阅读说明：本技术 一种易分解盐辅助制备二维纳米材料的方法 (A kind of method that easy salt decomposition auxiliary prepares two-dimension nano materials ) 是由 毋伟 李月微 王武 尹翔鹭 于 2019-09-09 设计创作，主要内容包括：一种易分解盐辅助制备二维纳米材料的方法,属于二维纳米材料制备技术领域。将层状材料(石墨、二硫化钼等)与低温易分解盐混合球磨后,通过退火处理,得到预插层粉末,将其配成分散液,通过超声或高剪切剥离,可得到小于十层的二维纳米材料。本发明以易分解盐作为剥离助剂,有利于粉碎层状材料并防止片层重堆叠,此外,部分易分解盐可插入层状粉末的层间,有利于剪切剥离,得到的二维纳米片层数少、纳米片尺寸可控,产量高。该方法剥离效率高、制备简单、具有工业化应用前景等优点。(A kind of method that easy salt decomposition auxiliary prepares two-dimension nano materials, belongs to two-dimension nano materials preparation technical field.After stratified material (graphite, molybdenum disulfide etc.) and the easy salt decomposition mixing and ball milling of low temperature, by annealing, pre- intercalation powder is obtained, dispersion liquid is made into, removed by ultrasound or high shear, the two-dimension nano materials less than ten layers can be obtained.The present invention is conducive to crush stratified material and prevents lamella from stacking again, furthermore using easy salt decomposition as removing auxiliary agent, part easily salt decomposition can be inserted into the interlayer of Layering powder, be conducive to shearing removing, the obtained two-dimensional nano piece number of plies is few, nanometer chip size is controllable, and yield is high.This method charge stripping efficiency is high, preparation is simple, has many advantages, such as industrial applications prospect.)

1. a kind of method that easy salt decomposition auxiliary prepares two-dimension nano materials, which is characterized in that including process below and step:

1) it using bulky grain stratified material as raw material, after being mixed in a certain proportion ball milling with easy salt decomposition, is made annealing treatment, is annealed While remove extra easy salt decomposition, make the Layering powder interlamellar spacing tentatively crushed increase, obtain the powder of pre- intercalation；

2) powder for the pre- intercalation that step 1) obtains is made into dispersion liquid, ultrasound or high-shear mixer in, carry out removing and Processing obtains two-dimension nano materials.

2. the method that a kind of easy salt decomposition auxiliary described in accordance with the claim 1 prepares two-dimension nano materials, which is characterized in that step Rapid block stratified material 1) is various graphite (natural graphite, expanded graphite, crystalline flake graphite etc.), molybdenum disulfide (natural two sulphur Change molybdenum, synthesis of carbon/molybdenum disulfide) etc..

3. the method that a kind of easy salt decomposition auxiliary described in accordance with the claim 1 prepares two-dimension nano materials, which is characterized in that step Rapid easy salt decomposition 1), for any one or a few in carbonate and labile nitrate, oxalates and hydrochloride.

4. the method that a kind of easy salt decomposition auxiliary described in accordance with the claim 3 prepares two-dimension nano materials, which is characterized in that carbon Hydrochlorate is selected from ammonium hydrogen carbonate, ammonium carbonate and urea；Salt in nitrate, oxalates and hydrochloride is the salt of ammonium class.

5. the method that a kind of easy salt decomposition auxiliary described in accordance with the claim 1 prepares two-dimension nano materials, big of step 1) The mass ratio of grain stratified material and easy salt decomposition is 1:0.1-1:10.

6. the method that a kind of easy salt decomposition auxiliary described in accordance with the claim 1 prepares two-dimension nano materials, the ball milling of step 1) Time is 1-24h, rotational speed of ball-mill 50-350rpm.

7. the method that a kind of easy salt decomposition auxiliary described in accordance with the claim 1 prepares two-dimension nano materials, the annealing of step 1) Processing, carries out under inert gas protection, and minimum annealing temperature is easy salt decomposition temperature of initial decomposition, and highest annealing temperature is 900 DEG C, heating rate is 2-10 DEG C/min, annealing time 2h.

8. the method that a kind of easy salt decomposition auxiliary described in accordance with the claim 1 prepares two-dimension nano materials, step 2) it is pre-inserted Layer powder can be dispersed into different solutions, such as organic solvent, water, cosolvent.

