CN105098162A - Preparation method for titanium carbide nanosheet/graphene composite material capable of being used as anode of lithium ion battery - Google Patents

Preparation method for titanium carbide nanosheet/graphene composite material capable of being used as anode of lithium ion battery Download PDF

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CN105098162A
CN105098162A CN201510582413.XA CN201510582413A CN105098162A CN 105098162 A CN105098162 A CN 105098162A CN 201510582413 A CN201510582413 A CN 201510582413A CN 105098162 A CN105098162 A CN 105098162A
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powder
preparation
lithium ion
composite material
ion battery
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CN105098162B (en
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段小明
刘博慧
贾德昌
杨治华
周玉
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/5835—Comprising fluorine or fluoride salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method for a titanium carbide nanosheet/graphene composite material capable of being used as an anode of a lithium ion battery, belonging to the field of synthesis and preparation of a nano ceramic material. The preparation method aims at solving the problems of complicated preparation process and low efficiency of the traditional Ti3C2T<x>/graphene composite material. The method comprises the following steps of: 1, preparing Ti3AlC2 powder; 2, preparing a stacked layered Ti3C2T<x> powder body; 3, preparing a suspension liquid; 4, taking the prepared layered Ti3C2T<x> powder body; and 5, combining with graphene oxide, and completing. According to the preparation method, only the Ti3C2T<x> powder body is needed to be prepared, the graphene oxide is taken as a raw material and can be directly bought in the market, the preparation period of the raw material is relatively short, and the surface of the graphene oxide also contains a functional group, is high in hydrophilic performance, and can be easily combined with the Ti3C2T<x>; and moreover, only one time of pumping filtration is required, efficiency is high, the process is simple, and the method has high promotion and application value.

Description

A kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative
Technical field
The invention belongs to nano ceramic material synthesis and preparation field, be specifically related to a kind of preparation method of MXene composite material.
Background technology
Ti 3c 2t xas a kind of novel two-dimensional material, its theoretical volume ratio capacitance, far above all material with carbon elements, has application prospect in lithium ion battery.Ti after stripping 3c 2t xits sandwich construction compared by material can store more lithium ion, but due to Ti in preparation process 3c 2t xlamella produces the phenomenon of stacking, limits the ability that it stores lithium ion; Ti in preparation process 3c 2t xcan and water and corrosive agent generation chemical reaction, make its surface there is functional group, had a strong impact on its electric conductivity, limit its application in lithium ion battery equally.Only has Ti at present 3c 2t xsuccessfully can prepare and carry out the tests such as chemical property, same to Ti 3alC 2compare its storage lithium ability and volumetric capacitance improve four times more than, have a extensive future.
Graphene has and Ti 3c 2t xsimilar two-dimensional layered structure, electron mobility is up to 200000cm 2v -1s -1, can be used as energy storage material, such as fuel cell, lithium ion battery etc.In graphene sheet layer, insert the stacking quantity that 0 ties up, 1 peacekeeping 2 dimension nano material effectively can reduce graphene film, improve its lithium ion storage capacity further.
By at Ti 3c 2t xinsert Graphene in lamella, increase Ti on the one hand 3c 2t xthe sheet interlayer spacing of material, improves the ability that it stores lithium ion; Improve the conductivity of titanium carbide nanometer sheet/graphene composite material on the other hand.The application prospect of further promotion titanium carbide nanometer sheet/graphene composite material in lithium ion battery.
At present, the method for alternately suction filtration is adopted to prepare the Ti of the sandwich shape of 6-10 thickness 3c 2t x/ graphene composite material: first by Ti 3c 2t xsuspension by the method suction filtration of vacuum-assisted suction filtration on a polypropylene film, then suction filtration one layer graphene on its basis, so alternately suction filtration, obtains the Ti of 6-10 layer 3c 2t x/ graphene composite material; This method needs to prepare Ti respectively 3c 2t xwith the suspension of Graphene, comparatively speaking complex process, raw material preparation time is longer, and suction filtration number of times is too much, and failed possibility is comparatively large, and therefore efficiency is lower.
Summary of the invention
The present invention seeks to solve existing Ti 3c 2t xthe complicated process of preparation of/graphene composite material and inefficient problem, and a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative is provided.
