CN103881139B - A kind of multi-functional compound between graphite layers and preparation method and application - Google Patents
A kind of multi-functional compound between graphite layers and preparation method and application Download PDFInfo
- Publication number
- CN103881139B CN103881139B CN201410086223.4A CN201410086223A CN103881139B CN 103881139 B CN103881139 B CN 103881139B CN 201410086223 A CN201410086223 A CN 201410086223A CN 103881139 B CN103881139 B CN 103881139B
- Authority
- CN
- China
- Prior art keywords
- graphite
- master batch
- obtains
- compound
- graphite layers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of multi-functional compound between graphite layers and preparation method and application.The compound between graphite layers of the present invention includes that Ni Fe alloy is as intercalator, suitably shield the low frequency electromagnetic radiation of 3mm 8mm wavelength, can polynary with other intercalator, multistage again combine, reach the most wide band electromagnetic wave-shielded effect, and it is multi-functional to possess antistatic, reduction thermal resistance etc., it is achieved that the breakthrough in field.Additionally provide the easy to process and preparation method of low cost, and the further application that expanded graphite product is in preparing various end product simultaneously, particularly make the application of functional expandability particle.
Description
Technical field
The invention belongs to compound between graphite layers field, be specifically related to a kind of maskable electromagnetic wave and antistatic, reduction
The multi-functional compound between graphite layers of thermal resistance, especially expanded graphite.
Background technology
Radiate the electronic product of various electromagnetic wave component such as to emerge rapidly in large numbersBamboo shoots after a spring rain appearance, such as: mobile phone, computer etc., the electricity of generation
Magnetic disturbance affects human health, it has also become the new problem of society's extensive concern, and electromagnetic wave proof, the Materials of electromagnetic shielding
Fail the most far away to reach gratifying level.Currently available most of electromagnetic shielding material, is making finished product of terminal company
Upper the worst just even cannot combine with chemical industry process equipment, therefore application is greatly limited.
Compound between graphite layers is to be increasingly subject to a kind of new material that people pay attention in recent years.Graphite crystal has by carbon unit
The galvanized hexagonal wire mesh plane layer structure of element composition, the carbon atom on layer plane combines with strong covalent bond, and layer and interlayer with
Van der Waals force combines, and in conjunction with the most weak, and interfloor distance is bigger.Therefore, under suitable condition, acid, alkali metal, salt etc.
Multiple chemical substance can be inserted into graphite layers, and be combined the chemical phase compound between graphite layers that formation is new with carbon atom
(Graphite Intercalation on Compounds is called for short GIC).This intercalation compound i.e. expansible graphite is adding
When heat is to proper temperature, can decompose rapidly moment, produce a large amount of gas, make graphite axially expand into vermiform new thing
Matter, i.e. expanded graphite.Expanded graphite due to the physical and chemical performance of its excellence preventing fires, seal, the aspect such as conduction is answered
With, but in terms of electromagnetic shielding, there is also deficiency.Root it was found that have the electromagnetic wave of injury mostly in low-frequency range to the mankind
(wavelength 3mm-8mm), and the expanded graphite of current research because of its electric conductivity reflection electromagnetic wave, to electromagnetic wave almost without magnetic
Loss absorbs, and frequency is the highest, and shielding reflectance is the highest, therefore the electromagnet shield effect of expanded graphite is along with frequency reduction drastically
Reduce, therefore in terms of the electromagnetic wave of shielding low-frequency range, there is also bigger defect.
Summary of the invention
In order to solve the problems referred to above, the present invention provides a kind of multi-functional compound between graphite layers and preparation method thereof and answers
With.
A kind of multi-functional compound between graphite layers, it is characterised in that the intercalator of interlayer includes Ni-Fe alloy.
Described intercalator also includes AsF5, SbF5, SbCl5, SbCl5, HNO3, FeCl3, CuCl3, AlCl3, MnCl2, CoCl2
Or CaCl3In one or more, preferably FeCl3。
The preparation method of a kind of multi-functional compound between graphite layers, it is characterised in that graphite raw material is dissolved in Ni-Fe alloy
The ethanol water of acetate react, then reduce.
The preparation method of a kind of multi-functional compound between graphite layers, it is characterised in that first that graphite raw material is anti-with oxidant
Should, adding intercalator and obtain expansible graphite, described intercalator is selected from AsF5, SbF5, SbCl5, SbCl5, HNO3, FeCl3,
CuCl3, AlCl3, MnCl2, CoCl2Or CaCl3In one or more, preferably FeCl3；Then described expansible graphite is entered
Row adds thermal expansion, grinding；The ethanol water of the acetate adding Ni-Fe alloy reacts；Finally product is carried out also
Former obtain powder.
