CN104016345B - The preparation method of one kind Graphene two-dimensional layer titanium carbide nanometer sheet - Google Patents
The preparation method of one kind Graphene two-dimensional layer titanium carbide nanometer sheet Download PDFInfo
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- CN104016345B CN104016345B CN201410243022.0A CN201410243022A CN104016345B CN 104016345 B CN104016345 B CN 104016345B CN 201410243022 A CN201410243022 A CN 201410243022A CN 104016345 B CN104016345 B CN 104016345B
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Abstract
The invention discloses the preparation method of a kind Graphene two-dimensional layer titanium carbide nanometer sheet, comprise in-situ hot pressing solid-liquid reaction preparation Ti
3alC
2powder, chemical liquid phase reaction preparation two-dimentional titanium carbide, vacuum calcining post-treating and other steps.Present invention process flow process is simple, processing parameter stable, process control, efficiency are high, cost is low, namely obtain the Ti that degree of crystallinity is good, purity is high under short period of time, low pressure
3alC
2precursor; Two-dimentional Ti prepared by the present invention can be seen from SEM photo
3c
2nanometer sheet lateral dimension can reach 5 ~ 10 microns, and individual layer mean thickness is about 10 ~ 20 nanometers, and after calcination processing, interlamellar spacing obviously increases, and synusia surface is regular smooth.
Description
Technical field
The invention belongs to the preparing technical field of nano material, relate to a kind of method of synthesizing class Graphene two-dimensional layer titanium carbide nanometer sheet particularly.
Background technology
Since the people such as Novoselov and Geim find Graphene, the synthesis of two-dimensional material, properties and application have become the most interested important research field of material supply section scholars, and academia has started the research boom of a new round to two-dimensional material thus.Material structure, after changing two dimension into by three-dimensional, shows unique surface tissue and characteristic electron, is provided with excellent mechanics, calorifics, electricity and optical property.Such as lamellar graphite simple micromechanics stripping method and the peelable Graphene obtained being had the performances such as high transmission rate, high thermal conductivity coefficient, high electron mobility and extremely low resistivity, is the material of most magnetism and scientific research value in recent years.Be that the two-dimensional nanostructure material of Typical Representative has shown wide application prospect comprising in the fields such as field-effect transistor, flexible transparent electrode, touch-screen, advanced composite material, sensor, support of the catalyst, energy storage device with Graphene.Extensively concerned class Graphene two-dimensional layer material mainly contains Transition-metal dichalcogenide, transition metal oxide and metal hydroxides at present, the precursor of these stratified materials because of the Van der Waals interaction force between synusia more weak, be easy to the sheet structure they being peeled off the single or multiple lift becoming two dimension.
2011, the Barsoum seminar of Drexel university of the U.S. synthesized the C/N compound (NaguibM., etal., Adv.Mater., 2011,23,4248-4253) of novel two-dimensional layer transition metal.The precursor that they are used for peeling off is that a class is called as M
n+1aX
nthe ternary layered melt-ceramic compound (M is early stage transition metal, and A is IIIA or IVA race element mainly, and X is C and/or N element, n=1,2 or 3) of phase.Although A atomic layer chemical activity is comparatively strong, compared with the layer structure materials such as the graphite more weak with interlaminar action power, BN, there is extremely strong bond energy between the three-dimensional synusia of this compounds and be difficult to be stripped.Although MAX phase at high temperature can go out A and obtain MX phase by decomposed, in pyrolysis process, the laminate structure of MX is destroyed and change three-dimensional cubic rock salt structure into.The research team of Barsoum solves this difficult problem, obtains with having separated A in the liquid phase stripping method MAX phase that chemically character is highly stable the two-dimentional MX structured material that original Lamellar character still exists.MAX powder containing aluminium element is at room temperature immersed in the aqueous solution of HF by they, is peeled off by the al atomic layer in MAX phase, has synthesized the two-dimentional MX nanometer sheet that laminate structure is still retained.
