloidal sol is obtained after deionized water, stirring 3h；Appropriate graphene oxide is weighed, in deionized water ultrasonic disperse 5h
Obtain 5g/L graphene oxide colloidal sols；Finally obtained titanium hydroxide colloidal sol and graphene oxide colloidal sol are mixed, after ultrasound
To titanium hydroxide/graphene oxide sol system A.
Then titanium source lithium source is Li by atomic ratio：Ti=0.86：1 ratio weighs appropriate lithium acetate and is dissolved in
In deionized water；PH=5 is adjusted with watery hydrochloric acid and 2g/L chitosan solution is prepared, and lithium source liquid is mixed with chitosan solution and stirred
Mixed liquid B is obtained after mixing.
Titanium hydroxide/graphene oxide sol system A is added in mixed liquid B again, the penta of 0.5g/L is added in stirring
Solid C is obtained after dialdehyde, freeze-drying 96h；By solid C in nitrogen atmosphere 800 DEG C calcining 8h after obtain nitrogen-doped titanic acid lithium/
Graphene nanocomposite material.
Primary variables in embodiment 4, the embodiment 4 is titanium source lithium source ratio and inert gas.
Weigh a certain amount of butyl titanate to be dispersed in absolute ethyl alcohol and adjust pH=5 with glacial acetic acid, add on a small quantity
Titanium hydroxide colloidal sol is obtained after deionized water, stirring 3h；Appropriate graphene oxide is weighed, in deionized water ultrasonic disperse 5h
Obtain 5g/L graphene oxide colloidal sols；Finally obtained titanium hydroxide colloidal sol and graphene oxide colloidal sol are mixed, after ultrasound
To titanium hydroxide/graphene oxide sol system A.
Then titanium source lithium source is Li by atomic ratio：Ti=0.8：1 ratio weighs appropriate lithium hydroxide and dissolved
In deionized water；PH=5 is adjusted with watery hydrochloric acid and 2g/L chitosan solution is prepared, and lithium source liquid is mixed with chitosan solution
Mixed liquid B is obtained after stirring.
Titanium hydroxide/graphene oxide sol system A is added in mixed liquid B again, the penta of 0.5g/L is added in stirring
Solid C is obtained after dialdehyde, freeze-drying 72h；By solid C in argon gas atmosphere 800 DEG C calcining 8h after obtain nitrogen-doped titanic acid lithium/
Graphene nanocomposite material.
Primary variables in embodiment 5, the embodiment 5 is pH value and calcining heat.
Weigh a certain amount of butyl titanate to be dispersed in absolute ethyl alcohol and adjust pH=6 with glacial acetic acid, add on a small quantity
Titanium hydroxide colloidal sol is obtained after deionized water, stirring 3h；Appropriate graphene oxide is weighed, in deionized water ultrasonic disperse 5h
Obtain 5g/L graphene oxide colloidal sols；Finally obtained titanium hydroxide colloidal sol and graphene oxide colloidal sol are mixed, after ultrasound
To titanium hydroxide/graphene oxide sol system A.
Then titanium source lithium source is Li by atomic ratio：Ti=0.86：1 ratio weighs appropriate lithium hydroxide and dissolved
In deionized water；PH=4 is adjusted with watery hydrochloric acid and 2g/L chitosan solution is prepared, and lithium source liquid is mixed with chitosan solution
Mixed liquid B is obtained after stirring.
Titanium hydroxide/graphene oxide sol system A is added in mixed liquid B again, the penta of 0.5g/L is added in stirring
Solid C is obtained after dialdehyde, freeze-drying 72h；By solid C in nitrogen atmosphere 600 DEG C calcining 8h after obtain nitrogen-doped titanic acid lithium/
Graphene nanocomposite material.
Primary variables in embodiment 6, the embodiment 6 is the concentration and calcination time of crosslinking agent.
Weigh a certain amount of butyl titanate to be dispersed in absolute ethyl alcohol and adjust pH=5 with glacial acetic acid, add on a small quantity
Titanium hydroxide colloidal sol is obtained after deionized water, stirring 3h；Appropriate graphene oxide is weighed, in deionized water ultrasonic disperse 5h
Obtain 5g/L graphite oxide colloidal sol alkene；Finally obtained titanium hydroxide colloidal sol and graphene oxide colloidal sol are mixed, after ultrasound
To titanium hydroxide/graphene oxide sol system A.
