CN108467019A - A kind of Ti2The preparation method of N two-dimensional materials - Google Patents

A kind of Ti2The preparation method of N two-dimensional materials Download PDF

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Publication number
CN108467019A
CN108467019A CN201810426924.6A CN201810426924A CN108467019A CN 108467019 A CN108467019 A CN 108467019A CN 201810426924 A CN201810426924 A CN 201810426924A CN 108467019 A CN108467019 A CN 108467019A
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powder
preparation
dimensional materials
ball milling
solid solution
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CN201810426924.6A
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Inventor
刘毅
刘卓
刘一卓
张利锋
郑鹏
原晓艳
王晓飞
霍京浩
郭守武
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A kind of Ti2The preparation method of N two-dimensional materials, first, it is raw material to weigh Ti, Al, Ga, In, Sn and TiN according to molar ratio, and Ti powder, Al powder, In powder, Sn powder, TiN powder are first carried out ball milling mixing, it is dry, Ga blocks are added, grinding uniformly obtains mixed powder, secondly, gained mixed powder is pressed into green body, it is sintered under the conditions of certain temperature, grinds off surface oxide layer, obtain Ti2The solid solution of AlN finally after the broken obtained powder sieving of solid solution, is placed in hydrochloric acid and stirs, centrifuged to product, washing to neutrality is dry, obtains two-dimensional material, can prepare Ti under mild process conditions2N two-dimensional materials have the characteristics that simple for process, mild condition.