From the lamellar character of atomic structure, MAX phase can think that two-dimensional layer transition metal C/N compound and A atomic shell are bonded together.Strong M-X key in MAX phase has the feature of covalent linkage, metallic bond and ionic linkage, and M-A key is metallic bond.With other stratified materials as graphite is compared with the weak Van der Waals interaction supporting structure of Transition-metal dichalcogenide etc., the key of each interlayer of MAX phase is too strong and can not break with shearing or any similar mechanical means.But utilize the difference of M-A key and M-X key relative intensity, can A atomic shell be removed to chemically and not interrupt M-X key, thus gain freedom without the MX thin slice supporting two-dirnentional structure.Three-dimensional MAX phase factor removes A becomes two-dimentional MX phase later, the MX phase factor of this two-dimensional layer sheet its have similar attribute to Graphene and be called as MXene.The individual layer synusia thickness of MXene material is less than 1 nanometer, and lateral dimension can reach 10 microns, and resistivity is close with Graphene, and conductivity is good.Although Graphene has attracted more attention than other two-dimensional material, but the weak Van der Waals force of its simple chemical formula and interlayer limits its practical application, and the interlayer structure comprising 2 ~ 3 kinds of elements of MXene complexity, the combination that a large amount of difference in functionality may be provided to roll into a ball thus obtain some comparatively special performances.Theoretical prove with experiment, this kind of material may be applied in multiple technical field, such as catalysis, energy storage device, electrical condenser and lithium ion battery and the enhancing as polymkeric substance equal.
Ti
3alC
2being typical ternary metal ceramic compound, is also the three-layer laminated precursor being stripped out at most two-dimensional nano sheet at first of research at present.Ti
3alC
2structure can regard C atom as and be filled in the octahedron of closelypacked Ti atom, Al atom then intercalation at Ti
3c
2among synusia.By Ti
3alC
2powder is immersed in after in the aqueous solution of HF, and HF selectivity acid etching falls Al atomic shell and do not break the laminate structure of Ti-C key and generate two-dimentional Ti
3c
2sheet.In the water surrounding being rich in fluorion and hydroxyl, Ti
3alC
2after Al atomic shell in parent phase is stripped, Ti-Al key by the F ion of surface adsorption and OH ion replace, the actual product obtained is Ti
3c
2f
2and Ti
3c
2(OH)
2nano ply.Document (KhazaeiM., etal., Adv..Funct.Mater., 2013,23,2185-2192) utilize the free energy band structure without supporting two-dimentional titanium carbide and derivative thereof of Density function theory, result shows: pure two-dimentional titanium carbide structure has eka-gold attribute, but the derivative after the surface adsorption functional group such as OH, F ion is that the semi-conductor of narrow band gap is (as Ti
3c
2f
2and Ti
3c
2(OH)
2band gap be respectively 0.1 and 0.05eV).The structure that two dimension titanium carbide opens, interlayer weak interaction combine than with its electroconductibility with larger surface volume, make this two-dimensional layered-structure material have good application prospect in lithium ion battery electrode material, fuel cell, ultracapacitor and water treatment.Such as, two-dimentional Ti used by document (NaguibMetal., J, ElectroChem.Commun., 2012,16,61-64)
2lithium ion battery negative material prepared by C, electrical capacity is high, have extended cycle life, and document (Tang.Q, etal., J.Am.Chem.Soc., 2012,134,16909-16916) utilizes First Principle to have studied two-dimentional Ti
3c
2storage lithium performance, theoretical prediction shows Ti
3c
2the diffusion of lithium is had to the characteristic of low energy barrier and high-selenium corn, but the absorption of F or OH ion on synusia surface can cause storing up lithium performance weaken the minimizing with reversible capacity, its stability also can be affected.
