CN104817060B - A kind of preparation method of two dimension lithium doping Graphene - Google Patents
A kind of preparation method of two dimension lithium doping Graphene Download PDFInfo
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- CN104817060B CN104817060B CN201510229439.6A CN201510229439A CN104817060B CN 104817060 B CN104817060 B CN 104817060B CN 201510229439 A CN201510229439 A CN 201510229439A CN 104817060 B CN104817060 B CN 104817060B
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Abstract
The present invention discloses the preparation method of a kind of two dimension lithium doping Graphene, specifically comprises the following steps that and is added to by brucite in appropriate sodium butyrate solution, stirring, aging, separate, dry, obtain the brucite that sodium butyrate is modified；The brucite modified by sodium butyrate; join under nitrogen protection n-BuLi pentane solution is dried after stirring and grind again; powder will be obtained and put in vacuum tube furnace; it is heated to 400～600 DEG C under vacuum, calcines 2～4h, be then added in hydrochloric acid solution; by precipitate and separate the most under vacuum; it is heated to 2000～2500 DEG C, thermally treated 3～6h, i.e. obtain two dimension lithium doping Graphene after cooling.The method material is simple, mild condition.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly relate to a kind of two dimension lithium doping stone
The preparation method of ink alkene.
Background technology
In the R&D process of new material, dimension has become a weight of modulating substance structure and characteristic
Want parameter.When material is changed to two dimension, a peacekeeping zero dimension by three dimensional structure, its geometry and thing
Physical chemistry characteristic will occur significant change.Two-dimension nano materials is because having anisotropy and uniqueness
Photoelectric properties and be widely used in numerous necks such as solid nano device, sensing and function film
Territory.Particularly high starch breeding carbon 001 is in the face of the resistivity of lonizing radiation uniqueness, it is expected to be used for
Medical low energy neutron radiation resistance material, X-Ray monochromator radiation resistance material and nuclear fusion
The radiation resistance material of device, it is by the one becoming advanced science and technology field novel radioprotective material
Material.
As two-dimensional material, general thickness direction is monoatomic layer or diatomic layer carbon atom.Graphite
The theoretical implications that two-dimension single layer atomic crystal can not exist has been broken in the discovery of alkene, has caused at present
People's research boom to two dimension monoatomic layer material.This not only becomes generation in nano science field
One of important source of new knowledge, and provide for developing performance function nano material and device
Opportunity.One of the study hotspot in this field is that monoatomic layer material is carried out functional modification at present.
Along with going deep into of research, the demand of two-dimension nano materials is also stepped up, is badly in need of simple
Synthetic method.
But owing to two-dimension nano materials surface free energy is higher, often use in preparation process
Unconventional method, such as can prepare the large-area Graphene of high-quality two by CVD
Dimension nano material, but the expensive of preferable substrate material monocrystalline nickel, this is to affect stone
The key factor of ink alkene industrialized production, the most relatively costly, complex process.Additionally also
Having oxidation-reduction method, its shortcoming is the graphite that magnanimity preparation easily brings waste liquor contamination and preparation
There is certain defect, such as, the topological defect such as five-membered ring, heptatomic ring or existence-OH base in alkene
The fault of construction of group, these will cause Graphene part electrical property loss of energy, make Graphene
Application is restricted.
One of study hotspot of field of graphene is that monoatomic layer material is carried out functionalization at present
Modify.People dream of always can be regular and introduce gold discretely in these monoatomic layer materials
Belong to atom to constitute novel monoatomic layer magnetic material, catalysis material and gas adsorption material,
But owing to transition metal atoms is easily assembled, this dream fails at Graphene and monatomic always
Realize in Ceng.
Quasiconductor can be doped, and the semiconductor energy gap after doping can change.Depend on
According to the difference of alloy, between the energy gap of intrinsic semiconductor, there will be different energy rank.Execute
Body atom can produce new energy rank near the local of conduction band, and acceptor atom is then
New energy rank are being produced near the place of valence band.Alloy is for another of band structure
Significant impact is the position changing fermi level.Fermi level under thermally equilibrated state
Still can keep definite value, this characteristic can draw a lot of other useful electrical characteristics.
(Layered Double Hydroxides is called for short layered di-hydroxyl composite metal oxidate
LDH), also known as brucite, it is the important inorganic functional material of a class.The stratiform knot of its uniqueness
The adjustable degeneration of structure and laminate element and interlayer anion gets more and more people's extensive concerning, through ion
Exchange and layer structure and composition can be made to produce corresponding change to the new object anion of interlayer introducing
Change, thus a big class can be prepared there is the functional material of special nature.Hydrotalcite material belongs to
Anion type laminated compound.Lamellar compound refers to have layer structure, interlayer ion has
One compounds of interchangeability, utilizes lamellar compound main body institute under highly polar molecular action
The intercalation having and the interchangeability of interlayer ion, introduce some functional guest species
Laminate distance is also strutted thus forms layer-pillared compound by bedding void.