Described graphite raw material is the natural flake graphite of the 100 above phosphorus content of mesh more than 99%.
Described graphite raw material is preferably greater than 500 mesh.
Described oxidant is selected from CrO3、CH3NO2、KMnO4、HClO4、C2H5COOH, n-butyric acie or H3PO4In one or several
Kind.
The mass fraction that mass fraction is 18-25%, Fe of Ni in the ethanol water of the acetate of described Ni-Fe alloy
For 2-5%, the mass fraction of ethanol is 0.2-3%.
The powder of the compound between graphite layers above-mentioned preparation method prepared can carry out following processing further to realize
Prepare the further application in various end product:
Mixing agglomerating with macromolecular compound, coupling agent, antioxidant, then put into twin screw granulator and prepare master batch；
It is added to the water stirring and obtains soft graphite breast；
Described powder first activates, then carries out suspension polymerisation together with water and styrene, prepares polystyrene functional
Master batch；
Described powder is first to insert centrifugal in centrifuge and to be dried after organic solvent washing, then is put into reactor,
By deionized water, a small amount of anion surfactant and PVA and graphite at temperature 60-90 DEG C, rotating speed 200-400r/min,
After 5-9 hour, sucking filtration, and centrifugal drying, obtain activation soft graphite；With deionized water and styrene monomer, the oil of 3-7:1
Phase and water are compared, and carry out suspension polymerisation, are sequentially added into deionized water, living fossil powdered ink the most in a kettle., and BPO causes
Agent, inorganic dispersant, emulsifying agent, anhydrous slufuric acid etc., give uniform mix suspending, in temperature 60-90 DEG C, mixing speed 80-
130r/min, forms polystyrene particle；After above-mentioned PS suspension polymerisation, input pentane in a kettle. with one-step method；Reaction
Still temperature keeps 60-90 DEG C, uniform stirring, after 3-7 hour, and derivation of being stopped, obtain PS expandability particle, wash with acidity
After washing agent cleaning, dry, become the multi-functional expandability PS particles such as there is anti-infrared ray, antistatic and wideband anti-electromagnetic wave.
Inventive technique effect:
Creative the achieving using Ni-Fe alloy as intercalator of the compound between graphite layers of the present invention, improves shielding
Material relative electric conductivity and the product of pcrmeability, improve the absorption loss of electromagnetism, suitably shield the low-frequency electrical of 3mm-8mm wavelength
Magnetic radiation, combines because electric conductivity can to a certain degree reflect high frequency electromagnetic radiation with graphite self, can well shielding wide band
Electromagnetic wave, it is achieved that the breakthrough in field.Additionally provide simultaneously and can realize the easy to process of Ni-Fe alloy efficient stable intercalation
And the preparation method of low cost.
The most first use oxidant (strong acid) graphite layers distance to be expanded, be inserted into intercalator, i.e. with Intercalation reaction first
Form expansible graphite, more expanded formation soft graphite.Its advantage essentially consists in lightization, easily shapes, and easily processes, the most modified etc..
Also can be further inserted into the insert of different electric conductivity, make conductivity diversification i.e. shield electromagnetic wave wideband, enter
One step expands effectiveness to such as 1-2GHz, simultaneously because of the electric conductivity of interposed layer obtain more efficient antistatic and
Reduction thermal resistances etc. are multi-functional.Different inserts is because the difference of reaction principle and condition (i.e. can inserted with different exponent numbers
Graphite layers is after the different numbers of plies) or quantity insertion, in graphite, multi-layer multi-order one plays, and then can be in wider frequency range
There is magnetic screen function, preferably increase iron halide system etc., because the oxide that can form ferrum during high temperature puffing has ferromagnetism,
To strengthen its wave-sucking performance.The metal-oxide generated during this external high temperature puffing reduction reaction after Ni-Fe alloy intercalation
The middle restriction because of reaction condition will not occur reduction reaction, does not interferes with ethanol solution and the graphite of the acetate of Ni-Fe alloy
Internal microstructure and the character with shielding low frequency electromagnetic wave energy product is formed after completing intercalation process.
Additionally, currently available electromagnetic shielding material, make on finished product of terminal company the worst just, even cannot be with change
Work process equipment combines.The powder of the functionalization that the present invention prepares can process below:
1, making with PE by extrusion granulator method, the macromolecule resin such as PP, EVA is the master batch of base material, reaches anti-electromagnetic wave, anti-
The functional master batch such as electrostatic, it is provided that downstream manufactures the various products with above-mentioned functions.
2, by above-mentioned powder suspension in water, make graphite suspension, be used as the coating and bonding needing to insert with liquid
In agent, it is provided that reach the product of above-mentioned functions.
3, it is polymerized with styrene monomer with suspension polymerization, immerses pentane, make expandability PS particle (EPS), except
Outside expandable, also can have anti-electromagnetic wave (wideband), thermal resistance improves, anlistatig function.
4, with above-mentioned expandability particle foamed after, prepare the container of various abnormity, container and packing timber by die pressing,
Wideband ability, antistatic, diamagnetic ripple sexual function it is also equipped with in addition to insulation.Present invention spy is grafted in suspension polymerisation mode
Remaining olefin monomer, forms master batch, can carry out reeling off raw silk from cocoons with rubber and plastic family macromolecule easily, extrude, penetrate, hot pressing, the processing such as coating
Mode forms required finished product of terminal company.
Detailed description of the invention
Embodiment 1
The present embodiment uses 100 mesh, phosphorus content > 99% natural flake graphite, with CrO3, CH3NO2As hybrid oxidant with
Chemical oxidization method is according to graphite: CH3NO2: FeCl3: CrO3Above-mentioned raw materials is constantly being stirred by the mass ratio of=1:3.2:1:0.4 successively
Mix down the reactor being equipped with reflux condensate device and agitator.Keep 30 DEG C of constant temperature in still, stir with the speed of 100r/min
After mixing 60min, wash solution is to colourless, and pH value is measured as neutrality.Intercalation compound is dried 5 hours to obtain at a temperature of 60 DEG C.
Above-mentioned is to use FeCl3The expansible graphite formed as intercalator.Allowance for expansion is big, has micropore number
Many, microcellular structure parameter is the most more uniform, FeCl3Insert and increase compound between graphite layers magnetic property.FeCl during GIC high temperature puffing3Warp
Redox reaction generates iron oxides, ferrum oxide (Fe2O3) and ferroso-ferric oxide (Fe3O4) adsorb in space and micella,
Ferrum oxide and ferroso-ferric oxide compare FeCl3There is higher ferromagnetism.
This intercalation compound is placed in 900W microwave power heating 5min, it can be made to expand volume and increase 235 times, be formed
Expanded graphite, is placed into after grinding in ball grinder becomes soft graphite to 50 μm, adding it to be dissolved with Ni-Fe alloy acetic acid
The ethanol water of salt, wherein the mass fraction of Ni is 22%, and the mass fraction of Fe is 3%, and the mass fraction of ethanol is 1.5%,
It is sufficiently stirred in still.Solvent is steamed in water-bath mode.It is dried 5.5 hours at 110 DEG C.Then at H2Reducing under atmosphere, condition can
It is set to 450 DEG C, 2.75 hours, after cooling, obtains the powder of maskable wide band electromagnetic wave.Wherein tenor is to add respectively
The mass fraction ratio of Ni, Fe.
Above-mentioned product is about 6000 oersteds and intensity of magnetization δ at applied field strengthssIt is about 0.55emug -1Situation
Under show paramagnetism with USM measurement.
Measure with net analysis instrument, frequency sweeping ranges 300KHz～1.5GHz, detect (ASTM D4395 99 standard)
Result is excellent.
| 30MHZ | The SE of EG is up to 70db |
| 1.5GHz | The SE of EG is up to 105db |
| 300kHz | The SE of EG is up to 70db |
(EG=expanded graphite, SE=magnetic shield usefulness)
Above-mentioned product again with3mm, 8mmRipple is tested, i.e. at present significant but lack effective shielding means
Low-frequency electromagnetic wave, obtaining result is:
| 3mm | 8mm | |
| Tradition | 4.48dB | 8.21dB |
| The present invention | 6.77dB | 12.22dB |
Compare more traditional intercalation to achieve and be substantially improved.
The present embodiment initial oxidation opens graphite layers, inserts conduction intercalation, further intercalation Ni-Fe alloy, on the one hand
Comprehensive high-efficiency antistatic and the expansible graphite in wide frequency range inner shield can be obtained, on the other hand formerly open interlayer and carry out
In the case of first step intercalation so that interlamellar spacing is sufficiently opened, it is also beneficial to the further intercalation of Ni-Fe alloy.
If certainly only for realizing the shielding of shielding low-frequency electromagnetic wave, an intercalation Ni-Fe alloy also can realize.Press
According to above-mentioned in the ethanol solution of the acetate of Ni-Fe alloy reaction can ensure that Ni-Fe alloy can intercalation obtaining smoothly
Stable product, preferably carries out certain heating (60-90 DEG C).
Above-mentioned intercalator also can select table 1 listed or single or mashed up according to demand and antistatic condition, prepares and efficiently leads
Electricity rate and the functional powder of efficient anti-static.
Table 1
| Insert | Exponent number | Conductivity |
| AsF5 | 1,2,3 | (5～6.3) 105 |
| SbF5 | 1,2,3,6 | (3.5～10) 105 |
| SbCl5 | 1,2,3 | (0.6～4.4) 105 |
| HNO3 | 1,2,3,4 | (1.7～3.5) 105 |
| FeCl3 | 1,2 | (1.7～2.5) 105 |
| CuCl3 | 1,2,3,5 | (1.1～2.5) 105 |
| AlCl3 | 1,2 | (0.8～1.6) 105 |
| MnCl2 | 1, | (2～2.5) 105 |
| CoCl2 | 1,2 | 2.5ⅹ105 |
| CaCl3 | 2 | 2ⅹ105 |
The factors such as wherein combined reaction condition, environment and cost performance, the FeCl that the present embodiment is selected3It is preferred.Additionally, by
In the above-mentioned intercalator of antistatic effect that realizes according to different conditions and reaction principle, the stratum that may insert is different (i.e.
It is spaced the different graphite numbers of plies and carries out intercalation), the insert of different rank therefore can be selected to carry out interspersed intercalation, to greatest extent
Realize wideband shielding and anti-static function.
Further, it is also possible to choose oxidant with the following ratio in table 2 and intercalator carries out the preparation of expansible graphite, its
Middle graphite and all oxidants mentioned above and the mass ratio of insert and reaction condition can be formed by numerical value in the following table
In the range of arbitrarily select, the speed of the simply reaction distinguished and efficiency.
Table 2
Above-mentioned prepared powder can also add in deionized water and stirs, and i.e. can obtain having efficient anti-static
Aqueous suspension soft graphite breast, the functional interpolation of the liquid state of various multi-form can be realized, reach antistatic, conduction and
The diamagnetic ripple of wideband etc., such as coating, binding agent etc..
Embodiment 2
The soft graphite powder that the present embodiment will produce in embodiment 1, according to table 3, with different macromolecules as base material, with matter
Measure and make antistatic, the functional master batch of wide frequency range anti-electromagnetic wave than 1:4.First added in high speed dispersor, put into matter
The titanate coupling agent mashed up esters of silicon acis coupling agent (mass ratio 1:1) of amount 1%-2% gives surface active, rotating speed 500r/min, time
Between 30mins, temperature 100 DEG C.Insert after discharging in mixing roll, (now should carry out design temperature, such as table 2 according to different base materials), and
The POE and 1% antioxidant that are added 5% carry out mixing, until after the most agglomerating, putting into twin screw granulator with carriage,
Setting twin screw granulator rotation speed requirements (such as table) according to Biao Zhongge district temperature, drawn prepares this merit after becoming bar, cooling, pelletizing
Can sexupara grain.
Table 3
| Macromolecule base material | MI value | Muller temperature sets | Twin screw granulator temperature sets | Rotating speed |
| LLDPE | 2.0 | 150 | 95,100,170,170,100 | 25 |
| All advise PP | 2.5 | 180 | 100,150,200,200,150 | 20 |
| PP | 2.0 | 180 | 100,150,220,220,180 | 20 |
| EVA | 1.8 | 145 | 95,100,165,165,100 | 25 |
| PVC | 2.2 | 150 | 95,100,170,180,100 | 25 |
Above-mentioned obtained efficient anti-static and can the functional master batch of anti-wide band electromagnetic wave be provided to extrusion, injection,
The chemical industry processor such as spinning and calendering and be worth finished product of terminal company.
Embodiment 3
Prepare the special master batch of functional PS and expandability function PS master batch.
The soft graphite powder that embodiment 1 is prepared by the present embodiment, first with insert after organic solvent washing in centrifuge from
The heart is also dried, then be put into reactor, with deionized water: anion surfactant, PVA: graphite=20:1:1, in temperature
70 DEG C, under rotating speed 300r/min, after 7 hours, sucking filtration, and centrifugal drying, obtain activation soft graphite.
With deionized water and styrene monomer, oil phase and the water of 5:1 are compared, and carry out suspension polymerisation.First at reactor
In be sequentially added into deionized water, activate soft graphite powder, BPO initiator, inorganic dispersant, emulsifying agent, anhydrous slufuric acid etc.,
Giving uniform mix suspending, temperature 80 DEG C, mixing speed 110r/min goes through mode and the program of suspension polymerisation, forms polyphenyl
Beta particles.This PS particle can be as multi-functional sexuparas such as polystyrene ABS, HIPS, the conduction of the engineering plastics such as GPS, hot biographies
The application of material.
Function graphite powder embodiment 1 prepared, after above-mentioned PS suspension polymerisation, inputs in a kettle. with one-step method
Pentane.Temperature of reaction kettle keeps 80 DEG C, uniform stirring, after 5 hours, and derivation of being stopped, obtain PS expandability particle.With
After acid detergent cleans, dry, become the multi-functional expandability PS such as there is anti-infrared ray, antistatic and wideband anti-electromagnetic wave
Particle.
With above-mentioned expandability particle foamed after, prepare the container of various abnormity, container and packing timber by die pressing, remove
Wideband ability, antistatic, diamagnetic ripple sexual function it is also equipped with outside insulation.
The above detailed description of the invention can make those skilled in the art that the present invention is more fully understood, but not to appoint
Where formula limits the scope of protection of present invention, and all are without departing from the technical scheme of the spirit and scope of this patent and change
Entering, the reasonable change etc. of the preparation process conditions such as such as conventional activation, mixing, suspension polymerisation, needing as long as meeting General reactions
The condition asked, it is encompassed by the middle of the protection domain of this patent.
Claims (8)
1. a multi-functional compound between graphite layers, it is characterised in that the intercalator of interlayer includes Ni-Fe alloy, the matter of Ni Yu Fe
Amount ratio is 18-25:2-5,
Described intercalator also includes AsF5, SbF5, SbCl5, SbCl5, HNO3, FeCl3, CuCl3, AlCl3, MnCl2, CoCl2Or
CaCl3In one or more, the optional insertion exponent number of each intercalator is as follows:
The preparation method of a kind of multi-functional compound between graphite layers the most according to claim 1, it is characterised in that first by stone
Ink raw material reacts with oxidant, adds intercalator and obtains expansible graphite, and described intercalator is selected from AsF5, SbF5, SbCl5,
SbCl5, HNO3, FeCl3, CuCl3, AlCl3, MnCl2, CoCl2Or CaCl3In one or more；Then to described inflatable stone
Ink carries out adding thermal expansion, grinding；The ethanol water of the acetate adding Ni-Fe alloy carries out reacting intercalation；Finally to product
Thing carries out reduction and obtains powder.
Preparation method the most according to claim 2, it is characterised in that the ethanol water of the acetate of described Ni-Fe alloy
The mass fraction of middle Ni be the mass fraction of 18-25%, Fe be 2-5%, the mass fraction of ethanol is 0.2-3%.
Preparation method the most according to claim 2, it is characterised in that described oxidant is selected from CrO3、CH3NO2、KMnO4、
HClO4、C2H5COOH, n-butyric acie or H3PO4In one or more.
The compound between graphite layers that method the most according to claim 2 obtains application in preparing electromagnetic shielding material master batch,
Described master batch obtains using the following method: by mixing agglomerating, then to described powder and macromolecular compound, coupling agent, antioxidant
Put into twin screw granulator and prepare master batch.
The compound between graphite layers that method the most according to claim 2 obtains application in preparing electromagnetic shielding aquadag, institute
State aquadag to obtain using the following method: described powder is added to the water stirring and obtains soft graphite breast.
The compound between graphite layers that method the most according to claim 2 obtains application in preparing electromagnetic shielding material master batch,
Described master batch obtains using the following method: first activated by described powder, then carries out suspension polymerisation together with water and styrene, system
Obtain polystyrene master batch.