Can be used for a preparation method for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative, realize according to the following steps:
One, by Ti, Al, C powder according to mol ratio 3:(1.1 ~ 1.3): 2 mixing after, at 1400 DEG C ~ 1500 DEG C, synthesize Ti by pressureless sintering 3alC 2phase ceramics, then pulverizes, and obtains Ti 3alC 2powder;
Two, by Ti 3alC 2powder puts into hydrofluoric acid corrosion 4 ~ 24h that concentration is 20wt.% ~ 50wt.%, and the rear solution of corrosion adds deionized water and carries out centrifugal treating, is then dried by sediment, obtains the lamellar Ti of stacking 3c 2t xpowder;
Three, by the lamellar Ti of stacking 3c 2t xpowder and organic solvent are 1:(10 ~ 100 according to mass ratio) mix, then carry out centrifugal treating, obtain suspension;
Four, get the supernatant of suspension, add deionized water and ultrasonic vibration dispersion 2 ~ 24h, after oven dry, obtain the Ti of sheet 3c 2t xpowder;
Five, by the Ti of sheet 3c 2t xpowder and graphene oxide join in organic solvent simultaneously, stirring at room temperature 6 ~ 24h, then carry out suction filtration, remove organic solvent, then dry at 80 DEG C, namely complete the preparation of the titanium carbide nanometer sheet/graphene composite material that can be used for lithium ion battery negative;
The wherein lamellar Ti of step 2 stacking 3c 2t xin powder, T is the-F group or-OH group that after corrosion, powder are formed.
The present invention has following beneficial effect:
1, in this method by regulating the concentration of hydrofluoric acid and etching time, Ti 3c 2t ximprove the performance of titanium carbide/graphene composite material with the mass ratio of Graphene and mixing time, centrifugal time and number of times, ultrasonic power and time of vibration etc., obtain two-dimentional titanium carbide/graphene sheet layer.
2, preparation method of the present invention only needs to prepare Ti 3c 2t xpowder, adopt graphene oxide as raw material, can commercially directly buy, not only raw material cycle of preparing is relatively short, and surface of graphene oxide is equally containing functional group, and hydrophily is better, more easily and Ti 3c 2t xbe combined with each other; And suction filtration only needs 1 time, efficiency is high.
3, the Ti for preparing of the present invention 3c 2t xpowder has a kind of structure of lamellar, and this similar is in Graphene, and lithium ion can spread between synusia, plays the effect storing lithium ion, can be applicable to do electrode material in lithium ion battery.Simultaneously at Ti 3c 2t xmiddle doped graphene, not only in order to improve its conductivity, can also suppress the generation of reuniting, improving its electrochemical performance (capacity, charge-discharge characteristic, cycle performance, multiplying power property), expands its range of application in lithium ion battery.
4, doped graphene in the present invention, effectively can increase Ti 3c 2t xthe sheet interlayer spacing of material, improve the storage lithium performance of titanium carbide nanometer sheet/graphene composite material, range of application is more wide.
5, this method is owing to adopting suction method, and more easily prepare and mix, the titanium carbide nanometer sheet/graphene composite material of excellent performance, compares Ti 3c 2t xmaterial property is more excellent, and technique is simple, production efficiency is high, has stronger promotion and application and is worth.
Accompanying drawing explanation
Fig. 1 is that in embodiment 1, concentration is the Ti corroding 4h in the hydrofluoric acid of 30wt.% 3c 2t xsEM figure;
Fig. 2 is that in embodiment 2, concentration is the Ti corroding 12h in the hydrofluoric acid of 30wt.% 3c 2t xsEM figure.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: present embodiment can be used for the preparation method of the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative, realizes according to the following steps:
One, by Ti, Al, C powder according to mol ratio 3:(1.1 ~ 1.3): 2 mixing after, at 1400 DEG C ~ 1500 DEG C, synthesize Ti by pressureless sintering 3alC 2phase ceramics, then pulverizes, and obtains Ti 3alC 2powder;
Two, by Ti 3alC 2powder puts into hydrofluoric acid corrosion 4 ~ 24h that concentration is 20wt.% ~ 50wt.%, and the rear solution of corrosion adds deionized water and carries out centrifugal treating, is then dried by sediment, obtains the lamellar Ti of stacking 3c 2t xpowder;
Three, by the lamellar Ti of stacking 3c 2t xpowder and organic solvent are 1:(10 ~ 100 according to mass ratio) mix, then carry out centrifugal treating, obtain suspension;
Four, get the supernatant of suspension, add deionized water and ultrasonic vibration dispersion 2 ~ 24h, after oven dry, obtain the Ti of sheet 3c 2t xpowder;
Five, by the Ti of sheet 3c 2t xpowder and graphene oxide join in organic solvent simultaneously, stirring at room temperature 6 ~ 24h, then carry out suction filtration, remove organic solvent, then dry at 80 DEG C, namely complete the preparation of the titanium carbide nanometer sheet/graphene composite material that can be used for lithium ion battery negative;
The wherein lamellar Ti of step 2 stacking 3c 2t xin powder, T is the-F group or-OH group that after corrosion, powder are formed.