Brucite chemical structure of general formula is: [M2+ 1-xM3+x(OH)2]x+[(An-)x/n·mH2O],
Wherein M2+For Mg2+、Ni2+、Mn2+、Zn2+、Ca2+、Fe2+、Cu2+Etc. bivalence
Metal cation；M3+For Al3+、Cr3+、Fe3+、Co3+Deng trivalent metal cation；
An-For anion, such as CO3 2-、NO3 -、Cl-、OH-、SO4 2-、PO4 3-、C6H4(COO)2 2-
Etc. inorganic and organic ion and complex ion, when interlevel inorganic anion is different, neatly
The interlamellar spacing of stone is different.
Summary of the invention
It is an object of the invention to as overcoming complicated process of preparation in prior art, expensive etc.
Not enough, it is provided that the preparation method of a kind of two dimension lithium doping Graphene.
To this end, the invention provides techniques below scheme, the system of a kind of two dimension lithium doping Graphene
Preparation Method, in turn includes the following steps:
1) according to the amount of the corresponding 0.5～1mmol sodium butyrate of every gram of brucite, by 20-50 mesh
The brucite of sieve joins in the sodium butyrate solution that mass percent concentration is 0.1%～1%,
Stirring 5～6h in 60～70 DEG C of waters bath with thermostatic control, aging 12～24h, then by this precipitate from liquid
Middle separation, is washed with deionized water precipitate 2～3 times, dries, and obtains the neatly that sodium butyrate is modified
Stone；
2) take the brucite of the sodium butyrate modification that 1g is dried, join 3～5ml percent mass
Specific concentration is to stir 2～3h in 10%～15% n-BuLi pentane solution, has stirred from joining
Become the most under nitrogen protection, be vacuum dried 15～30h at 60～80 DEG C, grind, cross 20～40
Mesh sieve obtains powder；
3) powder obtained is put in vacuum tube furnace, be heated under vacuum
400～600 DEG C, vacuum calcining 2～4h, it is cooled to room temperature；
4) powder after calcining is joined the hydrochloric acid that mass percent concentration is 20%～40% molten
In liquid, every gram of corresponding 5～10 milliliters of hydrochloric acid solutions of powder, stirring 3～4h under nitrogen protection,
Precipitate and separate, dries；
5) by the product that obtains under vacuum, it is heated to 2000～2500 DEG C, at heat
Reason 3～6h, i.e. obtains two dimension lithium doping Graphene after cooling.
Compared with prior art, the present invention has a following useful technique effect:
1. prepare this nano material source simple, utilize common anion surfactant
Sodium butyrate, exchanges to hydrotalcite layers by anion exchange effect by butanoic acid root, and recycling has
Distributional effects between machine thing, is adsorbed onto hydrotalcite layers by n-BuLi pentane solution, and
Lithium atom can compare and is evenly distributed between Organic substance, through drying, carbonization, stripping
The lamella material with carbon element with nanoscale can be prepared.
2. utilize the special construction of brucite, it is ensured that interlayer Organic substance is being with one layer or two
The monomolecular dispersion of layer, forms two dimension polymerizable aromatic carbon structure after 400～600 DEG C of carbonizations.
3. the material after carbonization is after overpickling, and the structure of brucite itself is broken
Bad, metal-oxide is dissolved by acid, and the carbonaceous material of interlayer is peeled off naturally, process is simple,
Gentle.
4. the two-dimentional lithium doping Graphene after heat treatment still can keep original interlayer thick
Degree.
Detailed description of the invention
Describe the present invention in detail below in conjunction with embodiment, but the present invention is not limited to this.
Embodiment 1
According to the amount of every gram of brucite correspondence 1mmol sodium butyrate, the commercially available magnesium of 50 mesh sieves will be crossed
Aluminum hydrotalcite joins in the sodium butyrate solution that mass percent concentration is 0.1%, 70 DEG C of perseverances
Tepidarium is stirred 6h, aging 24h, then this precipitate is separated from liquid, spend from
Sub-water washing and precipitating thing 3 times, dries, and obtains the brucite that sodium butyrate is modified；Take what 1g was dried
The brucite that sodium butyrate is modified, joining 5ml mass percent concentration is 15% n-BuLi
Pentane solution stirs 3h, completes the most under nitrogen protection from joining stirring, at 80 DEG C
Vacuum drying 30h, grinds, and crosses 40 mesh sieves and obtains powder；The powder obtained is put into vacuum
In tube furnace, it is heated to 600 DEG C under vacuum, vacuum calcining 4h, it is cooled to room temperature；
Powder after calcining is joined in the hydrochloric acid solution that mass percent concentration is 40%, every gram of powder
Foot couple answers 10 milliliters of hydrochloric acid solutions, stirs 4h, precipitate and separate under nitrogen protection, dries；
By the product that obtains under vacuum, being heated to 2500 DEG C, thermally treated 6h, after cooling
I.e. obtain two dimension lithium doping Graphene.
