CN105098162B - A kind of preparation method of titanium carbide nanometer sheet/graphene composite material available for negative electrode of lithium ion battery - Google Patents
A kind of preparation method of titanium carbide nanometer sheet/graphene composite material available for negative electrode of lithium ion battery Download PDFInfo
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Abstract
A kind of preparation method of titanium carbide nanometer sheet/graphene composite material available for negative electrode of lithium ion battery, it belongs to nano ceramic material synthesis and preparation field.It will solve existing Ti3C2TxThe problem of preparation technology complexity and low efficiency of/graphene composite material.Method：First, Ti is prepared3AlC2Powder；2nd, the lamellar Ti of stacking is prepared3C2TxPowder；3rd, suspension is prepared；4th, the Ti for preparing sheet is taken3C2TxPowder；5th, it is combined, that is, completes with graphene oxide.The preparation method of the present invention only needs to prepare Ti3C2TxPowder, using graphene oxide as raw material, commercially can directly buy, and the cycle that not only prepared by raw material is relatively short, and surface of graphene oxide equally contains functional group, and hydrophily is more preferable, it is easier to and Ti3C2TxIt is combined with each other；And suction filtration is only needed to 1 time, efficiency high, technique is simple, be worth with stronger promotion and application.
Description
Technical field
The invention belongs to nano ceramic material synthesis and preparation field, and in particular to a kind of preparation of MXene composites
Method.
Background technology
Ti3C2TxAs a kind of new two-dimensional material, its theoretical volume specific capacitance is far above all carbon materials, in lithium
Great application prospect in terms of ion battery.Ti after stripping3C2TxMaterial compared to its sandwich construction can store more lithiums from
Son, but be due to Ti in preparation process3C2TxLamella produces the phenomenon of stacking, limits its ability for storing lithium ion；Prepared
Ti in journey3C2TxIt can be chemically reacted with water and corrosive agent, its surface is there is functional group, had a strong impact on its electric conductivity,
Equally limit its application in terms of lithium ion battery.There was only Ti at present3C2TxIt can successfully prepare and carry out chemical property
Deng test, same to Ti3AlC2Lithium ability is stored up compared to it and volumetric capacitance improves as many as four times, is had a extensive future.
Graphene has and Ti3C2TxSimilar two-dimensional layered structure, electron mobility is up to 200000cm2v-1s-1, can use
Make energy storage material, such as fuel cell, lithium ion battery etc..The dimension of insertion 0, the dimension nano material of 1 peacekeeping 2 can in graphene sheet layer
Effectively the stacking quantity of reduction graphene film, further improves its lithium ion storage capacity.
By in Ti3C2TxGraphene is inserted in lamella, on the one hand increase Ti3C2TxThe piece interlamellar spacing of material, improves its storage
Deposit the ability of lithium ion；On the other hand the electric conductivity of titanium carbide nanometer sheet/graphene composite material is improved.Further promote carbonization
Titanium nanometer sheet/application prospect of the graphene composite material in terms of lithium ion battery.
At present, the Ti of the sandwich shape of 6-10 thickness is prepared using the method for alternately suction filtration3C2Tx/ graphene is combined
Material：First by Ti3C2TxSuspension by the method suction filtration of vacuum aided suction filtration a to polypropylene film, then at it
On the basis of the layer graphene of suction filtration one, such alternately suction filtration obtains 6-10 layers of Ti3C2Tx/ graphene composite material；This method
Need to prepare Ti respectively3C2TxWith the suspension of graphene, comparatively complex process, raw material preparation time is longer, and suction filtration
Number is excessive, and failure possibility is larger therefore less efficient.
The content of the invention
The invention aims to solve existing Ti3C2TxThe preparation technology of/graphene composite material is complicated and efficiency is low
Problem, and a kind of preparation method of titanium carbide nanometer sheet/graphene composite material available for negative electrode of lithium ion battery is provided.