Being used for peeling off the typical MAX phase that A atomic shell prepares two-dimentional MX nanometer sheet is at present Ti
3alC
2.The integrity degree of the level and smooth and lattice of this powder synusia determines the quality of two-dimensional nano sheet, pattern and performance.At preparation Ti
3alC
2powder aspect, in order to the impurity phases such as TiC in inhibited reaction process generation and prevent the generation of thermal explosion phenomenon in building-up process, generally with the addition of the sintering aid of low melting point, as Chinese patent CN1699159A (Zhai Hongxiang, a kind of titanium aluminium carbide powder and take tin as the synthetic method of reaction promoter) and Chinese patent CN101070248A (Li Shibo, a kind of atmospheric synthesizing method of aluminium-titanium carbonate ceramic powder) in, all make auxiliary agent with Sn, these sintering aids have been solid-solubilized in Ti after the reaction
3alC
2lattice in, cause the destruction of lattice imperfection and three-dimensional synusia characteristic, this is unfavorable for the stripping of follow-up Al atomic shell and the smooth and regular of two-dimensional layer surface.In addition, the grain-size of two-dimension nano materials and pattern, condition of surface and microstructure directly affect its physicochemical property and purposes.Optical, electrical, the thermal and magnetic of nanoparticle uniqueness and the performance such as catalysis, absorption have size and pattern (AliofkhazraeiM., etal., Two-DimensionalNanostructures, CRCPress, the 2012) dependency of height.Chemical liquid phase stripping method is prepared two-dimensional layered-structure material and is had the features such as technique is simple, process control, efficiency are high, cost is low, but three-layer laminated Ti
3alC
2al atomic shell is mutually after being stripped, two-dimentional titanium carbide nanometer sheet prepared by chemical liquid phase reaction inevitably has serious textural defect, as document (ChangF., etal., Mater.Lett., 2013,109, two-dimentional titanium carbide nanometer sheet lattice imperfection 295-297) is more, and synusia is smooth not.Ti prepared by these class methods
3c
2its specific conductivity of synusia can diminish along with increasing of defect.Meanwhile, Ti
3alC
2after there is chemical reaction with HF in aqueous, Ti
3c
2a large amount of OH functional groups can be adsorbed in synusia surface, and this functional group increases the variation exacerbating conductivity further, have impact on the application of two-dimentional titanium carbide nanometer sheet in electricity and chemical property.Therefore, preparing the little and hydroxy functional group poor two-dimensional layer titanium carbide nanometer sheet of regular appearance, smooth surface, grain-size is the key promoting that the conductivity of this material is fully utilized.
Summary of the invention
Goal of the invention: for solving prior art Problems existing, the present invention proposes the preparation method of a kind of regular appearance, smooth surface and hydroxy functional group poor class Graphene two-dimensional layer titanium carbide nanometer sheet, to improve its electricity and chemical property.
Technical scheme: solving the problems of the technologies described above adopted technical scheme is: first with Ti, Al and C powder for Ti prepared by raw material
3alC
2powder, and then use Ti
3alC
2powder and HF reactant aqueous solution obtain Ti
3c
2, finally to Ti
3c
2after carrying out vacuum calcining process, obtain the smooth complete and two-dimensional layer Ti that conductivity is good of synusia
3c
2nanometer sheet.Particularly, comprise the following steps:
(1) Ti
3alC
2the preparation of powder: after shaping for the dry grinding of Ti, Al and C powder, the Ti of the loose bulk that original position solid-liquid reaction obtains occurs in the hot pressing furnace of argon shield
3alC
2, then to the Ti obtained
3alC
2carry out grinding, sieving obtains Ti
3alC
2powder;
(2) preparation of two-dimentional titanium carbide: by the Ti obtained in step (1)
3alC
2powder is dipped in the aqueous solution of HF, and magnetic agitation issues biochemical liquid phase reaction, obtains suspension, by above-mentioned suspension after filtration, washing, alcohol wash, centrifugal after low-temperature vacuum drying again, obtain two-dimentional titanium carbide powder;
(3) vacuum calcining aftertreatment: the two-dimentional titanium carbide powder obtained in step (2) is placed in calcining in vacuum crystallization furnace and obtains class Graphene two-dimensional layer titanium carbide nanometer sheet.