By Ti in present embodiment step 2 3alC 2powder puts into hydrofluoric acid corrosion 4 ~ 24h that concentration is 20wt.% ~ 50wt.%, and object makes Ti 3alC 2al is mutually corroded.
In present embodiment step 2, after corrosion, solution adds deionized water and carries out centrifugal treating, and object removes hydrofluoric acid.
Embodiment two: present embodiment and embodiment one unlike, in step one by Ti, Al, C powder according to after mol ratio 3:1.2:2 mixing, at 1450 DEG C, synthesize Ti by pressureless sintering 3alC 2phase ceramics.Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike, by Ti in step 2 3alC 2it is that the hydrofluoric acid of 40wt.% corrodes 12h that powder puts into concentration.Other step and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike, by the lamellar Ti of stacking in step 3 3c 2t xpowder and organic solvent are that 1:20 mixes according to mass ratio.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike in, step 2 and step 3 centrifugal speed is 100rpm ~ 4000rpm, centrifugation time is 30min ~ 120min, centrifugal number of times is 1 ~ 10 time.Other step and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike, add deionized water in step 4 and ultrasonic vibration dispersion 12h.Other step and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike, in step 4, ultrasonic power is 300W ~ 600W, ultrasonic frequency is 20 ~ 40KHz.Other step and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike, have Ti in the supernatant of step 4 suspension 3c 2t x, Ti 3c 2t xbe 1:(200 ~ 1000 with the mass ratio of deionized water).Other step and parameter identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight are unlike, the Ti of sheet in step 5 3c 2t xthe gross mass of powder and graphene oxide and the mass ratio of organic solvent are 1:(10 ~ 100).Other step and parameter identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine are unlike, stirring at room temperature 12h in step 5.Other step and parameter identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten are unlike, the Ti of graphene oxide and sheet in step 5 3c 2t xthe mass ratio of powder is 1:(1 ~ 99).Other step and parameter identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one are dimethyl sulfoxide (DMSO), dimethyl formamide or TritonX100 unlike organic solvent in, step 3 and step 5.Other step and parameter identical with one of embodiment one to ten one.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment 1:
Can be used for the preparation method of the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative, realize according to the following steps:
One, after being mixed according to mol ratio 3:1.2:2 by Ti, Al, C powder, at 1400 DEG C, Ti is synthesized by pressureless sintering 3alC 2phase ceramics, then pulverizes, and obtains Ti 3alC 2powder;
Two, by Ti 3alC 2it is that the hydrofluoric acid of 30wt.% corrodes 4h that powder puts into concentration, and after corrosion, solution adds deionized water and carries out centrifugal treating, is then dried by sediment, obtains the lamellar Ti of stacking 3c 2t xpowder;
Three, by the lamellar Ti of stacking 3c 2t xpowder and dimethyl sulfoxide (DMSO) are that 1:20 mixes according to mass ratio, then carry out centrifugal treating, obtain suspension;
Four, get the supernatant of suspension, add deionized water and ultrasonic vibration dispersion 6h, after oven dry, obtain the Ti of sheet 3c 2t xpowder;
Five, by the Ti of sheet 3c 2t xpowder and graphene oxide join in dimethyl sulfoxide (DMSO) simultaneously, stirring at room temperature 6h, then carry out suction filtration, remove organic solvent, then dry at 80 DEG C, namely complete the preparation of the titanium carbide nanometer sheet/graphene composite material that can be used for lithium ion battery negative;
The wherein lamellar Ti of step 2 stacking 3c 2t xin powder, T is the-F group or-OH group that after corrosion, powder are formed.
In the present embodiment step 2 and step 3 centrifugal speed is 1000rpm, centrifugation time is 60min, centrifugal number of times is 3 times.