A kind of preparation method of titanium carbide nanometer sheet/graphene composite material available for negative electrode of lithium ion battery, by with
Lower step is realized：
First, by Ti, Al, C powder according to mol ratio 3:(1.1~1.3):After 2 mix, pass through at 1400 DEG C~1500 DEG C
Pressureless sintering synthesizes Ti3AlC2Phase ceramics, are then crushed, and obtain Ti3AlC2Powder；
2nd, by Ti3AlC2Powder, which is put into the hydrofluoric acid that concentration is 20wt.%~50wt.%, corrodes 4~24h, after corrosion
Solution adds deionized water and carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
3rd, by the lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with organic solvent:(10~100) mix, then
Centrifugal treating is carried out, suspension is obtained；
4th, the supernatant of suspension is taken, deionized water is added and ultrasonic vibration disperses 2~24h, sheet is obtained after drying
Ti3C2TxPowder；
5th, by the Ti of sheet3C2TxPowder and graphene oxide are added in organic solvent simultaneously, it is stirred at room temperature 6~
24h, then carries out suction filtration, removes organic solvent, then is dried at 80 DEG C, that is, completes the carbonization available for negative electrode of lithium ion battery
The preparation of titanium nanometer sheet/graphene composite material；
The wherein lamellar Ti of step 2 stacking3C2TxT is the-F group or-OH bases formed after corroding on powder in powder
Group.
The invention has the advantages that：
1st, can be by adjusting concentration and etching time, the Ti of hydrofluoric acid in this method3C2TxWith the mass ratio of graphene and stirring
Mix time, the time of centrifugation and number of times, ultrasonic power and time of vibration etc. and improve the property of titanium carbide/graphene composite material
Can, obtain two-dimentional titanium carbide/graphene sheet layer.
2nd, preparation method of the invention only needs to prepare Ti3C2TxPowder, raw material, Ke Yi are used as using graphene oxide
In the market is directly bought, and the cycle that not only prepared by raw material is relatively short, and surface of graphene oxide equally contains functional group, parent
It is aqueous more preferable, it is easier to and Ti3C2TxIt is combined with each other；And suction filtration only needs to 1 time, efficiency high.
3rd, Ti prepared by the present invention3C2TxPowder has a kind of structure of lamellar, and this structure is similar to graphene, lithium
Ion can spread between synusia, play a part of storing lithium ion, can be applied to do electrode material in lithium ion battery.
Simultaneously in Ti3C2TxMiddle doped graphene can also suppress the generation reunited not only to improve its electric conductivity, improve its electrification
Performance (capacity, charge-discharge characteristic, cycle performance, multiplying power property), expands its application in terms of lithium ion battery.
4th, doped graphene in the present invention, can effectively increase Ti3C2TxThe piece interlamellar spacing of material, improves titanium carbide and receives
The storage lithium performance of rice piece/graphene composite material, application is broader.
5th, this method is due to using suction method, it is easier to prepare well mixed, titanium carbide nanometer sheet/stone of excellent performance
Black alkene composite, compares Ti3C2TxMaterial property is more excellent, and technique is simple, production efficiency is high, with stronger popularization and should
With value.
Brief description of the drawings
Fig. 1 be in embodiment 1 concentration to corrode 4h Ti in 30wt.% hydrofluoric acid3C2TxSEM figure；
Fig. 2 be in embodiment 2 concentration to corrode 12h Ti in 30wt.% hydrofluoric acid3C2TxSEM figure.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment
Any combination.