The compound between graphite layers that method the most according to claim 2 obtains is in preparing electromagnetic shielding material expandability master batch
Application, described master batch obtains using the following method: first activated by described powder, then it is poly-to carry out suspension together with water and styrene
Close, then prepare polystyrene expandability master batch with one-step method input pentane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410086223.4A CN103881139B (en) | 2014-03-10 | 2014-03-10 | A kind of multi-functional compound between graphite layers and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410086223.4A CN103881139B (en) | 2014-03-10 | 2014-03-10 | A kind of multi-functional compound between graphite layers and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103881139A CN103881139A (en) | 2014-06-25 |
| CN103881139B true CN103881139B (en) | 2016-10-19 |
Family
ID=50950291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410086223.4A Active CN103881139B (en) | 2014-03-10 | 2014-03-10 | A kind of multi-functional compound between graphite layers and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103881139B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558768B (en) * | 2014-12-23 | 2017-05-31 | 贾纬民 | A kind of environmentally friendly environmental preparation method of expanded material of decrement cleaning and the expanded material of preparation and finished product of terminal company |
| CN107500286A (en) * | 2017-09-30 | 2017-12-22 | 湖南国盛石墨科技有限公司 | Micro crystal graphite bulking process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580747A (en) * | 2011-12-23 | 2012-07-18 | 湖南大学 | Composite catalyst for diamond synthesis and preparation method |
| CN103578678A (en) * | 2013-11-20 | 2014-02-12 | 南京工程学院 | Magnetic iron-based graphite intercalation compound and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101179921B (en) * | 2006-11-09 | 2010-05-12 | 南京大学 | Method for preparing electromagnetic shielding light graphite based nanometer magnetic metal composite material |
-
2014
- 2014-03-10 CN CN201410086223.4A patent/CN103881139B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580747A (en) * | 2011-12-23 | 2012-07-18 | 湖南大学 | Composite catalyst for diamond synthesis and preparation method |
| CN103578678A (en) * | 2013-11-20 | 2014-02-12 | 南京工程学院 | Magnetic iron-based graphite intercalation compound and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103881139A (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6163662B2 (en) | Graphene composite powder material and manufacturing method thereof | |
| CN108084906B (en) | Electromagnetic wave-absorbing plate for electric appliance product | |
| CN107096916B (en) | A kind of preparation method of silver-coated copper powder | |
| CN101875718B (en) | Conductive polyester/graphite oxide composite material and preparation method thereof | |
| TWI230743B (en) | Electronic conductive flake compound and electronic conductive composition | |
| CN107734950A (en) | Hollow zinc ferrite@manganese dioxide@graphenes layering core shell structure composite wave-suction material and preparation method thereof | |
| CN108251054A (en) | A kind of composite wave-suction material and preparation method thereof | |
| CN111285671B (en) | Low-frequency wave-absorbing material and preparation method thereof | |
| CN103881139B (en) | A kind of multi-functional compound between graphite layers and preparation method and application | |
| CN110724493B (en) | Multi-walled carbon nanotube/ferroferric oxide/nano oxide hybrid wave-absorbing material and preparation method thereof | |
| CN104437372A (en) | Method for preparing ferroferric oxide/carbon /nano-graphite sheet nanocomposite material in situ | |
| CN104356646B (en) | The preparation method of ferrite/conducting polymer multiphase composite wave-suction material | |
| CN105348421A (en) | Nanocomposite produced by compounding graphene through polymer polymerization method and preparation method thereof | |
| CN104941543A (en) | Method for preparing graphene/ferrite composite nanometer microspheres having high magnetic-electric performances | |
| CN102366839A (en) | Method for preparing rod-like ferrocobalt alloy powder without adopting template | |
| CN108864622A (en) | A kind of preparation method of polymer-based dielectric composite material | |
| CN105315964B (en) | A kind of synthetic method of ferroso-ferric oxide conducting polymer graphene tri compound wave absorbing agent | |
| CN106753238A (en) | A kind of preparation method of lamination Wave suction composite material | |
| TW201100514A (en) | Binder for positive electrode of lithium ion secondary battery, and positive electrode material | |
| CN111073296B (en) | Wave-absorbing patch and preparation method thereof | |
| CN108003520A (en) | A kind of preparation method of high dielectric property Kynoar titanium carbide nanosheet composite material | |
| CN107293412A (en) | A kind of capacitor enhanced electrode material of halloysite nanotubes and preparation method thereof | |
| CN110041565A (en) | A kind of biology based flameproofing and its preparation method and application | |
| CN106587037A (en) | Preparation method of Z-type ferrite and r-GO tape casting lamination microwave-absorbing composite material | |
| CN109509876A (en) | A kind of preparation process of compound cladding lithium cell cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 074000 West Street, Gaobeidian, Hebei, China, No. 59, No. Patentee after: Hebei shun new graphene New Material Co. Ltd. Address before: 074000 West Street, Gaobeidian, Hebei, China, No. 59, No. Patentee before: GAOBEIDIAN SHUNXIN CHEMICAL CO., LTD. |