In the present embodiment step 4, ultrasonic power is 500W, ultrasonic frequency is 30KHz.
Ti is had in the supernatant of the present embodiment step 4 suspension 3c 2t x, Ti 3c 2t xbe 1:600 with the mass ratio of deionized water.
The Ti of sheet in the present embodiment step 5 3c 2t xthe gross mass of powder and graphene oxide and the mass ratio of organic solvent are 1:50.
The Ti of graphene oxide and sheet in the present embodiment step 5 3c 2t xthe mass ratio of powder is 1:10.
The Ti of 4h is corroded in hydrofluoric acid in the present embodiment step 2 3c 2t xsEM figure, see Fig. 1, can Ti be found out 3c 2t xhave a kind of structure of lamellar, this similar is in Graphene, and lithium ion can spread between synusia, plays the effect storing lithium ion, can be applicable to do electrode material in lithium ion battery.But the functional group existed due to its surface has had a strong impact on Ti 3c 2t xconductivity, and the agglomeration of synusia have impact on Ti simultaneously 3c 2t xchemical property.Therefore add Graphene and form composite material to improve its conductivity, and at Ti 3c 2t xor mix the lamella quantity that other materials effectively can reduce reunion in the synusia of Graphene, so at Ti 3c 2t xmiddle doped graphene, not only in order to improve its conductivity, can also suppress the generation of reuniting, improving its electrochemical performance (capacity, charge-discharge characteristic, cycle performance, multiplying power property), expands its range of application in lithium ion battery.
Embodiment 2:
Can be used for the preparation method of the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative, realize according to the following steps:
One, after being mixed according to mol ratio 3:1.1:2 by Ti, Al, C powder, at 1500 DEG C, Ti is synthesized by pressureless sintering 3alC 2phase ceramics, then pulverizes, and obtains Ti 3alC 2powder;
Two, by Ti 3alC 2it is that the hydrofluoric acid of 30wt.% corrodes 12h that powder puts into concentration, and after corrosion, solution adds deionized water and carries out centrifugal treating, is then dried by sediment, obtains the lamellar Ti of stacking 3c 2t xpowder;
Three, by the lamellar Ti of stacking 3c 2t xpowder and organic solvent are that 1:20 mixes according to mass ratio, then carry out centrifugal treating, obtain suspension;
Four, get the supernatant of suspension, add deionized water and ultrasonic vibration dispersion 12h, after oven dry, obtain the Ti of sheet 3c 2t xpowder;
Five, by the Ti of sheet 3c 2t xpowder and graphene oxide join in organic solvent simultaneously, stirring at room temperature 6h, then carry out suction filtration, remove organic solvent, dry at 80 DEG C again, namely complete the preparation of the titanium carbide nanometer sheet/graphene composite material that can be used for lithium ion battery negative, obtain titanium carbide/graphene sheet layer;
The wherein lamellar Ti of step 2 stacking 3c 2t xin powder, T is the-F group or-OH group that after corrosion, powder are formed.
In the present embodiment step 2 and step 3 centrifugal speed is 2000rpm, centrifugation time is 40min, centrifugal number of times is 2 times.
In the present embodiment step 4, ultrasonic power is 400W, ultrasonic frequency is 30KHz.
Ti is had in the supernatant of the present embodiment step 4 suspension 3c 2t x, Ti 3c 2t xbe 1:700 with the mass ratio of deionized water.
The Ti of sheet in the present embodiment step 5 3c 2t xthe gross mass of powder and graphene oxide and the mass ratio of organic solvent are 1:60.
The Ti of graphene oxide and sheet in the present embodiment step 5 3c 2t xthe mass ratio of powder is 1:5.
The Ti of 12h is corroded in hydrofluoric acid in the present embodiment step 2 3c 2t xsEM figure, see Fig. 2, can Ti be found out 3c 2t xhave a kind of structure of lamellar, this similar is in Graphene, and lithium ion can spread between synusia, plays the effect storing lithium ion, can be applicable to do electrode material in lithium ion battery.But the functional group existed due to its surface has had a strong impact on Ti 3c 2t xconductivity, and the agglomeration of synusia have impact on Ti simultaneously 3c 2t xchemical property.Therefore add Graphene and form composite material to improve its conductivity, and at Ti 3c 2t xor mix the lamella quantity that other materials effectively can reduce reunion in the synusia of Graphene, so at Ti 3c 2t xmiddle doped graphene, not only in order to improve its conductivity, can also suppress the generation of reuniting, improving its electrochemical performance (capacity, charge-discharge characteristic, cycle performance, multiplying power property), expands its range of application in lithium ion battery.