Embodiment one：Present embodiment can be used for titanium carbide nanometer sheet/graphene of negative electrode of lithium ion battery multiple
The preparation method of condensation material, is realized according to the following steps：
First, by Ti, Al, C powder according to mol ratio 3:(1.1~1.3):After 2 mix, pass through at 1400 DEG C~1500 DEG C
Pressureless sintering synthesizes Ti3AlC2Phase ceramics, are then crushed, and obtain Ti3AlC2Powder；
2nd, by Ti3AlC2Powder, which is put into the hydrofluoric acid that concentration is 20wt.%~50wt.%, corrodes 4~24h, after corrosion
Solution adds deionized water and carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
3rd, by the lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with organic solvent:(10~100) mix, then
Centrifugal treating is carried out, suspension is obtained；
4th, the supernatant of suspension is taken, deionized water is added and ultrasonic vibration disperses 2~24h, sheet is obtained after drying
Ti3C2TxPowder；
5th, by the Ti of sheet3C2TxPowder and graphene oxide are added in organic solvent simultaneously, it is stirred at room temperature 6~
24h, then carries out suction filtration, removes organic solvent, then is dried at 80 DEG C, that is, completes the carbonization available for negative electrode of lithium ion battery
The preparation of titanium nanometer sheet/graphene composite material；
The wherein lamellar Ti of step 2 stacking3C2TxT is the-F group or-OH bases formed after corroding on powder in powder
Group.
By Ti in present embodiment step 23AlC2Powder is put into rotten in the hydrofluoric acid that concentration is 20wt.%~50wt.%
Lose 4~24h, it is therefore an objective to make Ti3AlC2Al in phase is corroded.
Solution adds deionized water and carries out centrifugal treating after corroding in present embodiment step 2, it is therefore an objective to remove dehydrogenation fluorine
Acid.
Embodiment two：Present embodiment from unlike embodiment one, by Ti, Al, C powder in step one
End is according to mol ratio 3:1.2:After 2 mix, Ti is synthesized by pressureless sintering at 1450 DEG C3AlC2Phase ceramics.Other steps and ginseng
Number is identical with embodiment one.
Embodiment three：Present embodiment in step 2 from unlike embodiment one or two, inciting somebody to action
Ti3AlC2Powder, which is put into the hydrofluoric acid that concentration is 40wt.%, corrodes 12h.Other steps and parameter and embodiment one or
Two is identical.
Embodiment four：, will in step 3 unlike one of present embodiment and embodiment one to three
The lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with organic solvent:20 mixing.Other steps and parameter and specific implementation
One of mode one to three is identical.
Embodiment five：Unlike one of present embodiment and embodiment one to four, step 2 and step
Centrifugal speed in rapid three be 100rpm~4000rpm, centrifugation time be 30min~120min, centrifugation number of times be 1~
10 times.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six：Unlike one of present embodiment and embodiment one to five, in step 4 plus
Enter deionized water and ultrasonic vibration disperses 12h.Other steps and parameter are identical with one of embodiment one to five.
Embodiment seven：Unlike one of present embodiment and embodiment one to six, surpass in step 4
Acoustic power is that 300W~600W, ultrasonic frequency are 20~40KHz.Other steps and parameter and embodiment one to six
One of it is identical.
Embodiment eight：Unlike one of present embodiment and embodiment one to seven, step 4 suspends
There is Ti in the supernatant of liquid3C2Tx, Ti3C2TxMass ratio with deionized water is 1:(200~1000).Other steps and parameter with
One of embodiment one to seven is identical.
Embodiment nine：Unlike one of present embodiment and embodiment one to eight, piece in step 5
The Ti of stratiform3C2TxThe mass ratio of the gross mass and organic solvent of powder and graphene oxide is 1:(10~100).Other steps
And parameter is identical with one of embodiment one to eight.
Embodiment ten：Unlike one of present embodiment and embodiment one to nine, room in step 5
Temperature stirring 12h.Other steps and parameter are identical with one of embodiment one to nine.
Embodiment 11：Unlike one of present embodiment and embodiment one to ten, in step 5
The Ti of graphene oxide and sheet3C2TxThe mass ratio of powder is 1:(1~99).Other steps and parameter and specific embodiment party
One of formula one to ten is identical.
Embodiment 12：Present embodiment from unlike embodiment one to one of 11, step 3
It is dimethyl sulfoxide (DMSO), dimethylformamide or Triton X100 with organic solvent in step 5.Other steps and parameter and tool
Body embodiment one to one of 11 is identical.
