CN108511735A - A kind of modified lithium titanate composite material and preparation method and lithium ion battery - Google Patents
A kind of modified lithium titanate composite material and preparation method and lithium ion battery Download PDFInfo
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Abstract
The present invention discloses a kind of modified lithium titanate composite material and preparation method and lithium ion battery.Lithium titanate is first carried out nitrogen treatment by the present invention, is then uniformly mixed lithium titanate and graphene oxide that nitrogen treatment is crossed, and 3~10min is calcined at 700~1100 DEG C to get to modified lithium titanate composite material in inert atmosphere or reducing atmosphere.The present invention is compared with prior art, using the great graphene of electronic conductivity, lithium titanate is compound prepares modified lithium titanate composite material with nitridation, preparation section simple and flexible, lithium titanate used can be synthesized by any method without influencing composite property, and can be adapted for the modified production to existing lithium titanate material.The big high rate performance of graphene-based lithium titanate composite material prepared is good, and has high specific capacity, can be widely applied to the lithium ion battery needed for various portable electronic devices and various electric vehicles.
Description
Technical field
The present invention relates to can charge and discharge field of lithium ion battery more particularly to a kind of modified lithium titanate composite material and its preparation
Method and lithium ion battery.
Background technology
Currently, the research emphasis of lithium ion battery negative material is just towards height ratio capacity, big multiplying power, high circulation performance and height
The motive-power battery material direction of security performance is developed.Traditional negative material is carbon negative pole material.Although Carbon anode at
It is commercialized to work(, but its existing cell safety problem is especially the safety problem under big multiplying power, and people is forced to find ratio
The safe and reliable novel anode material of embedding lithium under the slightly positive current potential of Carbon anode.Wherein low potential transition metal oxide and compound
Oxide causes the extensive of people note that especially zero strain material Li as the negative material of lithium ion battery4Ti5O12,
With its 1.5V (vs. Li/Li+) voltage, be widely noticed close to 1 efficiency for charge-discharge and superior cycle performance, it is a kind of to have very much
Electrode material of the potentiality as power-type lithium ion battery negative material.
But the electron conduction of lithium titanate is poor, which limits its high rate capabilities.Therefore it needs by changing to it
Property improves its electric conductivity, to improve the big high rate performance of lithium titanate to adapt to power battery demand, and needs to keep it
High reversible electrochemical capacity and good cyclical stability.Currently, the method that can improve lithium titanate high rate performance is mainly wrapped
It includes：Prepare the lithium titanate of nanometer particle size, lithium titanate bulk doped and introducing conductive phase etc..Existing method carries out carbon packet to lithium titanate
It covers, although having certain improvement to its performance, improves limited to its conductive capability and specific capacity is not improved.Graphene
The movement velocity of middle electronics has reached the 1/300 of the light velocity, is a kind of considerably beyond movement velocity of the electronics in general conductor
Fabulous electronic conductor, and graphite is dilute itself has very high storage lithium specific capacity.It is therefore, lithium titanate and graphene is compound,
The conductive capability of lithium titanate material will be greatly improved by preparing graphene-based lithium titanate composite electrode material, and effectively improve material
Specific capacity.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of modified lithium titanate composite material and its
Preparation method and lithium ion battery, it is intended to solve existing method and carbon coating is carried out to lithium titanate, centainly change although having to its performance
It is kind, but its conductive capability is improved limited and the problem of do not improved to specific capacity.
Technical scheme is as follows：
A kind of preparation method of modified lithium titanate composite material, wherein include the following steps：
（1）Prepare nano barium titanate powder for lithium：Lithium source and titanium source are dissolved in solvent respectively, mix two kinds of solution and acetic acid is added；
40~100 DEG C are heated to, constant temperature stirs 4~10h；Drying obtains presoma at 80~120 DEG C；The presoma is dispersed in
In deionized water, spray-dried obtained powder；The powder is calcined into 6~18h at 700~1000 DEG C；Again through cooling, grind
Mill is to get nano barium titanate powder for lithium；
（2）Prepare nitridation lithium titanate powdery：Gained nano barium titanate powder for lithium is heated to 700~1000 DEG C of progress in nitrogen atmosphere
5~10h of nitrogen treatment obtains nitridation lithium titanate powdery；
（3）Prepare graphene oxide：Natural flake graphite and sodium nitrate are mixed, are added the concentrated sulfuric acid, stirring 10 in ice-water bath~
20min adds potassium permanganate, 0.5~1h is reacted in ice-water bath, deionized water is added after stirring 24~48h at 20~25 DEG C
10~20min is reacted with hydrogen peroxide, is centrifuged；Separation product is washed, using centrifuging, be drying to obtain graphite oxide
Alkene；
（4）Prepare modified lithium titanate composite material：The nitridation lithium titanate powdery and graphene oxide that prepare are uniformly mixed,
3~10min is calcined in inert atmosphere or reducing atmosphere at 700~1100 DEG C to get to modified lithium titanate composite material.