Embodiment 3:
Can be used for the preparation method of the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative, realize according to the following steps:
One, after being mixed according to mol ratio 3:1.1:2 by Ti, Al, C powder, at 1400 DEG C, Ti is synthesized by pressureless sintering 3alC 2phase ceramics, then pulverizes, and obtains Ti 3alC 2powder;
Two, by Ti 3alC 2it is that the hydrofluoric acid of 40wt.% corrodes 24h that powder puts into concentration, and after corrosion, solution adds deionized water and carries out centrifugal treating, is then dried by sediment, obtains the lamellar Ti of stacking 3c 2t xpowder;
Three, by the lamellar Ti of stacking 3c 2t xpowder and organic solvent are that 1:20 mixes according to mass ratio, then carry out centrifugal treating, obtain suspension;
Four, get the supernatant of suspension, add deionized water and ultrasonic vibration dispersion 6h, after oven dry, obtain the Ti of sheet 3c 2t xpowder;
Five, by the Ti of sheet 3c 2t xpowder and graphene oxide join in organic solvent simultaneously, stirring at room temperature 6h, then carry out suction filtration, remove organic solvent, then dry at 80 DEG C, namely complete the preparation of the titanium carbide nanometer sheet/graphene composite material that can be used for lithium ion battery negative;
The wherein lamellar Ti of step 2 stacking 3c 2t xin powder, T is the-F group or-OH group that after corrosion, powder are formed.
In the present embodiment step 2 and step 3 centrifugal speed is 1000rpm, centrifugation time is 50min, centrifugal number of times is 3 times.
In the present embodiment step 4, ultrasonic power is 300W, ultrasonic frequency is 40KHz.
Ti is had in the supernatant of the present embodiment step 4 suspension 3c 2t x, Ti 3c 2t xbe 1:500 with the mass ratio of deionized water.
The Ti of sheet in the present embodiment step 5 3c 2t xthe gross mass of powder and graphene oxide and the mass ratio of organic solvent are 1:20.
The Ti of graphene oxide and sheet in the present embodiment step 5 3c 2t xthe mass ratio of powder is 1:5.
The Ti of 24h is corroded in hydrofluoric acid in the present embodiment step 2 3c 2t x, after testing, have a kind of structure of lamellar, this similar is in Graphene, and lithium ion can spread between synusia, plays the effect storing lithium ion, can be applicable to do electrode material in lithium ion battery.
Embodiment 4:
Can be used for the preparation method of the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative, realize according to the following steps:
One, after being mixed according to mol ratio 3:1.2:2 by Ti, Al, C powder, at 1500 DEG C, Ti is synthesized by pressureless sintering 3alC 2phase ceramics, then pulverizes, and obtains Ti 3alC 2powder;
Two, by Ti 3alC 2it is that the hydrofluoric acid of 50wt.% corrodes 6h that powder puts into concentration, and after corrosion, solution adds deionized water and carries out centrifugal treating, is then dried by sediment, obtains the lamellar Ti of stacking 3c 2t xpowder;
Three, by the lamellar Ti of stacking 3c 2t xpowder and organic solvent are that 1:30 mixes according to mass ratio, then carry out centrifugal treating, obtain suspension;
Four, get the supernatant of suspension, add deionized water and ultrasonic vibration dispersion 6h, after oven dry, obtain the Ti of sheet 3c 2t xpowder;
Five, by the Ti of sheet 3c 2t xpowder and graphene oxide join in organic solvent simultaneously, stirring at room temperature 12h, then carry out suction filtration, remove organic solvent, then dry at 80 DEG C, namely complete the preparation of the titanium carbide nanometer sheet/graphene composite material that can be used for lithium ion battery negative;
The wherein lamellar Ti of step 2 stacking 3c 2t xin powder, T is the-F group or-OH group that after corrosion, powder are formed.
In the present embodiment step 2 and step 3 centrifugal speed is 3000rpm, centrifugation time is 30min, centrifugal number of times is 4 times.
In the present embodiment step 4, ultrasonic power is 500W, ultrasonic frequency is 30KHz.
Ti is had in the supernatant of the present embodiment step 4 suspension 3c 2t x, Ti 3c 2t xbe 1:500 with the mass ratio of deionized water.