Beneficial effects of the present invention are verified using following examples：
Embodiment 1：
Available for the preparation method of titanium carbide nanometer sheet/graphene composite material of negative electrode of lithium ion battery, by following step
It is rapid to realize：
First, by Ti, Al, C powder according to mol ratio 3:1.2:After 2 mix, synthesized at 1400 DEG C by pressureless sintering
Ti3AlC2Phase ceramics, are then crushed, and obtain Ti3AlC2Powder；
2nd, by Ti3AlC2Powder, which is put into the hydrofluoric acid that concentration is 30wt.%, corrodes solution addition deionization after 4h, corrosion
Water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
3rd, by the lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with dimethyl sulfoxide (DMSO):20 mixing, are then carried out
Centrifugal treating, obtains suspension；
4th, the supernatant of suspension is taken, deionized water is added and ultrasonic vibration disperses 6h, sheet is obtained after drying
Ti3C2TxPowder；
5th, by the Ti of sheet3C2TxPowder and graphene oxide are added in dimethyl sulfoxide (DMSO) simultaneously, and 6h is stirred at room temperature,
Then suction filtration is carried out, organic solvent is removed, then dried at 80 DEG C, that is, completes to receive available for the titanium carbide of negative electrode of lithium ion battery
The preparation of rice piece/graphene composite material；
The wherein lamellar Ti of step 2 stacking3C2TxT is the-F group or-OH bases formed after corroding on powder in powder
Group.
Centrifugal speed in the present embodiment step 2 and step 3 is that 1000rpm, centrifugation time are 60min, centrifugation
Number of times is 3 times.
Ultrasonic power is that 500W, ultrasonic frequency are 30KHz in the present embodiment step 4.
There is Ti in the supernatant of the present embodiment step 4 suspension3C2Tx, Ti3C2TxMass ratio with deionized water is 1:
600。
The Ti of sheet in the present embodiment step 53C2TxThe matter of the gross mass and organic solvent of powder and graphene oxide
Amount is than being 1:50.
Graphene oxide and the Ti of sheet in the present embodiment step 53C2TxThe mass ratio of powder is 1:10.
Corrode 4h Ti in the present embodiment step 2 in hydrofluoric acid3C2TxSEM figure, see Fig. 1, it can be seen that Ti3C2TxTool
There is a kind of structure of lamellar, this structure is similar to graphene, and lithium ion can spread between synusia, play storage lithium
The effect of ion, can be applied to do electrode material in lithium ion battery.But it is due to that the functional group that its surface is present has a strong impact on
Ti3C2TxElectric conductivity, and the agglomeration of synusia simultaneously have impact on Ti3C2TxChemical property.Therefore graphene is added
Composite is formed to improve its electric conductivity, and in Ti3C2TxOr incorporation other materials is effectively reduced in the synusia of graphene
The piece layer number of reunion, so in Ti3C2TxMiddle doped graphene can also suppress what is reunited not only to improve its electric conductivity
Occur, improve the performance (capacity, charge-discharge characteristic, cycle performance, multiplying power property) of its electrochemistry, expand it in lithium ion battery
The application of aspect.
Embodiment 2：
Available for the preparation method of titanium carbide nanometer sheet/graphene composite material of negative electrode of lithium ion battery, by following step
It is rapid to realize：
First, by Ti, Al, C powder according to mol ratio 3:1.1:After 2 mix, synthesized at 1500 DEG C by pressureless sintering
Ti3AlC2Phase ceramics, are then crushed, and obtain Ti3AlC2Powder；
2nd, by Ti3AlC2Powder be put into the hydrofluoric acid that concentration is 30wt.% corrode after 12h, corrosion solution add go from
Sub- water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
3rd, by the lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with organic solvent:20 mixing, then carry out from
Heart processing, obtains suspension；
4th, the supernatant of suspension is taken, deionized water is added and ultrasonic vibration disperses 12h, sheet is obtained after drying
Ti3C2TxPowder；
5th, by the Ti of sheet3C2TxPowder and graphene oxide are added in organic solvent simultaneously, 6h are stirred at room temperature, so
After carry out suction filtration, remove organic solvent, then dried at 80 DEG C, that is, complete the titanium carbide nanometer available for negative electrode of lithium ion battery
The preparation of piece/graphene composite material, obtains titanium carbide/graphene sheet layer；
The wherein lamellar Ti of step 2 stacking3C2TxT is the-F group or-OH bases formed after corroding on powder in powder
Group.