The preparation method, wherein step（1）In, the lithium source is one in lithium hydroxide, lithium acetate and lithium nitrate
Kind or two or more mixtures；The titanium source is butyl titanate or tetraisopropyl titanate.
The preparation method, wherein step（1）In, in the lithium source and titanium source the molar ratio of Li and Ti be 0.8~
0.86。
The preparation method, wherein step（2）In, the nitrogen atmosphere is ammonia or nitrogen and hydrogen mixture.
The preparation method, wherein step（3）In, the mass ratio of the sodium nitrate and natural flake graphite is 1:1,
The volume of the concentrated sulfuric acid and the mass ratio of natural graphite scale are 50~60mL/g, the mass ratio of potassium permanganate and natural flake graphite
It is 6:1.
The preparation method, wherein step（3）In, a concentration of 30wt% of the hydrogen peroxide, the volume of hydrogen peroxide with
The mass ratio of natural flake graphite is 20~30mL/g；The volume of deionized water and the mass ratio of natural flake graphite be 75~
100mL/g。
The preparation method, wherein step（4）In, the reducing atmosphere is nitrogen and hydrogen mixture.
The preparation method, wherein step（4）In, the graphene oxide accounts for nitridation lithium titanate powdery and oxidation stone
1.0~19.4wt% of black alkene mixture.
The preparation method, wherein step（4）In, in the modified lithium titanate composite material, grapheme material accounts for institute
State 1.0~18.1wt% of modified lithium titanate composite material.
A kind of modified lithium titanate composite material, wherein be prepared using preparation method of the present invention.
A kind of lithium ion battery, including cathode, wherein the material of the cathode is multiple for modified lithium titanate of the present invention
Condensation material.
Advantageous effect：Compared with prior art, the present invention is dual modified to lithium titanate progress by adulterating and coating, specifically
Use the great graphene of electronic conductivity and N doping lithium titanate it is compound prepare modified lithium titanate electrode material, prepare work
Sequence simple and flexible, lithium titanate used can be synthesized by any method without influencing composite property, and can be applicable in
It is produced in the modified of existing lithium titanate material.The modified lithium titanate composite material of preparation has big high rate performance, excellent
Cycle performance and high temperature performance.
Description of the drawings
Fig. 1 is modified metatitanic acid made from lithium titanate and modified lithium titanate composite material made from embodiment 1 and embodiment 2
The XRD diagram of lithium composite material, wherein（a）XRD spectra for the spinel lithium titanate prepared by method described in embodiment 1；（b）
XRD spectra for the modified lithium titanate composite material prepared by method described in embodiment 1；（c）For by the side described in embodiment 2
The XRD spectra of modified lithium titanate composite material prepared by method；
Fig. 2 is the first charge-discharge curve graph of modified lithium titanate composite material 0.2C made from embodiment 1；
Fig. 3 is the first charge-discharge curve graph of modified lithium titanate composite material 5C made from embodiment 2；
Cycle performance figure when Fig. 4 is modified lithium titanate composite material 5C made from embodiment 2；
Cycle performance figure when Fig. 5 is modified lithium titanate composite material 10C made from embodiment 3；
Fig. 6 is graphene content and modified lithium titanate composite material first discharge specific capacity in embodiment 2,3 and 5（5C）Curve
Figure.