Embodiment 2
According to the amount of every gram of brucite correspondence 0.5mmol sodium butyrate, the commercially available of 20 mesh sieves will be crossed
Nickel-ferric spinel joins in the sodium butyrate solution that mass percent concentration is 1%, 60 DEG C of perseverances
Tepidarium is stirred 5h, aging 12h, then this precipitate is separated from liquid, spend from
Sub-water washing and precipitating thing 2 times, dries, and obtains the brucite that sodium butyrate is modified；Take what 1g was dried
The brucite that sodium butyrate is modified, joining 3ml mass percent concentration is 10% n-BuLi
Pentane solution stirs 2h, completes the most under nitrogen protection from joining stirring, at 60 DEG C
Vacuum drying 15h, grinds, and crosses 20 mesh sieves and obtains powder；The powder obtained is put into vacuum
In tube furnace, it is heated to 400 DEG C under vacuum, vacuum calcining 2h, it is cooled to room temperature；
Powder after calcining is joined in the hydrochloric acid solution that mass percent concentration is 20%, every gram of powder
Foot couple answers 5 milliliters of hydrochloric acid solutions, stirs 3h, precipitate and separate under nitrogen protection, dries；
By the product that obtains under vacuum, being heated to 2000 DEG C, thermally treated 3h, after cooling
I.e. obtain two dimension lithium doping Graphene.
Embodiment 3
Be first according to document (Hydrotalcite by Hydrothermal Method synthesize, applied chemistry, 2001,18,
70-72) synthesis prepares magnalium type brucite；Brucite is crossed 40 mesh sieves, standby.
According to the amount of every gram of brucite correspondence 1mmol sodium butyrate, being prepared into of 40 mesh sieves will be crossed
To magnesium aluminum-hydrotalcite join in the sodium butyrate solution that mass percent concentration is 0.2%,
65 DEG C of waters bath with thermostatic control are stirred 6h, aging 24h, then this precipitate are separated from liquid,
It is washed with deionized water precipitate 3 times, dries, obtain the brucite that sodium butyrate is modified；Take 1g
The brucite that the sodium butyrate dried is modified, joining 5ml mass percent concentration is 15% just
Butyl lithium pentane solution stirs 3h, completes the most under nitrogen protection from joining stirring,
It is vacuum dried 30h at 80 DEG C, grinds, cross 40 mesh sieves and obtain powder；The powder obtained is put
Enter in vacuum tube furnace, be heated to 500 DEG C under vacuum, vacuum calcining 4h, cooling
To room temperature；Powder after calcining is joined the hydrochloric acid solution that mass percent concentration is 40%
In, every gram of corresponding 10 milliliters of hydrochloric acid solutions of powder, stir 4h, precipitation point under nitrogen protection
From, dry；By the product that obtains under vacuum, it is heated to 2500 DEG C, thermally treated 5
H, i.e. obtains two dimension lithium doping Graphene after cooling.
Claims (1)
1. the preparation method of a two-dimentional lithium doping Graphene, it is characterised in that: in turn include the following steps:
1) according to the amount of the corresponding 0.5～1mmol sodium butyrate of every gram of brucite, the neatly of 20-50 mesh sieve will be crossed
Stone joins in the sodium butyrate solution that mass percent concentration is 0.1%～1%, in 60～70 DEG C of waters bath with thermostatic control
Stirring 5～6h, aging 12～24h, then this precipitate is separated from liquid, it is washed with deionized water precipitate
2～3 times, dry, obtain the brucite that sodium butyrate is modified；
2) taking the brucite of the sodium butyrate modification that 1g is dried, joining 3～5ml mass percent concentrations is
10%～15% n-BuLi pentane solution stirs 2～3h, completes to protect at nitrogen from joining stirring always
Under, it is vacuum dried 15～30h at 60～80 DEG C, grinds, cross 20～40 mesh sieves and obtain powder；
3) powder obtained is put in vacuum tube furnace, is heated to 400～600 DEG C under vacuum,
Vacuum calcining 2～4h, is cooled to room temperature；
4) powder after calcining is joined in the hydrochloric acid solution that mass percent concentration is 20%～40%, often
The corresponding 5～10 milliliters of hydrochloric acid solutions of gram powder, stirring 3～4h under nitrogen protection, precipitate and separate, dry；
5) by the product that obtains under vacuum, it is heated to 2000～2500 DEG C, thermally treated 3～6h,
Two dimension lithium doping Graphene is i.e. obtained after cooling.
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Effective date of registration: 20201118 Address after: 277300 Yuejin Middle Road, Yicheng Industrial Park, Zaozhuang City, Shandong Province Patentee after: Shandong Yikai Electrical Equipment Co., Ltd Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |