CN106683813A - Graphene-coated variable phase nano magnetic composite material and preparation method thereof - Google Patents

Graphene-coated variable phase nano magnetic composite material and preparation method thereof Download PDF

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CN106683813A
CN106683813A CN201611180118.2A CN201611180118A CN106683813A CN 106683813 A CN106683813 A CN 106683813A CN 201611180118 A CN201611180118 A CN 201611180118A CN 106683813 A CN106683813 A CN 106683813A
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plasma
phase
graphene
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CN106683813B (en
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王群
冯唐锋
王澈
李永卿
王明连
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Beijing University of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/0045Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
    • H01F1/0054Coated nanoparticles, e.g. nanoparticles coated with organic surfactant
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/10Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
    • H01F1/11Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
    • H01F1/112Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles with a skin
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/36Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Dermatology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biomedical Technology (AREA)
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  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Abstract

The invention provides a graphene-coated variable phase nano magnetic composite material with a core-shell structure. The shell is a graphene shell which is formed by multiple layers of graphene sheets, and the thickness of the shell layer is 5-50nm; and the core is a magnetic core and is a phase-variable nano magnetic particle with a particle diameter of 10-90nm. The invention also provides a preparation method of the graphene-coated variable phase nano magnetic composite material. According to the method provided by the invention, the ferrocene powder is taken as an iron source and a carbon source, and the plasma is taken as a synthetic environment so as to ensure that the toxicity and environmental pollution caused by reactants can be reduced and the mass production can be facilitated; the phase of the obtained magnetic nano particles can be controlled by controlling the nitrogen ratio of the plasma in the preparation process; and the graphene-coated nano magnetic powder prepared by adopting the method provided by the invention is fine in particle size, uniform in distribution, good in degree of sphericity and short in preparation process.

Description

A kind of variable phase nano magnetic composite materials of graphene coated and preparation method thereof
Technical field
The invention belongs to nano-function powder material and Preparation Technique of Powders field, and in particular to a kind of composite graphite alkene Functional material and preparation method thereof.
Background technology
Graphene (Graphene) be it is a kind of by carbon atom with sp2 hybridized orbits constitute hexangle type in honeycomb lattice plane Film, the two-dimentional carbon material of only one of which carbon atom thickness.Graphene has strong toughness, electrical conductance and thermal conductivity.Iron and iron Nitrogen compound has excellent magnetic property, but its chemical stability is poor, especially iron phase.By the use of Graphene as covering material The problem of chemical stability and the electrical conductance difference of magnetic-particle can very well be improved so that this composite can be answered well Used in magnetic fluid, targeted drug, electromagnetic wave absorbent material, electromagnetic shielding material, oxidation reduction catalyst, fine ceramics material and The multiple fields such as lithium battery.
In presently disclosed patent and document, report it is mostly be carbon-coated metallic nano-particles preparation method, such as be pyrolyzed Method, arc process, infusion process, CVD etc. obtain carbon-encapsulated iron nano particle;For the iron nitride nanometer of graphene coated Grain, not a kind of method can be directly obtained.
Application publication number is CN101347455A, and date of publication is on January 21st, 2009, and a kind of entitled carbon-encapsulated iron of patent is received Rice corpuscles and its application as treatment liver-cancer medicine carrier, it has invented a kind of carbon-encapsulated iron nanoparticles, particularly by straight Stream arc process is prepared.
Application publication number is CN102623696A, and date of publication is August in 2012 1, patent name:A kind of core-shell type cladding Nitrided iron nano-complex particle preparation method and application, it has invented a kind of core-shell type carbon coating nitrided iron nano-complex particle system Standby technique, particularly using the carbon-encapsulated iron nano particle of direct-current plasma fabricated in situ as presoma, then by nitridation work Skill obtains carbon coating nitrided iron nano-complex particle.
Application publication number is CN101710512A, and date of publication is on May 19th, 2010, the entitled Graphene of patent and carbon coating Ferromagnetic nano metal composite and preparation method thereof.It has invented a kind of by Graphene and the ferromagnetic nano of carbon coating Grain, and prepare this kind of composite powder material there is provided a kind of special CVD.
These methods all have respective advantage, but also have more deficiency, and such as testing equipment complexity, preparation condition are tight Lattice, flow are cumbersome etc., cause preparation cost higher, so as to influence graphene/carbon to coat the exploitation of iron and iron nitride powder With application.
The content of the invention
In view of the above-mentioned present state of the art, it is an object of the present invention to provide a kind of variable phase nanometer of graphene coated Magnetic composite.
Preparation side the present invention also aims to provide a kind of variable phase nano magnetic composite materials of graphene coated Method, and the method can be by regulating and controlling the nitrogenous than regulating and controlling the thing facies type of magnetic core of preparation process plasma.
The technical scheme for realizing above-mentioned purpose of the present invention is:
A kind of variable phase nano magnetic composite materials of graphene coated, with core shell structure, housing is Graphene shell, by Multi-layer graphene piece is constituted, and shell thickness is 5-50nm;Core is magnetic core, is that particle diameter is that 10-90nm phases are variable Nano magnetic particle.
Wherein, the phase of the nano magnetic particle is α-Fe, the γ-Fe of iron phase, and γ-Fe (N), γ '-Fe4N、ε- Fe3N、α”-Fe16N2One or more in the iron nitride of phase.
The preparation method for also proposing the described variable phase nano magnetic composite materials of graphene coated of the invention, including with Lower step:
(1) after the reaction cavity of continuous and multiple plasma generation device carries out inert gas purge, with indifferent gas Body is full of whole reaction cavity, completely cuts off air;
(2) after plasma electrical source excites the inert gas plasma stream stablized, by being input into reaction gas Source forms hybrid plasma stream, then by ferrocene powder thermal evaporation, ferrocene steam is sent into plasma in current-carrying gas form Body central area;
(3) plasma enthalpy high and chemical activation effect are utilized, after ferrocene to be pyrolyzed rapidly concurrent biochemical reaction, Grown up by forming core in plasma flame stream afterbody and obtain nano magnetic particle and in particle surface coated graphite alkene;
(4) reaction chamber is dropped into room temperature, the as composite granule that collection is obtained, Graphene under the conditions of inert gas shielding Cladding nano magnetic particle composite.
Plasma method prepares the variable phase nano magnetic particle of graphene coated, compared with other method, prepares particle Degree is smaller, particle diameter distribution is uniform and can obtain the magnetic core of not jljl phase by controlling the nitrogenous ratio in plasma.This hair Bright use ferrocene (C10H10Fe it is) reaction raw materials, promotes to react by plasma, directly obtaining graphene coated can be covert State nano magnetic particle composite granule.
Wherein, using ferrocene (C10H10Fe) as source of iron and carbon source, the evaporation fluidized bed temperature setting of ferrocene powder is 100~400 DEG C;The current-carrying gas be argon gas, nitrogen, one or more of ammonia.
Further, described plasma stream is inductive coupled plasma stream, capacitively coupled plasma stream and micro- One kind in ripple coupled plasma stream, is mixed to form by inert gas and reactant gas source, reactant gas source and inert gas Molar ratio is 0~5:1;Described inert gas be argon gas, helium, neon in one or more, reactant gas source be hydrogen, One or more in nitrogen, ammonia.
Wherein, the nitrogenous ratio of plasma is controlled by adjusting the flow of reactant gas source, inert gas and current-carrying gas, from And control the phase of nano magnetic particle to constitute so that the phase of nano magnetic particle be α-Fe, γ-Fe, γ-Fe (N), γ '- Fe4N、ε-Fe3N、α”-Fe16N2In one or more.
One of the preferred technical solution of the present invention is:The plasma it is nitrogenous than (it is always former that nitrogen-atoms accounts for plasma The mol ratio of son amount) for 0 when, the phase of the nano magnetic particle in gained composite is in α-Fe and the γ-Fe of iron phase One or two.
Another optimal technical scheme of the invention is:When the nitrogenous ratio of the plasma is 5~80%, gained composite wood The phase of the nano magnetic particle in material is γ-Fe (N), γ '-Fe4N、ε-Fe3One or more in N.
The advantage of the invention is that:
(1) method proposed by the present invention, by the use of ferrocene powder as source of iron and carbon source, using plasma as synthesis ring Border, reduces toxicity and environmental pollution that reactant brings, beneficial to a large amount of productions.