Centrifugal speed in the present embodiment step 2 and step 3 is that 2000rpm, centrifugation time are 40min, centrifugation
Number of times is 2 times.
Ultrasonic power is that 400W, ultrasonic frequency are 30KHz in the present embodiment step 4.
There is Ti in the supernatant of the present embodiment step 4 suspension3C2Tx, Ti3C2TxMass ratio with deionized water is 1:
700。
The Ti of sheet in the present embodiment step 53C2TxThe matter of the gross mass and organic solvent of powder and graphene oxide
Amount is than being 1:60.
Graphene oxide and the Ti of sheet in the present embodiment step 53C2TxThe mass ratio of powder is 1:5.
Corrode 12h Ti in the present embodiment step 2 in hydrofluoric acid3C2TxSEM figure, see Fig. 2, it can be seen that Ti3C2TxTool
There is a kind of structure of lamellar, this structure is similar to graphene, and lithium ion can spread between synusia, play storage lithium
The effect of ion, can be applied to do electrode material in lithium ion battery.But it is due to that the functional group that its surface is present has a strong impact on
Ti3C2TxElectric conductivity, and the agglomeration of synusia simultaneously have impact on Ti3C2TxChemical property.Therefore graphene is added
Composite is formed to improve its electric conductivity, and in Ti3C2TxOr incorporation other materials is effectively reduced in the synusia of graphene
The piece layer number of reunion, so in Ti3C2TxMiddle doped graphene can also suppress what is reunited not only to improve its electric conductivity
Occur, improve the performance (capacity, charge-discharge characteristic, cycle performance, multiplying power property) of its electrochemistry, expand it in lithium ion battery
The application of aspect.
Embodiment 3：
Available for the preparation method of titanium carbide nanometer sheet/graphene composite material of negative electrode of lithium ion battery, by following step
It is rapid to realize：
First, by Ti, Al, C powder according to mol ratio 3:1.1:After 2 mix, synthesized at 1400 DEG C by pressureless sintering
Ti3AlC2Phase ceramics, are then crushed, and obtain Ti3AlC2Powder；
2nd, by Ti3AlC2Powder be put into the hydrofluoric acid that concentration is 40wt.% corrode after 24h, corrosion solution add go from
Sub- water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
3rd, by the lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with organic solvent:20 mixing, then carry out from
Heart processing, obtains suspension；
4th, the supernatant of suspension is taken, deionized water is added and ultrasonic vibration disperses 6h, sheet is obtained after drying
Ti3C2TxPowder；
5th, by the Ti of sheet3C2TxPowder and graphene oxide are added in organic solvent simultaneously, 6h are stirred at room temperature, so
After carry out suction filtration, remove organic solvent, then dried at 80 DEG C, that is, complete the titanium carbide nanometer available for negative electrode of lithium ion battery
The preparation of piece/graphene composite material；
The wherein lamellar Ti of step 2 stacking3C2TxT is the-F group or-OH bases formed after corroding on powder in powder
Group.
Centrifugal speed in the present embodiment step 2 and step 3 is that 1000rpm, centrifugation time are 50min, centrifugation
Number of times is 3 times.
Ultrasonic power is that 300W, ultrasonic frequency are 40KHz in the present embodiment step 4.