Specific implementation mode
A kind of modified lithium titanate composite material and preparation method of present invention offer and lithium ion battery, to make the present invention's
Purpose, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that this place is retouched
The specific embodiment stated is only used to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of preparation method of modified lithium titanate composite material, wherein includes the following steps：
（1）Prepare nano barium titanate powder for lithium：Lithium source and titanium source are dissolved in solvent respectively（Such as ethyl alcohol）In, it mixes two kinds of solution and adds
Enter acetic acid；40~100 DEG C are heated to, constant temperature stirs 4~10h；Drying obtains presoma at 80~120 DEG C；By the forerunner
Body disperses in deionized water, spray-dried obtained powder；The powder is calcined into 6~18h at 700~1000 DEG C；Again
Through cooling, grind to get nano barium titanate powder for lithium；
（2）Prepare nitridation lithium titanate powdery：By gained nano barium titanate powder for lithium in nitrogen atmosphere（Such as ammonia or nitrogen and hydrogen mixture）
In be heated to 700~1000 DEG C progress 5~10h of nitrogen treatment, obtain nitridation lithium titanate powdery；
（3）Prepare graphene oxide：Natural flake graphite and sodium nitrate are mixed, are added the concentrated sulfuric acid, stirring 10 in ice-water bath~
20 minutes, potassium permanganate is added, 0.5~1h is reacted in ice-water bath, deionization is added after stirring 24~48h at 20~25 DEG C
Water and hydrogen peroxide react 10~20min, centrifuge；Separation product is washed, using centrifuging, be drying to obtain oxidation stone
Black alkene；
（4）Prepare modified lithium titanate composite material：The nitridation lithium titanate powdery and graphene oxide that prepare are uniformly mixed,
3~10min is calcined in inert atmosphere or reducing atmosphere at 700~1100 DEG C, obtains modified lithium titanate composite material.
Compared with prior art, the present invention the lithium titanate for using the great graphene of electronic conductivity and N doping is compound
Modified lithium titanate combination electrode material, preparation section simple and flexible are prepared, lithium titanate used can be synthesized by any method
Without influencing composite property, and it can be adapted for the modified production to existing lithium titanate material.The modification metatitanic acid of preparation
The big high rate performance of lithium composite material is good, and has high specific capacity, can be widely applied to various portable electronic devices and each
Lithium ion battery needed for kind electric vehicle.
Preferably, step（1）In, the lithium source be one or both of lithium hydroxide, lithium acetate and lithium nitrate etc. with
On mixture.
Preferably, step（1）In, the titanium source is that butyl titanate or tetraisopropyl titanate etc. are without being limited thereto.
Preferably, step（1）In, the molar ratio of Li and Ti is 0.8~0.86 in the lithium source and titanium source.
Step（3）It specifically includes：Natural flake graphite and sodium nitrate are mixed, the concentrated sulfuric acid is added, 10 are stirred in ice-water bath
~20min, is slow added into potassium permanganate, and react 0.5~1h in ice-water bath adds after continuously stirring 24~48h at 20~25 DEG C
Enter deionized water and hydrogen peroxide reacts 10~20min, centrifuges；Separation product uses the mixing of sulfuric acid and hydrogen peroxide molten successively
Liquid and deionized water are washed, using centrifuging, be dried in vacuo up to graphene oxide.
Preferably, step（3）In, the mass ratio of the sodium nitrate and natural flake graphite is 1:1, the volume of the concentrated sulfuric acid with
The mass ratio of natural graphite scale is 50~60mL/g, and the mass ratio of potassium permanganate and natural flake graphite is 6:1.
Preferably, step（3）In, when deionized water and hydrogen peroxide reaction is added, a concentration of 30wt% of the hydrogen peroxide,
The volume of hydrogen peroxide and the mass ratio of natural flake graphite are 20~30mL/g；The volume of deionized water and natural flake graphite
Mass ratio is 75~100mL/g.
Preferably, step（3）In, when washing the sulfuric acid and hydrogen peroxide mixed solution in sulfuric acid account for 6wt%, hydrogen peroxide
Account for 1wt%.
Step（4）It specifically includes：The nitridation lithium titanate powdery and graphene oxide that prepare are uniformly mixed, in indifferent gas
3~10min is calcined in atmosphere or reducing atmosphere at 700~1100 DEG C, obtains modified lithium titanate composite material.The titanium nitride
In inert atmosphere or reducing atmosphere after calcining, the graphene oxide is reduced and wraps for sour powder for lithium and graphene oxide
It is overlying on the lithium titanate surface of N doping, obtains the nitridation lithium titanate powdery of graphene coated, i.e., the described modified lithium titanate composite wood
Material.
Preferably, step（4）In, the inert atmosphere is argon gas, nitrogen or helium；The reducing atmosphere is mixed for nitrogen hydrogen
Close gas.
Preferably, step（4）In, the graphene oxide accounts for nitridation lithium titanate powdery and graphene oxide mixture
1.0~19.4wt%.