9. the method that a kind of easy salt decomposition auxiliary described in accordance with the claim 1 prepares two-dimension nano materials, described in step 2) Ultrasonic treatment is removed, ultrasonic power using the ultrasound cavitation effect that the instruments such as ultrasonic cleaner, probe sonication generate 200W, splitting time 1-6h.

10. the method that a kind of easy salt decomposition auxiliary described in accordance with the claim 1 prepares two-dimension nano materials, described in step 2) High-shear mixer processing generates higher local energy-dissipation rate that is, using gap narrow between the dynamic rotor of mixer And greatly shear rate is removed, and removes revolving speed 300-18000rpm/min, splitting time 1-6h.

Technical field

The invention belongs to two-dimension nano materials preparation technical fields more particularly to liquid phase shearing removing to prepare two-dimensional nano material The application in material field.

Background technique

Nano material has small size, surface and interface, quantum size, macroscopic quantum tunneling etc. compared to body phase material Effect, just because of these special properties and rule, nano material has extensively in fields such as optics, magnetics, electronics, biology Wealthy application prospect.Since two thousand four, Novoselov et al. prepares graphene by micromechanics stripping method, it was demonstrated that two dimension Nano material can be stabilized at ambient conditions.Everybody traditional cognitive to two-dimension nano materials has been broken in this discovery, Promote the preparation of more and more researcher's study two-dimensional ultrathin nanometer materials, property and application.For example graphene, transition gold Belong to sulfide (such as molybdenum disulfide, tungsten disulfide), transition metal oxide (such as molybdenum oxide, titanium oxide), Mxene two-dimensional nano Material has very big development potentiality in device, energy storage, sensing, catalysis, medicine and other fields, still, it is desirable to realize two-dimensional nano Material is badly in need of developing a kind of side of preparation high quality nanometer sheet simple, efficient, at low cost in the industrial applications in each field Method is one of bottleneck for being nowadays badly in need of capturing and present research emphasis and difficult point.

Currently, the common mode for preparing two-dimension nano materials includes that (such as hydrothermal synthesis method is vapor-deposited method from bottom to top Method, epitaxial growth method), method (such as lithium ion graft process, oxidation-reduction method, electrochemical stripping method, supercritical fluid stripping from top to bottom From method, liquid phase stripping method).Wherein, method and lithium ion graft process from bottom to top, although preparation product quality is high, yield is high, Operating environment requirement is harsh, and post-processing is cumbersome, easily introducing impurity, influences properties of product；Redox rule is often accompanied by product Defect is more, easily causes the problem of environmental pollution；And electrochemical stripping method drives yin-yang in electrolyte solution using electric field action The intercalation repeatedly of ion, the final two-dimension nano materials for obtaining few layer, the cost is relatively high for this method, it is difficult to realize extensive raw It produces；In addition, the supercritical fluid stripping method risen in the recent period, although simple process, advantage of lower cost, operating process needs Higher pressure is kept for a long time, promotes supercritical fluid intercalation stripping, and the safety operation problem of this method becomes industry amplification Difficult point；In view of productivity and operation cost, liquid phase stripping method is considered as one of the mode that pole is easy to realize industrial production, because It is easy to operate, efficient for this method, nano material can be prepared without particular surroundings.In liquid phase stripping process, equipment is needed Enough energy are provided, such as ultrasound, shearing equipment, the Van der Waals force for overcoming stratified material interlayer weaker, also needs selection suitable Auxiliary agent and solvent up-stripping are dispersed in water, You Jirong for example by natural block raw material or chemically synthesized raw material In agent, cosolvent or ionic liquid, and suitable auxiliary agent, such as surfactant are selected, salt, metal hydroxides or polymer etc. Up-stripping improves the yield and dispersion stabilization of nanometer sheet.Although liquid phase stripping method prepares the method layer of two-dimension nano materials It is not poor out, but yield is relatively low at present, it usually needs pretreatment improves yield, as Microwave Pretreatment, dry ice assist ball milling Deng generally requiring the additive of special environment or valuableness, cause process costs to increase, be unfavorable for industrialized production.Therefore, it opens It sends out one kind at normal temperatures and pressures, yield and product quality can be improved, be conducive to industry amplification, the removing of efficient liquid phase Method is the research hotspot of nowadays field of nano material preparation.