Wherein, in step (1), the mol ratio of Ti, Al and C powder is 3: 1: 2.
In step (1), shaping condition of dry grinding is: the mixture of Ti, Al and C powder and agate ball are dry mixed 8 ~ 12h by weight 1: 2 in ball grinder, and adopt graphite molds, forming pressure is 5 ~ 15MPa.
The condition of step (1) situ solid-liquid reaction is: the temperature in hot pressing furnace is with behind ramp to 1300 ~ 1400 of 10 ~ 25 DEG C/min DEG C, 20 ~ 30 minutes are incubated under 20 ~ 30Mpa pressure, then be cooled to 50 ~ 70 DEG C, obtain loose block Ti
3alC
2.
The sub-sieve sieved in step (1) is 100 ~ 200 orders.
In step (2), Ti
3alC
2the mass volume ratio of powder and the HF aqueous solution is (6 ~ 10): the concentration of (100 ~ 120) g/ml, HF aqueous solution is 45 ~ 55wt%, and temperature is 45 ~ 55 DEG C.
In step (2), the speed of magnetic agitation is 1000 ~ 2500r/min, and churning time is 6 ~ 40 hours.
The suspension obtained after chemical liquid phase reaction in step (2) after filtration, washing, centrifugal condition after alcohol wash be: first the centrifugal 20 ~ 30min of 3000 ~ 5000r/min removes oarse-grained particle, then centrifugal 10 ~ 20min under 8000 ~ 10000r/min, collects the solid obtained.
In step (2), the temperature of low-temperature vacuum drying is 40 ~ 60 DEG C, and time of drying is 20 ~ 30h.
In step (3), the vacuum tightness in vacuum crystallization furnace is 0.5 × 10
-3~ 2 × 10
-3pa, calcining temperature is 450 ~ 750 DEG C, and calcination time is 1 ~ 2h.By vacuum calcining, reduce the impact of surface hydroxyl on material, obtain regular appearance, smooth surface, two-dimensional layer titanium carbide nanometer sheet that grain-size is little.
Beneficial effect: present invention process flow process is simple, processing parameter stable, process control, efficiency are high, cost is low, namely obtain the Ti that degree of crystallinity is good, purity is high under short period of time, low pressure
3alC
2precursor; Two-dimentional Ti prepared by the present invention can be seen from SEM photo
3c
2nanometer sheet lateral dimension can reach 5 ~ 10 microns, and individual layer mean thickness is about 10 ~ 20 nanometers, and after calcination processing, interlamellar spacing obviously increases, and synusia surface is regular smooth.Two-dimentional Ti after calcining
3c
2the thin discs four probe method of powder after tabletting machine is colded pressing records resistivity between 0.5 ~ 10 Ω cm.The present invention can be used for ultracapacitor, lithium ion battery electrode material, catalysis and sorbing material and the field such as energy storage device and matrix material.
Accompanying drawing explanation
Ti in Fig. 1 embodiment 1
3alC
2the XRD figure spectrum of powder and the two-dimensional layer titanium carbide nanometer sheet that obtains after HF acid etching.
The SEM photo of two-dimentional titanium carbide powder after vacuum calcining in Fig. 2 embodiment 2.