Preferably, step（4）In, in the modified lithium titanate composite material, grapheme material accounts for the modified lithium titanate
1.0~18.1wt% of composite material.
The present invention also provides a kind of modified lithium titanate composite materials, wherein is prepared using preparation method of the present invention
It obtains.In the modified lithium titanate composite material, grapheme material account for the modified lithium titanate composite material 1.0~
18.1wt%。
Modified lithium titanate composite material prepared by the present invention, it is dual modified by nitrogen treatment and graphene coated, effectively
Improve electrode material electric conductivity and chemical property.It is that half-cell is made to electrode with lithium metal, first charge-discharge holds when 10C
Amount still has 180mAh/g.Charge and discharge cycles 100 times, discharge capacity are higher than 120mAh/g.It is prepared into 25Ah by anode of cobalt acid lithium
Power battery, charge and discharge cycles 1000 are enclosed under the conditions of 10C multiplying powers, and reversible capacity decaying is less than 20%, and can be in -40 ~ 60 DEG C of ranges
Interior work.
Below by several embodiments, the present invention is described in detail.
Embodiment 1
It is Li in molar ratio:Ti=0.86:1 ratio weighs anhydrous lithium acetate 3.9975g and butyl titanate 23.9539g, with
Ethyl alcohol is dispersant, and anhydrous lithium acetate and butyl titanate are dissolved in ethyl alcohol respectively, two kinds of solution is mixed under stirring condition, so
10mL acetic acid is added dropwise afterwards.Constant temperature stirs 4 hours under the conditions of 80 DEG C, and presoma is dried to obtain under the conditions of 120 DEG C.By the forerunner
Body dispersion forms suspension in deionized water, and carries out being spray-dried obtained powder, hot air temperature 140 to suspension
℃.The powder is warming up to 800 DEG C, constant temperature 12h in Muffle furnace with 5 DEG C/min, after cooled to room temperature, grinding, mistake
150 mesh sieve to get nano barium titanate powder for lithium.Through X-ray powder diffraction（XRD）It is the nanometer of single spinel structure after test
Lithium titanate powdery is shown in a in Fig. 1.
By gained nano barium titanate powder for lithium in nitrogen and hydrogen mixture（Hydrogen accounts for 5vol%）In be heated to 700 DEG C and carry out at nitridation
10h is managed, nitridation lithium titanate powdery is obtained.
2.0002g natural flake graphites and 2.0036g sodium nitrate are mixed, addition 116mL concentrated sulfuric acid solutions, in ice-water bath
10min is stirred, 12.0728g potassium permanganate is slow added into solution, 0.5h is reacted in ice-water bath, is continuously stirred at 20 DEG C
After mixing 48h, 184mL deionized waters, 40mL hydrogen peroxide is added（30wt%）20min is reacted, is centrifuged.Separation product is used successively
The mixed solution of sulfuric acid and hydrogen peroxide（Sulfuric acid accounts for 6wt%, and hydrogen peroxide accounts for 1wt%) and deionized water wash 3 times, then centrifuge simultaneously
It is dried in vacuo up to graphene oxide.
The 2.3960g prepared is nitrogenized into lithium titanate powdery and 0.0821g graphene oxides are uniformly mixed, in nitrogen atmosphere
In calcined, temperature is 1000 DEG C, and constant temperature time is 3min to get to modified lithium titanate composite material, and graphene accounts for modification
The 3.204wt% of lithium titanate composite material gross mass is still spinel structure after XRD is tested, sees b in Fig. 1.
Electro-chemical test is carried out in the following conditions：Using the modified lithium titanate composite material of preparation as active material, Super
P (super charcoal) is conductive agent, PVDF（Kynoar）It is binder, NMP（N-methyl-2-pyrrolidone）It is tuned into material for solvent
Slurry, which is applied on copper foil, is made pole piece.With lithium piece to electrode, concentration of electrolyte 1mol/L, microporous polypropylene membrane be battery every
Film is assembled into test battery.It is assembled into button cell in the glove box full of argon gas, carries out electro-chemical test.Charge and discharge electricity
Press ranging from 1.0~2.5V.
Product is assembled as above into battery, discharge capacity is 192.8mAh/g for the first time when 0.2C, and charging capacity is
176.9mAh/g, as shown in Figure 2.