The Ti of sheet in the present embodiment step 5 3c 2t xthe gross mass of powder and graphene oxide and the mass ratio of organic solvent are 1:20.
The Ti of graphene oxide and sheet in the present embodiment step 5 3c 2t xthe mass ratio of powder is 1:15.
The Ti of 6h is corroded in hydrofluoric acid in the present embodiment step 2 3c 2t x, after testing, have a kind of structure of lamellar, this similar is in Graphene, and lithium ion can spread between synusia, plays the effect storing lithium ion, can be applicable to do electrode material in lithium ion battery.
Embodiment 5:
Can be used for the preparation method of the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative, realize according to the following steps:
One, after being mixed according to mol ratio 3:1.2:2 by Ti, Al, C powder, at 1450 DEG C, Ti is synthesized by pressureless sintering 3alC 2phase ceramics, then pulverizes, and obtains Ti 3alC 2powder;
Two, by Ti 3alC 2it is that the hydrofluoric acid of 30wt.% corrodes 16h that powder puts into concentration, and after corrosion, solution adds deionized water and carries out centrifugal treating, is then dried by sediment, obtains the lamellar Ti of stacking 3c 2t xpowder;
Three, by the lamellar Ti of stacking 3c 2t xpowder and organic solvent are that 1:30 mixes according to mass ratio, then carry out centrifugal treating, obtain suspension;
Four, get the supernatant of suspension, add deionized water and ultrasonic vibration dispersion 8h, after oven dry, obtain the Ti of sheet 3c 2t xpowder;
Five, by the Ti of sheet 3c 2t xpowder and graphene oxide join in organic solvent simultaneously, stirring at room temperature 10h, then carry out suction filtration, remove organic solvent, then dry at 80 DEG C, namely complete the preparation of the titanium carbide nanometer sheet/graphene composite material that can be used for lithium ion battery negative;
The wherein lamellar Ti of step 2 stacking 3c 2t xin powder, T is the-F group or-OH group that after corrosion, powder are formed.
In the present embodiment step 2 and step 3 centrifugal speed is 4000rpm, centrifugation time is 30min, centrifugal number of times is 4 times.
In the present embodiment step 4, ultrasonic power is 600W, ultrasonic frequency is 20KHz.
Ti is had in the supernatant of the present embodiment step 4 suspension 3c 2t x, Ti 3c 2t xbe 1:500 with the mass ratio of deionized water.
The Ti of sheet in the present embodiment step 5 3c 2t xthe gross mass of powder and graphene oxide and the mass ratio of organic solvent are 1:30.
The Ti of graphene oxide and sheet in the present embodiment step 5 3c 2t xthe mass ratio of powder is 1:20.
The Ti of 16h is corroded in hydrofluoric acid in the present embodiment step 2 3c 2t x, after testing, have a kind of structure of lamellar, this similar is in Graphene, and lithium ion can spread between synusia, plays the effect storing lithium ion, can be applicable to do electrode material in lithium ion battery.
Embodiment 6:
Can be used for the preparation method of the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative, realize according to the following steps:
One, after being mixed according to mol ratio 3:1.3:2 by Ti, Al, C powder, at 1500 DEG C, Ti is synthesized by pressureless sintering 3alC 2phase ceramics, then pulverizes, and obtains Ti 3alC 2powder;
Two, by Ti 3alC 2it is that the hydrofluoric acid of 50wt.% corrodes 4h that powder puts into concentration, and after corrosion, solution adds deionized water and carries out centrifugal treating, is then dried by sediment, obtains the lamellar Ti of stacking 3c 2t xpowder;
Three, by the lamellar Ti of stacking 3c 2t xpowder and organic solvent are that 1:50 mixes according to mass ratio, then carry out centrifugal treating, obtain suspension;
Four, get the supernatant of suspension, add deionized water and ultrasonic vibration dispersion 2h, after oven dry, obtain the Ti of sheet 3c 2t xpowder;
Five, by the Ti of sheet 3c 2t xpowder and graphene oxide join in organic solvent simultaneously, stirring at room temperature 20h, then carry out suction filtration, remove organic solvent, then dry at 80 DEG C, namely complete the preparation of the titanium carbide nanometer sheet/graphene composite material that can be used for lithium ion battery negative;
The wherein lamellar Ti of step 2 stacking 3c 2t xin powder, T is the-F group or-OH group that after corrosion, powder are formed.