Description

A kind of Ti2The preparation method of N two-dimensional materials
Technical field
The present invention relates to field of inorganic nano-material preparation, more particularly to a kind of Ti2The preparation method of N two-dimensional materials.
Background technology
MAX phases are ternary layered compound, general formula Mn+1AXn(n=1,2,3), wherein M represents transition metal element, A For group IIIA or IV A races element, X is carbon or nitrogen.Pass through after carrying out A layers of atom of selective etch to MAX phase materials Stripping can obtain new two-dimentional MXene materials.Such material has various electricity, magnetics, thermoelectricity capability and excellent There is very wide answer in fields such as ion battery, ultracapacitor, hydrogen storages in the characteristics such as electrochemistry, heavy metal ion adsorbed Use foreground.
Most common carbon-based MXenes has Ti3C2, fallen by hydrofluoric acid or villiaumite mixing hydrochloric acid selective etch Ti3AlC2In the obtained two-dimentional Ti of Al layers3C2.Compared with carbon-based MXenes, nitrogen base MXenes is due to its higher electronic conduction Property, transition metal nitride is considered being hopeful to be applied to plasma, electrochemical capacitor, optics and Meta Materials device.
And nitrogen base MAX is due to active larger at present, it is difficult to which carrying out selective etch by hydrofluoric acid obtains corresponding two dimension Nitride.It is directed to Ti therein2AlN strippings prepare Ti2There are prodigious technical difficulty, 1 [Dissertations＆ of document by N Theses-Gradworks,2014,45(4):787-99.] pass through the HF acid processing Ti of low concentration2AlN is formed on its surface Oxide but stratiform Ti is not obtained yet2N.Document 2 [Acs Nano, 2017,11 (9)] passes through KF the and HCl mixing low temp short time Handle Ti2AlN obtains Ti2N.The above technology has certain danger using hydrofluoric acid or villiaumite mixing hydrochloric acid, and cannot have Effect leniently prepares Ti2N two-dimensional materials, it would be highly desirable to develop new preparation means.
Invention content
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of Ti2The preparation of N two-dimensional materials Method can prepare Ti under mild process conditions2N two-dimensional materials have the characteristics that simple for process, mild condition.
In order to achieve the above object, the technical solution that the present invention takes is：
A kind of Ti2The preparation method of N two-dimensional materials, steps are as follows：
Step 1：According to Ti：(Al, Sn, In and Ga)：The molar ratio of TiN is 1：(1-1.1)：1, wherein Al：Sn：In：Ga Molar ratio be (0.7-0.9)：(0-0.3)：(0-0.3)：(0-0.3) weighs raw material, first by Ti powder, Al powder, In powder, Sn powder, TiN powder carries out ball milling mixing, dry, adds Ga blocks, and grinding uniformly obtains mixed powder；
Step 2：Step 1 gained mixed powder is pressed into green body, 2-5min is sintered under 600-800 DEG C of temperature condition, Surface oxide layer is ground off, Ti is obtained2The solid solution of AlN；
Step 3：After the broken obtained powder of solid solution is crossed 300 mesh sieve, be placed in hydrochloric acid and stir, to product carry out from The heart, washing to neutrality is dry, obtains two-dimensional material.
The pellet mass ratio 1 of step 1 ball milling mixing：5.
The medium of step 1 ball milling mixing is absolute ethyl alcohol.
Step 2 blank sintering uses air furnace.
Concentration of hydrochloric acid 1-3mol/L in the step 3.
Step 3 mixing time is 4-24h.
The present invention having the beneficial effect that compared with prior art：
Nitrogen base Ti at present2AlN is larger due to activity, it is difficult to selective etch be effectively performed by prior art ideal and fall Al layers are prepared Ti2Ga, In, Sn are solid-solubilized in Ti by N two-dimensional materials, the present invention first with thermal explosion method2Al layers in AlN, greatly Al layers of activity is improved, active layer is then removed by pickling, to obtain Ti2N two-dimensional materials, preparation process is simple, item Part is mild, safely and effectively.
Description of the drawings
Fig. 1 is Ti prepared by thermal explosion method2The XRD diagram of AlN and solid solution.
Fig. 2 is the energy spectrum analysis figure of gained solid solution.
Fig. 3 is the SEM figures of product after gained solid solution HCl treatment.
Specific implementation mode
The present invention is described in further details with reference to embodiment.
Embodiment one：
Step 1：By Ti, Al, Ga, In, Sn and TiN powder according to mol ratio 1：0.9：0.05：0.05：0：1 weighs, so First the Ti powder that weighs up, Al powder, In powder, Sn powder, TiN powder are placed in agate jar afterwards, carried out by medium of absolute ethyl alcohol Ball milling mixing, the pellet mass ratio 1 of ball milling mixing：5, the slurry after ball milling is taken out, it is dry, dry powder is obtained, is added The Ga blocks weighed up, ground and mixed are uniform.
Step 2：Powder is poured into stainless steel mould, compression moulding, green compact is put into 700 DEG C of air furnace and is reacted It is taken out after 5min, grinds off surface oxide layer, obtain Ti2The solid solution of AlN.
Step 3：Solid solution is broken into powder, after crossing 300 mesh screens, with 1mol/L HCl treatments, is stirred at room temperature for 24 hours, Product is washed through multiple deionized water, and centrifugation to supernatant pH value obtains two-dimensional material close to neutrality, vacuum drying.
Referring to Fig. 1, it can be seen that apparent offset has occurred in diffraction maximum, show that Ga, In, Sn are dissolved into Ti2AlN's In lattice.
Referring to Fig. 2, show that there are Ga, In, Sn, Ti, Al, N elements in solid solution.
Referring to Fig. 3, it can be seen that product Ti2N is stratiform two-dimensional structure.
Embodiment two：
Step 1：By Ti, Al, Ga, In, Sn and TiN powder according to mol ratio 1：0.9：0.06：0.03：0.01：1 claims Then the Ti powder that weighs up, Al powder, In powder, Sn powder, TiN powder are first placed in agate jar, using absolute ethyl alcohol as medium by amount Carry out ball milling mixing, the pellet mass ratio 1 of ball milling mixing：5, the slurry after ball milling is taken out, it is dry, dry powder is obtained, then The Ga blocks weighed up are added, ground and mixed is uniform.
Step 2：Powder is poured into stainless steel mould, compression moulding, green compact is put into 600 DEG C of air furnace and is reacted It is taken out after 3min, grinds off surface oxide layer, obtain Ti2The solid solution of AlN.
Step 3：Solid solution is broken into powder, after crossing 300 mesh screens, with 1mol/L HCl treatments, 12h is stirred at room temperature, Product is washed through multiple deionized water, and centrifugation to supernatant pH value obtains two-dimensional material close to neutrality, vacuum drying.
Embodiment three：
Step 1：By Ti, Al, Ga, In, Sn and TiN powder according to mol ratio 1：0.9：0.05：0.03：0.02：1 claims Then the Ti powder that weighs up, Al powder, In powder, Sn powder, TiN powder are first placed in agate jar, using absolute ethyl alcohol as medium by amount Carry out ball milling mixing, the pellet mass ratio 1 of ball milling mixing：5, the slurry after ball milling is taken out, it is dry, dry powder is obtained, then The Ga blocks weighed up are added, ground and mixed is uniform.
Step 2：Powder is poured into stainless steel mould, compression moulding, green compact is put into 700 DEG C of air furnace and is reacted It is taken out after 5min, grinds off surface oxide layer, obtain Ti2The solid solution of AlN.
Step 3：Solid solution is broken into powder, after crossing 300 mesh screens, with 2mol/L HCl treatments, 8h is stirred at room temperature, is produced Object is washed through multiple deionized water, and centrifugation to supernatant pH value obtains two-dimensional material close to neutrality, vacuum drying.
Example IV：
Step 1：By Ti, Al, Ga, In, Sn and TiN powder according to mol ratio 1：0.9：0.05：0.02：0.03：1 claims Amount, then first the Ti powder weighed up, Al powder, In powder, Sn powder, TiN powder are placed in agate jar, using absolute ethyl alcohol as medium into Row ball milling mixing, the pellet mass ratio 1 of ball milling mixing：5, the slurry after ball milling is taken out, it is dry, dry powder is obtained, then add Enter the Ga blocks for taking and weighing up, ground and mixed is uniform.
Step 2：Powder is poured into stainless steel mould, compression moulding, green compact is put into 800 DEG C of air furnace and is reacted It is taken out after 2min, grinds off surface oxide layer, obtain Ti2The solid solution of AlN.
Step 3：It is broken into powder, crosses 300 mesh screens, use 3mol/L HCl treatments afterwards, 4h is stirred at room temperature, product is through multiple Deionized water is washed, centrifugation to the close neutrality of supernatant pH value.Vacuum drying, obtains two-dimensional material.