Embodiment
Embodiment 1
By the molar ratio ingredient of Ti: Al: C=3: 1: 2, its mixture is dry mixed 10 hours by ratio of grinding media to material 2: 1 together with agate ball in ball grinder; The batching mixed is put into graphite jig real at the pressure of 5MPa; be placed in the hot pressing furnace of argon shield; by the temperature of hot pressing furnace with the ramp to 1350 DEG C of 15 DEG C/min, then under 25MPa pressure, be incubated 25 minutes, after being cooled to 60 DEG C, obtain loose block Ti
3alC
2, through broken, ground 200 mesh sieves, obtain Ti
3alC
2powder.By the Ti of 8 grams
3alC
2powder is dipped in the HF aqueous solution of 100mL50wt% under room temperature, reacts 20 hours, obtain suspension with the rotating speed magnetic agitation of 1500r/min; The suspension obtained being washed to after filtration, repeatedly pH value is repeatedly clean with dehydrated alcohol after neutrality again, then with centrifugal 20 minutes of 5000r/min except the larger particle of degranulation, then with 8000r/min 40 DEG C of dryings 24 hours in vacuum drier after centrifugal 10 minutes; Powder after vacuum drying treatment being placed in vacuum tightness is 2 × 10
-3in the crystallization furnace of pa, 550 DEG C of temperature lower calcinations 1 hour, obtain two-dimensional layer titanium carbide nanometer sheet.To the Ti obtained
3alC
2powder and the two-dimensional layer titanium carbide nanometer sheet obtained after HF acid treatment carry out XRD test, and result as shown in Figure 1.As can be seen from the figure, three-layer laminated Ti
3alC
2in the strongest characteristic peak almost completely dissolve at 39 degree of places, the Ti becoming two-dimensional layer after Al is stripped is described
3c
2.The two-dimentional Ti of preparation
3c
2nanometer sheet lateral dimension is 5 ~ 10 microns, and thickness in monolayer is about 10-20 nanometer, the two-dimentional Ti after calcining
3c
2it is 7 Ω cm that the thin discs four probe method of powder after tabletting machine is colded pressing records resistivity.
Embodiment 2
By the molar ratio ingredient of Ti: Al: C=3: 1: 2, in ball grinder, be dry mixed 8 hours by ratio of grinding media to material 2: 1 together with agate ball; The pressure batching mixed being put into graphite jig 10MPa is real, be placed in the hot pressing furnace of argon shield, with the ramp to 1300 DEG C of 10 DEG C/min, under 30MPa pressure, be incubated 20 minutes, after being cooled to 60 DEG C, obtain loose block Ti
3alC
2, after fragmentation, grinding, cross 200 mesh sieves; By the Ti of 6 grams
3alC
2powder is dipped in the HF aqueous solution of 100 milliliters of 50wt% under room temperature, reacts 40 hours with the rotating speed magnetic agitation of 2000r/min; It is repeatedly clean with dehydrated alcohol after neutrality that gained suspension is washed to pH value after filtration, repeatedly again, then with centrifugal 30 minutes of 4000r/min except the larger particle of degranulation, then with 8000r/min 50 DEG C of dryings 30 hours in vacuum drier after centrifugal 10 minutes; Powder after vacuum drying treatment being placed in vacuum tightness is 1 × 10
-3in the crystallization furnace of pa, 650 DEG C of temperature lower calcinations 1 hour, obtain two-dimensional layer titanium carbide nanometer sheet.Carry out SEM sign to the two-dimensional layer titanium carbide nanometer sheet obtained, result is as shown in Figure 2, upper as can be seen from figure, two-dimentional Ti
3c
2nanometer sheet lateral dimension can reach 5-10 micron, and individual layer mean thickness is about 10 ~ 20 nanometers, and resistivity is 5 Ω cm.
Embodiment 3
By the molar ratio ingredient of Ti: Al: C=3: 1: 2, in ball grinder, be dry mixed 12 hours by ratio of grinding media to material 2: 1 together with agate ball; The pressure batching mixed being put into graphite jig 5MPa is real, be placed in the hot pressing furnace of argon shield, with the ramp to 1400 DEG C of 20 DEG C/min, under 20MPa pressure, be incubated 30 minutes, after being cooled to 55 DEG C, obtain loose block Ti
3alC
2, after fragmentation, grinding, cross 200 mesh sieves; By the Ti of 10 grams
3alC
2powder is dipped in the HF aqueous solution of 100 milliliters of 50wt% of 50 DEG C, reacts 6 hours with the rotating speed magnetic agitation of 1000r/min; It is repeatedly clean with dehydrated alcohol after neutrality that gained suspension is washed to pH value after filtration, repeatedly again, then with centrifugal 20 minutes of 5000r/min except the larger particle of degranulation, then with 10000r/min 60 DEG C of dryings 24 hours in vacuum drier after centrifugal 10 minutes; Powder after vacuum drying treatment being placed in vacuum tightness is 1.5 × 10
-3in the crystallization furnace of pa, 450 DEG C of temperature lower calcinations 1 hour, obtain two-dimensional layer titanium carbide nanometer sheet, the two-dimentional Ti of preparation
3c
2nanometer sheet lateral dimension is 5-10 micron, and individual layer mean thickness is about 10 ~ 20 nanometers, and resistivity is 10 Ω cm.