Embodiment 2
It is Li in molar ratio:Ti=0.81:1 ratio weighs anhydrous lithium acetate 4.3015g and butyl titanate 27.2309g, with
Ethyl alcohol is dispersant, and anhydrous lithium acetate and butyl titanate are dissolved in ethyl alcohol respectively, and two kinds of solution, drop are mixed under stirring condition
Add 10mL acetic acid.Constant temperature stirs 10 hours under the conditions of 40 DEG C, and presoma is dried to obtain under the conditions of 80 DEG C.Presoma is dispersed in
Suspension is formed in deionized water, and suspension is carried out to be spray-dried obtained powder, and hot air temperature is 140 DEG C.It will be described
Powder is warming up to 1000 DEG C, constant temperature 6h in Muffle furnace with 5 DEG C/min, and after cooled to room temperature, grinding crosses 150 mesh sieve, i.e.,
Obtain nano barium titanate powder for lithium.
Gained nano barium titanate powder for lithium is heated to 800 DEG C of progress nitrogen treatment 5h in ammonia atmosphere, obtains titanium nitride
Sour powder for lithium.
2.0006g natural flake graphites and 2.0021g sodium nitrate are mixed, addition 120mL concentrated sulfuric acid solutions, in ice-water bath
15min is stirred, 12.0036g potassium permanganate is slow added into solution, 1h is reacted in ice-water bath, is continuously stirred at 25 DEG C
After 36h, 150mL deionized waters, 50mL hydrogen peroxide is added（30wt%）15min is reacted, is centrifuged.Separation product uses sulphur successively
The mixed solution of acid and hydrogen peroxide（Sulfuric acid accounts for 6wt%, and hydrogen peroxide accounts for 1wt%) and deionized water wash 3 times, then centrifuge and true
Sky is drying to obtain graphene oxide.
The 2.0164g prepared is nitrogenized into lithium titanate powdery and 0.0742g graphene oxides are uniformly mixed, is mixed in nitrogen hydrogen
Gas（Hydrogen accounts for 10vol%）It is calcined in atmosphere, temperature is 800 DEG C, and it is compound to obtain modified lithium titanate by constant temperature time 10min
Material, graphene account for the 3.241wt% of modified lithium titanate composite material gross mass, unchanged through XRD test crystal forms, such as c in Fig. 1
Show.
Obtained product is assembled into battery as described in Example 1, and discharge capacity is 159.0mAh/g, charging for the first time when 5C
Capacity is 153.2mAh/g, as shown in Figure 3.And cycle performance is good, and capacity is not less than 123.4mAh/g after 100 cycles,
As shown in Figure 4.
Embodiment 3
It is 0.8 in molar ratio:1 weighs anhydrous lithium acetate 6.2043g and butyl titanate 40.0000g, using ethyl alcohol as dispersant,
Anhydrous lithium acetate and butyl titanate are dissolved in ethyl alcohol respectively, two kinds of solution are mixed under stirring condition, 10mL second is then added dropwise
Acid.Constant temperature stirs 8 hours under the conditions of 60 DEG C, and presoma is dried to obtain under the conditions of 100 DEG C.Presoma is dispersed in deionized water
Middle formation suspension, and suspension is carried out to be spray-dried obtained powder, hot air temperature is 140 DEG C.By the powder in horse
Not 700 DEG C, constant temperature 18h are warming up to 5 DEG C/min, after cooled to room temperature, grinding crosses 150 mesh sieve to get nano-titanium in stove
Sour powder for lithium.
Gained nano barium titanate powder for lithium is heated to 1100 DEG C of progress nitrogen treatment 8h in ammonia atmosphere, obtains titanium nitride
Sour powder for lithium.
1.9998g natural flake graphites and 2.0007g sodium nitrate are mixed, addition 100mL concentrated sulfuric acid solutions, in ice-water bath
20min is stirred, 12.0015g potassium permanganate is slow added into solution, 0.75h is reacted in ice-water bath, is continuously stirred at 20 DEG C
After mixing for 24 hours, 200mL deionized waters, 60mL hydrogen peroxide is added（30wt%）10min is reacted, is centrifuged.Separation product is used successively
The mixed solution of sulfuric acid and hydrogen peroxide（Sulfuric acid accounts for 6wt%, and hydrogen peroxide accounts for 1wt%) and deionized water wash 3 times, then centrifuge simultaneously
It is dried in vacuo up to graphene oxide.