The present invention is using easy salt decomposition as auxiliary agent, under ball milling, the processing of ultrasound/high-shear mixer, with it is simple, efficient, Economic mode, successfully prepares the high two-dimensional nano piece of surface cleaning, yield.Advantage using easy salt decomposition as auxiliary agent exists In: (1) play the role of physical grinding, accelerates raw material ball mill grinding process, while preventing lamella from stacking again.(2) easy salt decomposition It easily decomposes, post-processing is simple, and i.e. separable by high temperature, product quality is high, is not introduced into impurity.(3) easily salt decomposition can be inserted partially Enter stratified material interlayer, weaken interlayer Van der Waals force, improves removing yield.(4) it is at low cost to compare other auxiliary agents for easy salt decomposition.Together When, using ball milling, ultrasound or the high-shear mixer of easily scale amplification as peel-off device, improves this method and realize industry Change manufacturing feasibility.

Summary of the invention

The present invention provides the new method that a kind of easy salt decomposition auxiliary prepares two-dimension nano materials.Using easy salt decomposition as helping Agent, assist ball milling, by annealing after obtain pre- intercalation powder, by pre- intercalation powder dispersion in a solvent, by ultrasound or High shear removing, obtained two-dimension nano materials quality is high, defect is few.

The invention discloses a kind of methods that easy salt decomposition auxiliary prepares two-dimension nano materials, including process below and step It is rapid:

1) it using bulky grain stratified material as raw material, after being mixed in a certain proportion ball milling with easy salt decomposition, is made annealing treatment, Extra easy salt decomposition is removed while annealing, is increased the Layering powder interlamellar spacing tentatively crushed, is obtained the powder of pre- intercalation；

2) powder for the pre- intercalation that step 1) obtains is made into dispersion liquid, in ultrasound or high-shear mixer, is shelled Two-dimension nano materials are obtained from processing.

The block stratified material of step 1) includes and is not limited to: various graphite (natural graphite, expanded graphite, crystalline flake graphites Deng), molybdenum disulfide (natural molybdenum disulfide, synthesis of carbon/molybdenum disulfide) etc..

The easy salt decomposition of step 1), including and be not limited to: labile carbonate, such as: ammonium hydrogen carbonate, ammonium carbonate and urea Deng；Labile nitrate, oxalates and hydrochloride, the salt in nitrate, oxalates and hydrochloride are the salt of ammonium class, etc..

The bulky grain stratified material of step 1) and the mass ratio of easy salt decomposition are 1:0.1-1:10.

The Ball-milling Time of step 1) is 1-24h, rotational speed of ball-mill 50-350rpm.

The annealing of step 1) carries out under inert gas protection, and minimum annealing temperature is easy salt decomposition initial decomposition Temperature, highest annealing temperature are 900 DEG C, and heating rate is 2-10 DEG C/min, and anneal 2h.

The pre- intercalation powder of step 2) can be dispersed into different solutions, such as organic solvent, water, cosolvent.

Ultrasonic treatment described in step 2), i.e., the ultrasonic cavitation generated using instruments such as ultrasonic cleaner, probe sonications Effect is removed, ultrasonic power 200W, splitting time 1-6h.

The processing of high-shear mixer described in step 2) moves narrow gap between rotor using mixer, generate compared with High local energy-dissipation rate and great shear rate are removed, and revolving speed 300-18000rpm/min, removing are removed Time 1-6h.

This method is easy to operate, efficient, at low cost, suitable for scale production, is with a wide range of applications.

Detailed description of the invention

It is described further in conjunction with picture for specific embodiments of the present invention；

The TEM figure of the two-dimentional molybdenum disulfide of the removing preparation of Fig. 1 embodiment of the present invention 1；

The TEM figure of the graphene of the removing preparation of Fig. 2 embodiment of the present invention 12；

The AFM figure of the graphene of the removing preparation of Fig. 3 embodiment of the present invention 12；

The conductivity of the graphene of the removing preparation of Fig. 4 embodiment of the present invention 12 is with pressure change curve graph；

Specific embodiment

It is of the invention for ease of understanding, following specific embodiments will be enumerated, is described in further detail, protection model of the invention Enclosing should include the full content of claim and specific embodiment, but be not limited to this, in the condition without departing substantially from the scope of the invention Under, various changes that those of ordinary skill in the art are able to carry out.