Embodiment 4
By the molar ratio ingredient of Ti: Al: C=3: 1: 2, in ball grinder, be dry mixed 10 hours by ratio of grinding media to material 2: 1 together with agate ball; The pressure batching mixed being put into graphite jig 15MPa is real, be placed in the hot pressing furnace of argon shield, with the ramp to 1350 DEG C of 20 DEG C/min, under 25MPa pressure, be incubated 25 minutes, after being cooled to 60 DEG C, obtain loose block Ti
3alC
2, through broken, ground 200 mesh sieves; By the Ti of 6 grams
3alC
2powder is dipped in the HF aqueous solution of 100 milliliters of 50wt% under room temperature, reacts 40 hours with the rotating speed magnetic agitation of 1500r/min; It is repeatedly clean with dehydrated alcohol after neutrality that gained suspension is washed to pH value after filtration, repeatedly again, then with centrifugal 20 minutes of 5000r/min except the larger particle of degranulation, then with 8000r/min 60 DEG C of dryings 20 hours in vacuum drier after centrifugal 10 minutes; Powder after vacuum drying treatment being placed in vacuum tightness is 0.8 × 10
-3in the crystallization furnace of pa, 750 DEG C of temperature lower calcinations 1 hour, obtain two-dimensional layer titanium carbide nanometer sheet, the two-dimentional Ti of preparation
3c
2nanometer sheet lateral dimension is 10-20 micron, and individual layer mean thickness is about 10 ~ 20 nanometers, and resistivity is 0.5 Ω cm.
Embodiment 5
By the molar ratio ingredient of Ti: Al: C=3: 1: 2, in ball grinder, be dry mixed 12 hours by ratio of grinding media to material 2: 1 together with agate ball; The pressure batching mixed being put into graphite jig 10MPa is real, be placed in the hot pressing furnace of argon shield, with the ramp to 1350 DEG C of 25 DEG C/min, under 20MPa pressure, be incubated 30 minutes, after being cooled to 65 DEG C, obtain loose block Ti
3alC
2, through broken, ground 200 mesh sieves; By the Ti of 8 grams
3alC
2powder is dipped in the HF aqueous solution of 120 milliliters of 50wt% at 50 DEG C, reacts 6 hours with the rotating speed magnetic agitation of 2500r/min; It is repeatedly clean with dehydrated alcohol after neutrality that gained suspension is washed to pH value after filtration, repeatedly again, then with centrifugal 30 minutes of 3000r/min except the larger particle of degranulation, then with 10000r/min 60 DEG C of dryings 20 hours in vacuum drier after centrifugal 10 minutes; Powder after vacuum drying treatment being placed in vacuum tightness is 0.5 × 10
-3in the crystallization furnace of pa, 450 DEG C of temperature lower calcinations 2 hours, obtain two-dimensional layer titanium carbide nanometer sheet, the two-dimentional Ti of preparation
3c
2nanometer sheet lateral dimension is 12-20 micron, and individual layer mean thickness is about 10 ~ 20 nanometers, and resistivity is 8 Ω cm.