In the present embodiment step 2 and step 3 centrifugal speed is 4000rpm, centrifugation time is 40min, centrifugal number of times is 4 times.
In the present embodiment step 4, ultrasonic power is 600W, ultrasonic frequency is 40KHz.
Ti is had in the supernatant of the present embodiment step 4 suspension 3c 2t x, Ti 3c 2t xbe 1:700 with the mass ratio of deionized water.
The Ti of sheet in the present embodiment step 5 3c 2t xthe gross mass of powder and graphene oxide and the mass ratio of organic solvent are 1:30.
The Ti of graphene oxide and sheet in the present embodiment step 5 3c 2t xthe mass ratio of powder is 1:40.
The Ti of 4h is corroded in hydrofluoric acid in the present embodiment step 2 3c 2t x, after testing, have a kind of structure of lamellar, this similar is in Graphene, and lithium ion can spread between synusia, plays the effect storing lithium ion, can be applicable to do electrode material in lithium ion battery.

Claims (10)

1. can be used for a preparation method for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative, it is characterized in that it realizes according to the following steps:
One, by Ti, Al, C powder according to mol ratio 3:(1.1 ~ 1.3): 2 mixing after, at 1400 DEG C ~ 1500 DEG C, synthesize Ti by pressureless sintering 3alC 2phase ceramics, then pulverizes, and obtains Ti 3alC 2powder;
Two, by Ti 3alC 2powder puts into hydrofluoric acid corrosion 4 ~ 24h that concentration is 20wt.% ~ 50wt.%, and the rear solution of corrosion adds deionized water and carries out centrifugal treating, is then dried by sediment, obtains the lamellar Ti of stacking 3c 2t xpowder;
Three, by the lamellar Ti of stacking 3c 2t xpowder and organic solvent are 1:(10 ~ 100 according to mass ratio) mix, then carry out centrifugal treating, obtain suspension;
Four, get the supernatant of suspension, add deionized water and ultrasonic vibration dispersion 2 ~ 24h, after oven dry, obtain the Ti of sheet 3c 2t xpowder;
Five, by the Ti of sheet 3c 2t xpowder and graphene oxide join in organic solvent simultaneously, stirring at room temperature 6 ~ 24h, then carry out suction filtration, remove organic solvent, then dry at 80 DEG C, namely complete the preparation of the titanium carbide nanometer sheet/graphene composite material that can be used for lithium ion battery negative;
The wherein lamellar Ti of step 2 stacking 3c 2t xin powder, T is the-F group or-OH group that after corrosion, powder are formed.
2. a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative according to claim 1, it is characterized in that in step one by Ti, Al, C powder according to mol ratio 3:1.2:2 mixing after, at 1450 DEG C, synthesize Ti by pressureless sintering 3alC 2phase ceramics.
3. a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative according to claim 1, is characterized in that Ti in step 2 3alC 2it is that the hydrofluoric acid of 40wt.% corrodes 12h that powder puts into concentration.
4. a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative according to claim 1, is characterized in that the lamellar Ti of stacking in step 3 3c 2t xpowder and organic solvent are that 1:20 mixes according to mass ratio.
5. a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative according to claim 1, is characterized in that the centrifugal speed in step 2 and step 3 is 100rpm ~ 4000rpm, centrifugation time is 30min ~ 120min, centrifugal number of times is 1 ~ 10 time.
6. a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative according to claim 1, is characterized in that in step 4, ultrasonic power is 300W ~ 600W, ultrasonic frequency is 20 ~ 40KHz.
7. a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative according to claim 1, is characterized in that there is Ti in the supernatant of step 4 suspension 3c 2t x, Ti 3c 2t xbe 1:(200 ~ 1000 with the mass ratio of deionized water).
8. a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative according to claim 1, is characterized in that the Ti of sheet in step 5 3c 2t xthe gross mass of powder and graphene oxide and the mass ratio of organic solvent are 1:(10 ~ 100).
9. a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative according to claim 1, is characterized in that the Ti of graphene oxide and sheet in step 5 3c 2t xthe mass ratio of powder is 1:(1 ~ 99).
10. a kind of preparation method that can be used for the titanium carbide nanometer sheet/graphene composite material of lithium ion battery negative according to claim 1, is characterized in that in step 3 and step 5, organic solvent is dimethyl sulfoxide (DMSO), dimethyl formamide or TritonX100.
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