Then titanium source lithium source is Li by atomic ratio：Ti=0.86：1 ratio weighs appropriate lithium hydroxide and dissolved
In deionized water；PH=5 is adjusted with watery hydrochloric acid and 2g/L chitosan solution is prepared, and lithium source liquid is mixed with chitosan solution
Mixed liquid B is obtained after stirring.
Titanium hydroxide/graphene oxide sol system A is added in mixed liquid B again, the penta 2 of 1g/L is added in stirring
Solid C is obtained after aldehyde, freeze-drying 72h；By solid C in nitrogen atmosphere 800 DEG C calcining 12h after obtain nitrogen-doped titanic acid lithium/
Graphene nanocomposite material.
In summary, the graphene in preparation method of the embodiment of the present invention can not only strengthen the conduction of lithium titanate particle
Property, moreover it is possible to prevent that lithium titanate from reuniting in high-temperature process, increase the specific surface area of material；Doping nitrogen-atoms can increase more
Many avtive spots, graphene provides good conductive network, prepared composite is had high conductivity and high power
Rate performance, so as to be used as the negative material of lithium-ion capacitor.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (7)
1. a kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material, it is characterised in that methods described includes：
Step 1, weigh a certain amount of titanium source be dispersed in absolute ethyl alcohol and with glacial acetic acid adjust pH value, add deionized water and stir
Mix and titanium hydroxide colloidal sol is obtained after a period of time；
Step 2, appropriate graphene oxide is weighed, obtain graphene oxide colloidal sol after ultrasonic disperse in deionized water；
Step 3, resulting titanium hydroxide colloidal sol and graphene oxide colloidal sol mixed, it is sonicated after obtain hydroxide
Titanium/graphene oxide mixed sols system；
Step 4, appropriate lithium source dissolving is weighed again in deionized water, add a certain amount of chitosan and simultaneously adjust pH with watery hydrochloric acid
To acid, mixed liquor is obtained after stirring；
Step 5, the titanium hydroxide obtained by step 3/graphene oxide mixed sols system is added to it is mixed obtained by step 4
Close in liquid, and add in whipping process appropriate crosslinking agent, it is freeze-dried after obtain solid；
Step 6, the solid obtained by step 5 is calcined in inert gas atmosphere after obtain nitrogen-doped titanic acid lithium/graphene
Nano composite material.
2. the preparation method of nano composite material according to claim 1, it is characterised in that selected in the step 1
Titanium source be butyl titanate, tetraethyl titanate, titanium tetrachloride, Titanium Nitrate and isopropyl titanate in one or more；
And the pH value range adjusted with glacial acetic acid is 5-7；Mixing time is 30-240min.
3. the preparation method of nano composite material according to claim 1, it is characterised in that resulting in the step 2
Graphene oxide colloidal sol concentration be 1g/L-15g/L；The time of ultrasonic disperse is 1-6h.
4. at the preparation method of nano composite material according to claim 1, it is characterised in that in the step 3, ultrasound
The time of reason is 15-180min.
5. the preparation method of nano composite material according to claim 1, it is characterised in that selected in the step 4
Lithium source be lithium acetate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride and lithium citrate in one or more；
And be Li according to lithium source and titanium source atomic ratio：Ti=0.8-0.86：1 ratio weighs lithium source；
The pH range adjusted with watery hydrochloric acid is 2-6；The concentration of the chitosan is 0.5g/L-5g/L.
6. the preparation method of nano composite material according to claim 1, it is characterised in that in the step 5, added
Crosslinking agent be cyanamide, silane, glutaraldehyde and citric acid in one or more；
The concentration of added crosslinking agent is 0g/L-1g/L；
And the time of freeze-drying is 24-120h.
7. the preparation method of nano composite material according to claim 1, it is characterised in that in the step 6, used
Inert gas be nitrogen, argon gas, helium in one or more；
And calcining heat is 500-1200 DEG C, calcination time is 6-18h, and heating rate is 2-10 DEG C/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108281300A (en) * | 2017-12-29 | 2018-07-13 | 华南师范大学 | A kind of preparation method of the nitrogen-doped titanic acid lithium micro-nano-sphere of graphene coated |
| WO2019223129A1 (en) * | 2018-05-25 | 2019-11-28 | 深圳大学 | Modified lithium titanate composite material and preparation method therefor, and lithium ion battery |
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| WO2019223129A1 (en) * | 2018-05-25 | 2019-11-28 | 深圳大学 | Modified lithium titanate composite material and preparation method therefor, and lithium ion battery |
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| CN107221647B (en) | 2019-10-22 |
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