Claims (7)
1. the preparation method of a kind Graphene two-dimensional layer titanium carbide nanometer sheet, is characterized in that, comprise the following steps:
(1) Ti
3alC
2the preparation of powder: after shaping for the dry grinding of Ti, Al and C powder, the Ti that original position solid-liquid reaction obtains loose bulk occurs in the hot pressing furnace of argon shield
3alC
2, then to the Ti obtained
3alC
2carry out grinding, sieving obtains Ti
3alC
2powder, wherein, the condition of step (1) situ solid-liquid reaction is: the temperature in hot pressing furnace, with behind ramp to 1300 ~ 1400 of 10 ~ 25 DEG C/min DEG C, is incubated 20 ~ 30 minutes under 20 ~ 30MPa pressure, then be cooled to 50 ~ 70 DEG C, obtain loose block Ti
3alC
2;
(2) preparation of two-dimentional titanium carbide: by the Ti obtained in step (1)
3alC
2powder is dipped in the aqueous solution of HF, and magnetic agitation issues biochemical liquid phase reaction, obtains suspension, by above-mentioned suspension after filtration, washing, alcohol wash, centrifugal after low-temperature vacuum drying again, obtain two-dimentional titanium carbide powder, wherein, Ti
3alC
2the mass volume ratio of powder and the HF aqueous solution is (6 ~ 10): the concentration of (100 ~ 120) g/ml, HF aqueous solution is 45 ~ 55wt%, and temperature is 45 ~ 55 DEG C;
(3) vacuum calcining aftertreatment: the two-dimentional titanium carbide powder obtained in step (2) is placed in calcining in vacuum crystallization furnace and obtains class Graphene two-dimensional layer titanium carbide nanometer sheet, wherein, the vacuum tightness in vacuum crystallization furnace is 0.5 × 10
-3~ 2 × 10
-3pa, calcining temperature is 450 ~ 750 DEG C, and calcination time is 1 ~ 2h.
2. preparation method according to claim 1, is characterized in that, in step (1), the mol ratio of Ti, Al and C powder is 3: 1: 2.
3. preparation method according to claim 1, it is characterized in that, in step (1), shaping condition of dry grinding is: the mixture of Ti, Al and C powder and agate ball are dry mixed 8 ~ 12h by weight 1: 2 in ball grinder, adopt graphite molds, forming pressure is 5 ~ 15MPa.
4. preparation method according to claim 1, is characterized in that, the sub-sieve sieved in step (1) is 100 ~ 200 orders.
5. preparation method according to claim 1, is characterized in that, in step (2), the speed of magnetic agitation is 1000 ~ 2500r/min, and churning time is 6 ~ 40 hours.
6. preparation method according to claim 1, it is characterized in that, the suspension obtained after chemical liquid phase reaction in step (2) after filtration, washing, centrifugal condition after alcohol wash be: first the centrifugal 20 ~ 30min of 3000 ~ 5000r/min removes oarse-grained particle, then centrifugal 10 ~ 20min under 8000 ~ 10000r/min, collects the solid obtained.
7. preparation method according to claim 1, is characterized in that, in step (2), the temperature of low-temperature vacuum drying is 40 ~ 60 DEG C, and time of drying is 20 ~ 30h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1352317A (en) * | 2000-11-06 | 2002-06-05 | 中国科学院金属研究所 | Method for preparing titanium aluminium carbon block material by in-situ hot pressing/solid-liquid phase reaction |
| CN103641119A (en) * | 2013-12-03 | 2014-03-19 | 江苏大学 | Preparation method of material similar to graphene |
-
2014
- 2014-06-03 CN CN201410243022.0A patent/CN104016345B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1352317A (en) * | 2000-11-06 | 2002-06-05 | 中国科学院金属研究所 | Method for preparing titanium aluminium carbon block material by in-situ hot pressing/solid-liquid phase reaction |
| CN103641119A (en) * | 2013-12-03 | 2014-03-19 | 江苏大学 | Preparation method of material similar to graphene |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis of a new graphene-like transition metal carbide by de-intercalating Ti3AlC2;Fangyuan Chang et al.;《Materials Letters》;20130802;第109卷;第295-298页 * |
| Two-Dimensional Transition Metal Carbides;Michael Naguib et al.;《ACS NANO》;20120126;第6卷(第2期);第1322页第3段、第1323页第1段及第1324页最后1段 * |
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