The 1.0324g prepared is nitrogenized into lithium titanate powdery and 0.1204g graphene oxides are uniformly mixed, in nitrogen atmosphere
In calcined, temperature be 900 DEG C, constant temperature time 6min, obtain modified lithium titanate composite material, graphene accounts for modified metatitanic acid
The 10.249wt% of lithium composite material gross mass.
Obtained product is assembled into battery as described in Example 1, and discharge capacity is more than 186mAh/g for the first time when 10C, is filled
100 circle of electric discharge, discharge capacity remain above 116mAh/g, and capacity retention ratio is up to 62.3%.Cycle performance figure is as shown in Figure 5.
Embodiment 4
Other conditions are same as Example 1, the difference is that nitrogenizing metatitanic acid in nitridation lithium titanate powdery and graphene oxide mixture
Powder for lithium is 5.8221g, and graphene oxide 0.0612g is equally calcined in nitrogen containing atmosphere, and temperature is 1000 DEG C, permanent
The warm time is 30min, obtains modified lithium titanate composite material, graphene accounts for modified lithium titanate composite material gross mass
1.011wt%。
Obtained product is assembled into battery as described in Example 1, and first charge-discharge capacity is about 150mAh/g when 5C,
Capacity is about 110mAh/g after 100 cycles.
Embodiment 5
Other conditions are same as Example 2, the difference is that nitrogenizing metatitanic acid in nitridation lithium titanate powdery and graphene oxide mixture
Powder for lithium is 0.5071g, graphene oxide 0.1201g, and in nitrogen and hydrogen mixture（Hydrogen accounts for 5vol%）It is forged in atmosphere
It burns, temperature is 900 DEG C, and constant temperature time is 30 minutes, obtains modified lithium titanate composite material, it is compound that graphene accounts for modified lithium titanate
The 18.102wt% of material gross mass.
Obtained product is assembled into battery as described in Example 1, and first charge-discharge capacity is up to 130mAh/g when 5C.
Capacity is not less than 100mAh/g after 100 cycles.Wherein, Fig. 6 is graphene content and modified lithium titanate in embodiment 2,3 and 5
Composite material first discharge specific capacity（5C）Curve graph.
In conclusion a kind of modified lithium titanate composite material and preparation method provided by the invention and lithium ion battery,
Compared with prior art, the present invention the lithium titanate for using the great graphene of electronic conductivity and nitridation is compound to prepare Modified Titanium
Sour lithium composite material, preparation section simple and flexible, lithium titanate used can be synthesize by any method it is compound without influencing
Material property, and can be adapted for the modified production to existing lithium titanate material.The modified lithium titanate composite material of preparation has
Big high rate performance, excellent cycle performance and high temperature performance, first charge-discharge capacity still has 180mAh/g, charge and discharge when 10C
10000 circle of electricity cycle, reversible capacity decaying is less than 20%, and can work within the scope of -40 ~ 60 DEG C.The modified lithium titanate of preparation is multiple
Condensation material can be widely applied to the lithium ion battery needed for various portable electronic devices and various electric vehicles.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of modified lithium titanate composite material, which is characterized in that include the following steps：
（1）Prepare nano barium titanate powder for lithium：Lithium source and titanium source are dissolved in solvent respectively, mix two kinds of solution and acetic acid is added；
40~100 DEG C are heated to, constant temperature stirs 4~10h；Drying obtains presoma at 80~120 DEG C；The presoma is dispersed in
In deionized water, spray-dried obtained powder；The powder is calcined into 6~18h at 700~1000 DEG C；Again through cooling, grind
Mill is to get nano barium titanate powder for lithium；
（2）Prepare nitridation lithium titanate powdery：Gained nano barium titanate powder for lithium is heated to 700~1000 DEG C of progress in nitrogen atmosphere
5~10h of nitrogen treatment obtains nitridation lithium titanate powdery；
（3）Prepare graphene oxide：Natural flake graphite and sodium nitrate are mixed, are added the concentrated sulfuric acid, stirring 10 in ice-water bath~
20min adds potassium permanganate, 0.5~1h is reacted in ice-water bath, deionized water is added after stirring 24~48h at 20~25 DEG C
10~20min is reacted with hydrogen peroxide, is centrifuged；Separation product is washed, using centrifuging, be drying to obtain graphite oxide
Alkene；
（4）Prepare modified lithium titanate composite material：The nitridation lithium titanate powdery and graphene oxide that prepare are uniformly mixed,
3~10min is calcined in inert atmosphere or reducing atmosphere at 700~1100 DEG C, obtains modified lithium titanate composite material.