There is Ti in the supernatant of the present embodiment step 4 suspension3C2Tx, Ti3C2TxMass ratio with deionized water is 1:
500。
The Ti of sheet in the present embodiment step 53C2TxThe matter of the gross mass and organic solvent of powder and graphene oxide
Amount is than being 1:20.
Graphene oxide and the Ti of sheet in the present embodiment step 53C2TxThe mass ratio of powder is 1:5.
Corrode 24h Ti in the present embodiment step 2 in hydrofluoric acid3C2Tx, after testing, with a kind of structure of lamellar,
This structure is similar to graphene, and lithium ion can spread between synusia, plays a part of storing lithium ion, can be applied to
Electrode material is done in lithium ion battery.
Embodiment 4：
Available for the preparation method of titanium carbide nanometer sheet/graphene composite material of negative electrode of lithium ion battery, by following step
It is rapid to realize：
First, by Ti, Al, C powder according to mol ratio 3:1.2:After 2 mix, synthesized at 1500 DEG C by pressureless sintering
Ti3AlC2Phase ceramics, are then crushed, and obtain Ti3AlC2Powder；
2nd, by Ti3AlC2Powder, which is put into the hydrofluoric acid that concentration is 50wt.%, corrodes solution addition deionization after 6h, corrosion
Water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
3rd, by the lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with organic solvent:30 mixing, then carry out from
Heart processing, obtains suspension；
4th, the supernatant of suspension is taken, deionized water is added and ultrasonic vibration disperses 6h, sheet is obtained after drying
Ti3C2TxPowder；
5th, by the Ti of sheet3C2TxPowder and graphene oxide are added in organic solvent simultaneously, and 12h is stirred at room temperature,
Then suction filtration is carried out, organic solvent is removed, then dried at 80 DEG C, that is, completes to receive available for the titanium carbide of negative electrode of lithium ion battery
The preparation of rice piece/graphene composite material；
The wherein lamellar Ti of step 2 stacking3C2TxT is the-F group or-OH bases formed after corroding on powder in powder
Group.
Centrifugal speed in the present embodiment step 2 and step 3 is that 3000rpm, centrifugation time are 30min, centrifugation
Number of times is 4 times.
Ultrasonic power is that 500W, ultrasonic frequency are 30KHz in the present embodiment step 4.
There is Ti in the supernatant of the present embodiment step 4 suspension3C2Tx, Ti3C2TxMass ratio with deionized water is 1:
500。
The Ti of sheet in the present embodiment step 53C2TxThe matter of the gross mass and organic solvent of powder and graphene oxide
Amount is than being 1:20.
Graphene oxide and the Ti of sheet in the present embodiment step 53C2TxThe mass ratio of powder is 1:15.
Corrode 6h Ti in the present embodiment step 2 in hydrofluoric acid3C2Tx, after testing, with a kind of structure of lamellar, this
Plant structure and be similar to graphene, lithium ion can spread between synusia, play a part of storing lithium ion, can be applied to lithium
Electrode material is done in ion battery.
Embodiment 5：
Available for the preparation method of titanium carbide nanometer sheet/graphene composite material of negative electrode of lithium ion battery, by following step
It is rapid to realize：
First, by Ti, Al, C powder according to mol ratio 3:1.2:After 2 mix, synthesized at 1450 DEG C by pressureless sintering
Ti3AlC2Phase ceramics, are then crushed, and obtain Ti3AlC2Powder；
2nd, by Ti3AlC2Powder be put into the hydrofluoric acid that concentration is 30wt.% corrode after 16h, corrosion solution add go from
Sub- water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
3rd, by the lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with organic solvent:30 mixing, then carry out from
Heart processing, obtains suspension；
4th, the supernatant of suspension is taken, deionized water is added and ultrasonic vibration disperses 8h, sheet is obtained after drying
Ti3C2TxPowder；
5th, by the Ti of sheet3C2TxPowder and graphene oxide are added in organic solvent simultaneously, and 10h is stirred at room temperature,
Then suction filtration is carried out, organic solvent is removed, then dried at 80 DEG C, that is, completes to receive available for the titanium carbide of negative electrode of lithium ion battery
The preparation of rice piece/graphene composite material；
The wherein lamellar Ti of step 2 stacking3C2TxT is the-F group or-OH bases formed after corroding on powder in powder
Group.
