CN107416830A - A kind of preparation method of even titanium carbide - Google Patents

A kind of preparation method of even titanium carbide Download PDF

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Publication number
CN107416830A
CN107416830A CN201710363193.0A CN201710363193A CN107416830A CN 107416830 A CN107416830 A CN 107416830A CN 201710363193 A CN201710363193 A CN 201710363193A CN 107416830 A CN107416830 A CN 107416830A
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titanium carbide
preparation
chloride
ethanol solution
carbide according
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CN107416830B (en
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姜再兴
方晓娇
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer

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Abstract

A kind of preparation method of even titanium carbide, belong to the technical field of nano titanium carbide.The invention solves chemical synthesis MXene materials to have the technical problem that cost of material is high, the dangerous big and operation cycle is long and is detrimental to health using hydrofluoric acid, and the material homogeneity for overcoming existing method preparation in addition is poor, pattern problem of non-uniform.The inventive method：First, nickel foam is placed on graphite block, is placed in together in the quartz ampoule of chemical vapor deposition stove, heating, is closed outlet valve after reaching design temperature while is opened vavuum pump；Two while uniformly it is passed through the ethanol solution of ethanol solution and aluminium chloride dissolved with titanium chloride；3rd, charging closes vavuum pump after terminating, and cools, is dipped into HCl and HF mixed solution, water-bath, is then centrifuged for, take clear liquid to drip on silicon chip, dries, produces nano titanium carbide.It is the thin slice that 100 200nm, thickness are about 10nm that the inventive method, which obtains length,.

Description

A kind of preparation method of even titanium carbide
Technical field
The invention belongs to the technical field of nano titanium carbide；More particularly to a kind of preparation method of even titanium carbide.
Background technology
MAX phases refer to the presoma before MXene etchings, and its formula is Mn+1Axn, include phase known to kind about more than 60 at present. MAX phases (such as Ti3SiC2、Ti3AlC2、Ti2AlC etc.) it is a kind of new processable ceramics material to receive much concern, it is a kind of intrinsic The nanometer layer ternary nitride and carbide of ductility.M represents transition metal, and A represents major element, and X represents carbon or nitrogen.From From the 1960s, MXene materials start widely to be studied in terms of energy storage, and generally these attributes are corresponding to it MAX phases also have concurrently.
At present, the existing method for preparing the material is chemical synthesis, and this method prepares production life cycle length, and cost is high and can Be applied to hydrofluoric acid during being, hydrofluoric acid is a kind of irritant smell, the moderate strength acid on the weak side of severe toxicity, but with skin After skin contact, fluorine ion constantly dissociates and penetrates into deep tissues, is restricted skin oxygen uptake capacity, seriously endangers human body and is good for Health.
The content of the invention
The invention solves chemical synthesis MXene materials have cost of material height, the dangerous big and operation cycle is long and answers The technical problem being detrimental to health with hydrofluoric acid, overcome in addition existing method preparation material homogeneity is poor, pattern inequality Even problem, and provide a kind of preparation method of even titanium carbide.
In order to solve the above technical problems, the preparation method of even carbon aluminium titanium is to follow the steps below in the present invention 's：
Step 1: the porous nickel mesh of pretreatment is placed on graphite block as substrate, the two is placed in chemical gas together In the quartz ampoule of phase cvd furnace, open air intake valve and go out valve, be passed through argon gas, be warming up under an argon atmosphere 500 DEG C- At 700 DEG C, close outlet valve and open vavuum pump simultaneously, quartzy overpressure is evacuated to close to absolute vacuum；
Step 2: control dual-channel peristaltic pump rotating speed makes it in being passed through in 20min-25min while uniformly the second of titanium chloride The intake of the ethanol solution of alcoholic solution and aluminium chloride, the ethanol solution of titanium chloride and the ethanol solution of aluminium chloride is equal, is passed through Measure as 5mL~20mL；
Step 3: charging closes vavuum pump after terminating, continue to be passed through argon gas to normal pressure, then open outlet valve, Temperature is down to 350 DEG C -400 DEG C in 30min-40min, taken out after cooling to room temperature with the furnace, piece is obtained on porous nickel mesh surface Shape nano material is carbon aluminium titanium；
Step 4: the porous nickel mesh that step 3 is obtained is dipped into mixed acid, the heating water bath under the conditions of 45 DEG C -50 DEG C 12h, then 8000r/min-10000r/min centrifuged, take clear liquid to drip on silicon chip, dry, produce nano titanium carbide；
Mixed acid wherein described in step 4 adds HF into HCl solution and is formulated.
Further limit, when being warming up to 520 DEG C -680 DEG C in step 1, close outlet valve and open vavuum pump simultaneously.
Quartzy overpressure is evacuated to -0.09MPa~-0.1MPa in step 1.
Low in raw material price of the present invention, therefore reduce and prepare cost；The present invention is molten using HCl solution and solid HF configuration acid Liquid, reduce danger.
Typically time-consuming 24-48 hours in the operation cycle of existing chemical synthesis process, by contrast, operation of the invention week Phase is short, can obtain nano titanium carbide material within general 6 hours.
The present invention is by controlling depositing temperature and time preferably to control the spies such as product thickness, pattern and smoothness Sign.
The present invention is smaller to air pollution, and hydrogen chloride gas caused by aluminium chloride and titanium chloride can more fully hereinafter be delayed Sodium bicarbonate solution in bottle is rushed to absorb.
It is the nano titanium carbide thin slice that 100-200nm, thickness are about 10nm that the inventive method, which obtains length, and thin skin table Face is smooth, pattern is uniform.
Products application of the present invention is in capacitor area.
Brief description of the drawings
Fig. 1 is titanium carbide scanning electron microscopic picture × 20000 prepared by the method for embodiment one；Fig. 2 is specific implementation Titanium carbide scanning electron microscopic picture × 50000 prepared by the method for mode one；Fig. 3 is titanium carbide ESEM prepared by comparative example method Picture × 20000；Fig. 4 is titanium carbide scanning electron microscopic picture × 50000 prepared by comparative example method.
Embodiment
Embodiment one：The method that present embodiment prepares even carbon aluminium titanium follows the steps below：
Step 1: nickel foam first is cut into 1cm × 1cm, then carry out ultrasound with absolute ethyl alcohol, acetone, absolute ethyl alcohol successively Ripple cleans, and completes the pretreatment of nickel foam, is then placed in the porous nickel mesh of pretreatment on graphite block as substrate, incite somebody to action the two It is placed in together in the quartz ampoule of chemical vapor deposition stove, opens air intake valve and valve of going out, be passed through argon gas, under an argon atmosphere When being warming up to 550 DEG C, close outlet valve and open vavuum pump simultaneously, quartzy overpressure is evacuated to -0.09MPa (close to definitely Vacuum)；
Step 2: dual-channel peristaltic pump rotating speed is controlled as 6.4r/min while is uniformly passed through the ethanol solution and chlorine of titanium chloride The intake of the ethanol solution of change aluminium, the ethanol solution of titanium chloride and the ethanol solution of aluminium chloride is equal, and intake is 20mL；
Step 3: charging closes vavuum pump after terminating, continue to be passed through argon gas to normal pressure, then open outlet valve, Temperature is down to 350 DEG C in 30min, taken out after cooling to room temperature with the furnace, obtaining flake nano material on porous nickel mesh surface is Carbon aluminium titanium；
Step 4: the porous nickel mesh that step 3 is obtained is dipped into mixed acid, the heating water bath 12h under the conditions of 48 DEG C, Then 8000r/min is centrifuged, and takes clear liquid to drip on silicon chip, is dried, is produced nano titanium carbide；
Wherein, it is 1 dissolved with the mass ratio of titanium chloride and ethanol in the ethanol solution of titanium chloride described in step 2:40；
Described in step 2 dissolved with the mass ratio of aluminium chloride and ethanol in the ethanol solution of aluminium chloride be 1:40；
HCl described in step 4 and HF mixed solution is that 6mol/LHCl and 1.5g HF are formed by 100mL concentration.
Comparative example：The method for preparing nano titanium carbide follows the steps below：
First, nickel foam is cut into 1cm × 1cm sizes and carries out ultrasonic wave with ethanol, acetone, ethanol and cleaned, then will bubble Foam nickel is impregnated in 12h in the mixed solution being made up of 0.45g nickel nitrates and 100mL ethanol, nickel foam is fully adsorbed nickel nitrate. Then nickel foam is taken out and is placed on graphite block and puts the two in chemical vapor deposition stove together into, start to warm up, in argon Atmosphere enclose under when temperature reaches 700 DEG C, be passed through hydrogen reducing 1h；
2nd, dual-channel peristaltic pump rotating speed is controlled to make it in being passed through in 20min while uniformly dissolved with titanium chloride for 6.4r/min Ethanol solution and aluminium chloride each 20mL of ethanol solution；
3rd, charging closes vavuum pump after terminating, and continues to be passed through argon gas to normal pressure, outlet valve is then opened, in 30min Temperature is down to 350 DEG C, nickel plate is taken out after machine naturally cools to room temperature, it is carbon aluminium titanium to obtain flake nano material；
4th, the nickel foam for obtaining step 3 is placed in the solution being made up of 100mL 6mol/LHCl and 1.5g HF, in 48 DEG C of water-bath 12h, then 8000r/min, takes clear liquid to drip on silicon chip, dries, produces titanium carbide.
Described in step 2 dissolved with the mass ratio of titanium chloride and ethanol in the ethanol solution of titanium chloride be 1:40.
Described in step 2 dissolved with the mass ratio of aluminium chloride and ethanol in the ethanol solution of aluminium chloride be 1:40.
Nickel foam in comparative example is impregnated with nickel nitrate solution, is reduced again, and depositing temperature is 700 DEG C so that the control of the pattern of product is more difficult, easy reunion and regularity are poor.The carbon aluminium titanium prepared using comparative example is from Fig. 3 and Fig. 4 Understand obtained titanium carbide material uneven surface, and material morphology heterogeneity.The carbon aluminium titanium prepared using embodiment one Understand that obtained titanium carbide material surfacing is uneven from Fig. 1 and Fig. 2, and material morphology is homogeneous.
Embodiment two：Present embodiment is unlike embodiment one：Make in step 3 in 35min Temperature is down to 380 DEG C.Other steps and parameter are identical with embodiment one.
Embodiment three：Present embodiment is unlike embodiment one：In 48 DEG C of water-baths in step 4 12h, then 9000r/min centrifuged.Other steps and parameter are identical with embodiment one.

Claims (10)

  1. A kind of 1. preparation method of even titanium carbide, it is characterised in that the preparation method of even carbon aluminium titanium be according to What lower step was carried out：
    Step 1: the porous nickel mesh of pretreatment is placed on graphite block as substrate, the two is placed in chemical vapor deposition together In the quartz ampoule of product stove, air intake valve and valve of going out are opened, argon gas is passed through, is warming up to 500 DEG C -700 DEG C under an argon atmosphere When, close outlet valve and open vavuum pump simultaneously, quartzy overpressure is evacuated to close to absolute vacuum；
    Step 2: control dual-channel peristaltic pump rotating speed make its in 20min-25min and meanwhile be uniformly passed through titanium chloride ethanol it is molten The intake of the ethanol solution of liquid and aluminium chloride, the ethanol solution of titanium chloride and the ethanol solution of aluminium chloride is equal, and intake is 5mL~20mL；
    Step 3: charging closes vavuum pump after terminating, continue to be passed through argon gas to normal pressure, outlet valve is then opened, in 30min- Temperature is down to 350 DEG C -400 DEG C in 40min, taken out after cooling to room temperature with the furnace, flake nano is obtained on porous nickel mesh surface Material is carbon aluminium titanium；
    Step 4: the porous nickel mesh that step 3 is obtained is dipped into mixed acid, the heating water bath 12h under the conditions of 45 DEG C -50 DEG C, Then 8000r/min-10000r/min is centrifuged, and takes clear liquid to drip on silicon chip, is dried, is produced nano titanium carbide；
    Mixed acid wherein described in step 4 adds HF into HCl solution and is formulated.
  2. 2. a kind of preparation method of even titanium carbide according to claim 1, it is characterised in that be warming up in step 1 At 520 DEG C -680 DEG C, close outlet valve and open vavuum pump simultaneously.
  3. 3. a kind of preparation method of even titanium carbide according to claim 1, it is characterised in that be warming up in step 1 At 550 DEG C, close outlet valve and open vavuum pump simultaneously.
  4. 4. a kind of preparation method of even titanium carbide according to claim 1, it is characterised in that by quartz in step 1 Overpressure is evacuated to -0.09MPa~-0.1MPa.
  5. 5. a kind of preparation method of even titanium carbide according to claim 1, it is characterised in that double described in step 2 Multi-channel peristaltic pump rotating speed is 6.4r/min.
  6. 6. a kind of preparation method of even titanium carbide according to claim 1, it is characterised in that molten described in step 2 It is 1 to have the mass ratio of titanium chloride and absolute ethyl alcohol in the ethanol solution of titanium chloride:40.
  7. 7. a kind of preparation method of even titanium carbide according to claim 1, it is characterised in that molten described in step 2 It is 1 to have the mass ratio of aluminium chloride and absolute ethyl alcohol in the ethanol solution of aluminium chloride:40.
  8. 8. a kind of preparation method of even titanium carbide according to claim 1, it is characterised in that in 35min in step 3 Temperature is inside set to be down to 380 DEG C.
  9. 9. a kind of preparation method of even titanium carbide according to claim 1, it is characterised in that in 48 DEG C in step 4 Water-bath 12h, then 9000r/min centrifuged.
  10. 10. a kind of preparation method of even titanium carbide according to claim 1, it is characterised in that mixed described in step 4 It is to add after 1.5g HF to mix in 6mol/LHCl to form that acid, which is closed, to 100mL concentration.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111849145A (en) * 2020-07-15 2020-10-30 福州大学 Halogen-free flame-retardant thermoplastic polyurethane nano composite material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104961131A (en) * 2015-07-03 2015-10-07 河海大学 Preparation method of sulfonated two-dimensional titanium carbide nanosheet
CN106083117A (en) * 2016-06-21 2016-11-09 中国科学院宁波材料技术与工程研究所 There is fiber reinforced ceramic matric composite of ternary layered MAX phase boundary surface layer and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104961131A (en) * 2015-07-03 2015-10-07 河海大学 Preparation method of sulfonated two-dimensional titanium carbide nanosheet
CN106083117A (en) * 2016-06-21 2016-11-09 中国科学院宁波材料技术与工程研究所 There is fiber reinforced ceramic matric composite of ternary layered MAX phase boundary surface layer and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
T. GOTO等: "CHEMICALLY VAPOR DEPOSITED Ti3SiC2", 《MAT. RES. BULL》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111849145A (en) * 2020-07-15 2020-10-30 福州大学 Halogen-free flame-retardant thermoplastic polyurethane nano composite material and preparation method thereof
CN111849145B (en) * 2020-07-15 2021-11-30 福州大学 Halogen-free flame-retardant thermoplastic polyurethane nano composite material and preparation method thereof

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