2. preparation method according to claim 1, which is characterized in that step（1）In, the lithium source is lithium hydroxide, vinegar
The mixture of one or more of sour lithium and lithium nitrate；The titanium source is butyl titanate or tetraisopropyl titanate；Institute
The molar ratio for stating Li and Ti in lithium source and titanium source is 0.8~0.86.
3. preparation method according to claim 1, which is characterized in that step（2）In, the nitrogen atmosphere is ammonia or nitrogen hydrogen
Gaseous mixture.
4. preparation method according to claim 1, which is characterized in that step（3）In, the sodium nitrate and natural scale stone
The mass ratio of ink is 1:1, the volume of the concentrated sulfuric acid and the mass ratio of natural graphite scale are 50~60mL/g, potassium permanganate with it is natural
The mass ratio of crystalline flake graphite is 6:1.
5. preparation method according to claim 1, which is characterized in that step（3）In, the hydrogen peroxide it is a concentration of
30wt%, the volume of hydrogen peroxide and the mass ratio of natural flake graphite are 20~30mL/g；The volume of deionized water and natural scale
The mass ratio of graphite is 75~100mL/g.
6. preparation method according to claim 1, which is characterized in that step（4）In, the reducing atmosphere is mixed for nitrogen hydrogen
Close gas.
7. preparation method according to claim 1, which is characterized in that step（4）In, the graphene oxide accounts for titanium nitride
1.0~19.4wt% of sour powder for lithium and graphene oxide mixture.
8. preparation method according to claim 1, which is characterized in that step（4）In, the modified lithium titanate composite material
In, grapheme material accounts for 1.0~18.1wt% of the modified lithium titanate composite material.
9. a kind of modified lithium titanate composite material, which is characterized in that use claim 1 ~ 8 any one of them preparation method system
It is standby to obtain.
10. a kind of lithium ion battery, including cathode, which is characterized in that the material of the cathode is the modification described in claim 9
Lithium titanate composite material.
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| CN109346710A (en) * | 2018-11-27 | 2019-02-15 | 深圳大学 | A kind of nitridation lithium titanate-nitriding and oxidizing aluminium composite material and the preparation method and application thereof |
| CN109473656A (en) * | 2018-11-27 | 2019-03-15 | 深圳大学 | A kind of nitridation lithium titanate/nitrided silicon dioxide titanium combination electrode material and preparation method thereof |
| CN111392766A (en) * | 2019-11-13 | 2020-07-10 | 中国人民解放军军事科学院防化研究院 | Method for preparing nano lithium titanate/graphene porous composite electrode material |
| CN111403721A (en) * | 2020-04-16 | 2020-07-10 | 旭派电源有限公司 | Preparation method of lithium titanate negative electrode material of lithium ion battery |
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| CN114551844A (en) * | 2022-03-01 | 2022-05-27 | 深圳博磊达新能源科技有限公司 | Lithium titanate composite negative electrode material and preparation method thereof |
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| CN107221647B (en) * | 2017-07-18 | 2019-10-22 | 华南师范大学 | A kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material |
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| CN109473656A (en) * | 2018-11-27 | 2019-03-15 | 深圳大学 | A kind of nitridation lithium titanate/nitrided silicon dioxide titanium combination electrode material and preparation method thereof |
| WO2020108132A1 (en) * | 2018-11-27 | 2020-06-04 | 深圳大学 | Nitrided lithium titanate-nitrided aluminum oxide composite material, preparation method therefor and application thereof |
| CN109346710B (en) * | 2018-11-27 | 2021-07-20 | 深圳大学 | Lithium titanate nitride-aluminum oxide nitride composite material and preparation method and application thereof |
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| CN111403721A (en) * | 2020-04-16 | 2020-07-10 | 旭派电源有限公司 | Preparation method of lithium titanate negative electrode material of lithium ion battery |
| CN111403721B (en) * | 2020-04-16 | 2021-06-29 | 旭派电源有限公司 | Preparation method of lithium titanate negative electrode material of lithium ion battery |
| CN114335456A (en) * | 2021-12-06 | 2022-04-12 | 桂林电子科技大学 | Fast-charging composite negative electrode material and preparation method and application thereof |
| CN114335456B (en) * | 2021-12-06 | 2024-05-17 | 桂林电子科技大学 | Quick-charging type composite anode material and preparation method and application thereof |
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