Centrifugal speed in the present embodiment step 2 and step 3 is that 4000rpm, centrifugation time are 30min, centrifugation
Number of times is 4 times.
Ultrasonic power is that 600W, ultrasonic frequency are 20KHz in the present embodiment step 4.
There is Ti in the supernatant of the present embodiment step 4 suspension3C2Tx, Ti3C2TxMass ratio with deionized water is 1:
500。
The Ti of sheet in the present embodiment step 53C2TxThe matter of the gross mass and organic solvent of powder and graphene oxide
Amount is than being 1:30.
Graphene oxide and the Ti of sheet in the present embodiment step 53C2TxThe mass ratio of powder is 1:20.
Corrode 16h Ti in the present embodiment step 2 in hydrofluoric acid3C2Tx, after testing, with a kind of structure of lamellar,
This structure is similar to graphene, and lithium ion can spread between synusia, plays a part of storing lithium ion, can be applied to
Electrode material is done in lithium ion battery.
Embodiment 6：
Available for the preparation method of titanium carbide nanometer sheet/graphene composite material of negative electrode of lithium ion battery, by following step
It is rapid to realize：
First, by Ti, Al, C powder according to mol ratio 3:1.3:After 2 mix, synthesized at 1500 DEG C by pressureless sintering
Ti3AlC2Phase ceramics, are then crushed, and obtain Ti3AlC2Powder；
2nd, by Ti3AlC2Powder, which is put into the hydrofluoric acid that concentration is 50wt.%, corrodes solution addition deionization after 4h, corrosion
Water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
3rd, by the lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with organic solvent:50 mixing, then carry out from
Heart processing, obtains suspension；
4th, the supernatant of suspension is taken, deionized water is added and ultrasonic vibration disperses 2h, sheet is obtained after drying
Ti3C2TxPowder；
5th, by the Ti of sheet3C2TxPowder and graphene oxide are added in organic solvent simultaneously, and 20h is stirred at room temperature,
Then suction filtration is carried out, organic solvent is removed, then dried at 80 DEG C, that is, completes to receive available for the titanium carbide of negative electrode of lithium ion battery
The preparation of rice piece/graphene composite material；
The wherein lamellar Ti of step 2 stacking3C2TxT is the-F group or-OH bases formed after corroding on powder in powder
Group.
Centrifugal speed in the present embodiment step 2 and step 3 is that 4000rpm, centrifugation time are 40min, centrifugation
Number of times is 4 times.
Ultrasonic power is that 600W, ultrasonic frequency are 40KHz in the present embodiment step 4.
There is Ti in the supernatant of the present embodiment step 4 suspension3C2Tx, Ti3C2TxMass ratio with deionized water is 1:
700。
The Ti of sheet in the present embodiment step 53C2TxThe matter of the gross mass and organic solvent of powder and graphene oxide
Amount is than being 1:30.
Graphene oxide and the Ti of sheet in the present embodiment step 53C2TxThe mass ratio of powder is 1:40.
Corrode 4h Ti in the present embodiment step 2 in hydrofluoric acid3C2Tx, after testing, with a kind of structure of lamellar, this
Plant structure and be similar to graphene, lithium ion can spread between synusia, play a part of storing lithium ion, can be applied to lithium
Electrode material is done in ion battery.