Claims (6)

1. a kind of Ti2The preparation method of N two-dimensional materials, which is characterized in that include the following steps：
Step 1：According to Ti：(Al, Sn, In and Ga)：The molar ratio of TiN is 1：(1-1.1)：1, wherein Al：Sn：In：Ga's rubs You are than being (0.7-0.9)：(0-0.3)：(0-0.3)：(0-0.3) weighs raw material, first by Ti powder, Al powder, In powder, Sn powder, TiN powder Ball milling mixing is carried out, it is dry, Ga blocks are added, grinding uniformly obtains mixed powder；
Step 2：Step 1 gained mixed powder is pressed into green body, 2-5min is sintered under 600-800 DEG C of temperature condition, grinds off Surface oxide layer obtains Ti2The solid solution of AlN；
Step 3：After the broken obtained powder of solid solution is crossed 300 mesh sieve, it is placed in hydrochloric acid and stirs, product is centrifuged, wash It washs to neutrality, it is dry, obtain two-dimensional material.
2. a kind of Ti according to claim 12The preparation method of N two-dimensional materials, which is characterized in that step 1 ball milling is mixed The pellet mass ratio 1 of conjunction：5.
3. a kind of Ti according to claim 12The preparation method of N two-dimensional materials, which is characterized in that step 1 ball milling is mixed The medium of conjunction is absolute ethyl alcohol.
4. a kind of Ti according to claim 12The preparation method of N two-dimensional materials, which is characterized in that step 2 green body is burnt Knot uses air furnace.
5. a kind of Ti according to claim 12The preparation method of N two-dimensional materials, which is characterized in that hydrochloric acid in the step 3 Concentration 1-3mol/L.
6. a kind of Ti according to claim 12The preparation method of N two-dimensional materials, which is characterized in that when step 3 stirring Between be 4-24h.
CN201810426924.6A 2018-05-07 2018-05-07 A kind of Ti2The preparation method of N two-dimensional materials Pending CN108467019A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586162A (en) * 2019-09-24 2019-12-20 华东师范大学 Layered titanium nitride nano composite material doped with molybdenum diselenide, preparation method and application
CN111847456A (en) * 2020-07-24 2020-10-30 盐城工学院 Method for preparing pure-phase MXene by using plasma etching technology
CN113060709A (en) * 2021-03-26 2021-07-02 中国科学技术大学 Ti2Preparation method of N MXene nano material and method for applying N MXene nano material to negative electrode of lithium ion battery
CN113830743A (en) * 2021-09-24 2021-12-24 北京科技大学 Preparation method of titanium nitride MXene nanosheet

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586162A (en) * 2019-09-24 2019-12-20 华东师范大学 Layered titanium nitride nano composite material doped with molybdenum diselenide, preparation method and application
CN111847456A (en) * 2020-07-24 2020-10-30 盐城工学院 Method for preparing pure-phase MXene by using plasma etching technology
CN113060709A (en) * 2021-03-26 2021-07-02 中国科学技术大学 Ti2Preparation method of N MXene nano material and method for applying N MXene nano material to negative electrode of lithium ion battery
CN113830743A (en) * 2021-09-24 2021-12-24 北京科技大学 Preparation method of titanium nitride MXene nanosheet

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