Claims (9)
1. a kind of preparation method of titanium carbide nanometer sheet/graphene composite material available for negative electrode of lithium ion battery, its feature
It is that it is realized according to the following steps：
First, by Ti, Al, C powder according to mol ratio 3:(1.1~1.3):After 2 mix, by without pressure at 1400 DEG C~1500 DEG C
Sintering synthesis Ti3AlC2Phase ceramics, are then crushed, and obtain Ti3AlC2Powder；
2nd, by Ti3AlC2Powder, which is put into the hydrofluoric acid that concentration is 40wt.%, corrodes solution addition deionized water after 12h, corrosion
Centrifugal treating is carried out, then sediment is dried, the lamellar Ti of stacking is obtained3C2TxPowder；
3rd, by the lamellar Ti of stacking3C2TxPowder is 1 according to mass ratio with organic solvent:(10~100) mix, then carry out
Centrifugal treating, obtains suspension；
4th, the supernatant of suspension is taken, deionized water is added and ultrasonic vibration disperses 2~24h, sheet is obtained after drying
Ti3C2TxPowder；
5th, by the Ti of sheet3C2TxPowder and graphene oxide are added in organic solvent simultaneously, 6~24h are stirred at room temperature, so
After carry out suction filtration, remove organic solvent, then dried at 80 DEG C, that is, complete the titanium carbide nanometer available for negative electrode of lithium ion battery
The preparation of piece/graphene composite material；
The wherein lamellar Ti of step 2 stacking3C2TxT is the-F group or-OH groups formed after corroding on powder in powder.
2. a kind of titanium carbide nanometer sheet/graphene composite wood available for negative electrode of lithium ion battery according to claim 1
The preparation method of material, it is characterised in that by Ti, Al, C powder according to mol ratio 3 in step one:1.2:After 2 mix, at 1450 DEG C
Ti is synthesized by pressureless sintering down3AlC2Phase ceramics.
3. a kind of titanium carbide nanometer sheet/graphene composite wood available for negative electrode of lithium ion battery according to claim 1
The preparation method of material, it is characterised in that by the lamellar Ti of stacking in step 33C2TxPowder is according to mass ratio with organic solvent
1:20 mixing.
4. a kind of titanium carbide nanometer sheet/graphene composite wood available for negative electrode of lithium ion battery according to claim 1
The preparation method of material, it is characterised in that the centrifugal speed in step 2 and step 3 is 100rpm~4000rpm, centrifugation time
Be 30min~120min, centrifugation number of times be 1~10 time.
5. a kind of titanium carbide nanometer sheet/graphene composite wood available for negative electrode of lithium ion battery according to claim 1
The preparation method of material, it is characterised in that ultrasonic power is that 300W~600W, ultrasonic frequency are 20~40KHz in step 4.
6. a kind of titanium carbide nanometer sheet/graphene composite wood available for negative electrode of lithium ion battery according to claim 1
The preparation method of material, it is characterised in that have Ti in the supernatant of step 4 suspension3C2Tx, Ti3C2TxWith the quality of deionized water
Than for 1:(200~1000).
7. a kind of titanium carbide nanometer sheet/graphene composite wood available for negative electrode of lithium ion battery according to claim 1
The preparation method of material, it is characterised in that the Ti of sheet in step 53C2TxThe gross mass of powder and graphene oxide with it is organic molten
The mass ratio of agent is 1:(10~100).
8. a kind of titanium carbide nanometer sheet/graphene composite wood available for negative electrode of lithium ion battery according to claim 1
The preparation method of material, it is characterised in that graphene oxide and the Ti of sheet in step 53C2TxThe mass ratio of powder is 1:(1~
99)。
9. a kind of titanium carbide nanometer sheet/graphene composite wood available for negative electrode of lithium ion battery according to claim 1
The preparation method of material, it is characterised in that in step 3 and step 5 organic solvent be dimethyl sulfoxide (DMSO), dimethylformamide or
Triton X100。
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| CN107732170A (en) * | 2017-09-19 | 2018-02-23 | 浙江大学 | A kind of efficiently lithium metal composite and preparation method thereof and the application as negative pole |
| CN107732170B (en) * | 2017-09-19 | 2019-10-29 | 浙江大学 | A kind of efficient lithium metal composite material and preparation method and the application as cathode |
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