(2) thing of obtained magnetic nanoparticle can be controlled by regulating and controlling the nitrogenous ratio of preparation process plasma Phase.
(3) nano-magnetic powder diameter by the carbon coating prepared by the approach is tiny, be evenly distributed, good sphericity, And preparation flow is brief.
Graphene coated prepared by the inventive method mutually can have good change by abnormal nano magnetic composite materials simultaneously Stability, magnetic property and electrical property are learned, therefore in targeted drug, magnetic fluid, absorbing material, lithium battery material and catalyst etc. are more Individual field has a wide range of applications potentiality.
Brief description of the drawings
The graphene coated that Fig. 1 is embodiment 1, embodiment 2 is prepared with embodiment 3 mutually abnormal nano-magnetic can be combined The XRD spectrum of material.
Fig. 2 is particle diameter distribution and the TEM figure of the variable phase nano particle composite material of graphene coated prepared by embodiment 1
Fig. 3 is the TEM figures of the variable phase nano particle composite material of graphene coated prepared by embodiment 2.
Fig. 4 is the TEM figures of the variable phase nano particle composite material of graphene coated prepared by embodiment 3.
Specific embodiment
Following examples further illustrate present disclosure, but should not be construed as limiting the invention.
Black alkene proposed by the present invention coats the preparation method of variable phase nano magnetic composite materials, comprises the following steps:
(1) after the reaction cavity of continuous and multiple plasma generation device carries out inert gas purge, with indifferent gas Body is full of whole reaction cavity, completely cuts off air;
(2) after plasma electrical source excites the inert gas plasma stream stablized, by being input into reaction gas Source forms hybrid plasma stream, then by ferrocene powder thermal evaporation, ferrocene steam is sent into plasma in current-carrying gas form Body central area;
(3) plasma enthalpy high and chemical activation effect are utilized, after ferrocene to be pyrolyzed rapidly concurrent biochemical reaction, Grown up by forming core in plasma flame stream afterbody and obtain nano magnetic particle and in particle surface coated graphite alkene;
(4) reaction chamber is dropped into room temperature, the as composite granule that collection is obtained, Graphene under the conditions of inert gas shielding Cladding nano magnetic particle composite.
The equipment for using can be existing plasma generating equipment, in embodiment, specifically using patent Equipment disclosed in CN104851548A.
Unless otherwise instructed, the means for being used in embodiment are this area conventional technology.
The concrete technology of the preparation of the variable phase nano magnetic composite materials of graphene coated is as follows in embodiment:
Embodiment 1:
With commercially available ferrocene powder as raw material, repeatedly with after argon purge reaction cavity, gas is formed as plasma with argon gas and is built The argon plasma of vertical stable operation, wherein argon flow amount are 5slpm, and side protection gas argon flow amount is 5slpm.Constant temperature fluidized bed temperature Degree be set to 120 DEG C, by flow for 3slpm argon gas by ferrocene steam send into plasma flame stream in, by plasma Body pyrolytic and priming reaction obtain the variable phase nano magnetic particle of graphene coated, the XRD of product as shown in figure 1, TEM schemes and particle diameter distribution is as shown in Figure 2.
As shown in Figure 1, the thing phase composition of embodiment 1 is α-Fe, γ-Fe and C.As shown in Figure 2, the graphene coated for obtaining Between 10~90nm, average grain diameter is in 26.3nm for variable phase nano magnetic composite materials particle diameter distribution.Particle is in ball substantially Shape or spheroid shape and coated by shell, measure core diameter and shell thickness and be about respectively 20nm and 5nm.By the crystalline substance to nucleocapsid Interlamellar spacing measures discovery, and the interplanar distance of shell is about 0.35nm, and the interplanar distance with (002) face of Graphene is approached, This explanation shell is collectively constituted by multi-layer graphene piece;The interplanar distance of core is 0.203nm, (110) interplanar distance with α-Fe And/or (111) interplanar distance of γ-Fe is approached, this is consistent with XRD data.Composite even particle size distribution, sphericity It is good.
Embodiment 2:
It is plasma shape with argon gas and nitrogen repeatedly with after argon purge reaction cavity with commercially available ferrocene powder as raw material Set up the argon-nitrogen plasma of stable operation jointly into gas, wherein argon flow amount is 5slpm, and nitrogen flow is 1slpm, side protection Gas argon flow amount is 10slpm.Constant temperature fluidized bed is set to 160 DEG C, and carrier gas flux is the argon gas of 1slpm, other same embodiments of operation 1.The XRD of graphene coated nitrided iron nano magnetic particle is obtained as shown in figure 1, TEM figures are as shown in Figure 3.
As shown in Figure 1, the thing phase composition of product prepared by embodiment 2 is γ-Fe (N), γ '-Fe4N、ε-Fe3N.By Fig. 3 It can be seen that, the variable phase nano magnetic composite materials particle diameter distribution of graphene coated for obtaining between 10~90nm, with obvious Core shell structure, the graphene sheet layer of core outer cladding multilayer.Being evenly distributed of composite, good sphericity.
Embodiment 3:
It is plasma shape with argon gas and nitrogen repeatedly with after argon purge reaction cavity with commercially available ferrocene powder as raw material Set up the argon nitrogen radio frequency plasma of stable operation jointly into gas, wherein argon flow amount is 5slpm, and nitrogen flow is 3slpm, side Protection gas argon flow amount is 10slpm.Constant temperature fluidized bed is set to 180 DEG C, and other operations are with embodiment 2.Obtain graphene coated nitrogen Change the XRD of iron nano magnetic particle as shown in figure 1, TEM figures are as shown in Figure 4.
As shown in Figure 1, the thing phase composition of embodiment 3 is γ-Fe (N), ε-Fe3N.From fig. 4, it can be seen that the Graphene bag for obtaining Variable phase nano magnetic composite materials particle diameter distribution is covered between 10~110nm, with obvious core shell structure, core outsourcing Cover the graphene sheet layer of multilayer.Being evenly distributed of composite, good sphericity.
Although above having used general explanation, specific embodiment and experiment, the present invention is made to retouch in detail State, but on the basis of the present invention, some modifications or improvement can be made to it, this is to those skilled in the art aobvious and easy See.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed Scope.

Claims (8)

1. variable phase nano magnetic composite materials of a kind of graphene coated, it is characterised in that with core shell structure, housing is stone Black alkene shell, is made up of multi-layer graphene piece, and shell thickness is 5-50nm;Core is magnetic core, is that particle diameter is 10-90nm phases The variable nano magnetic particle of state.
2. variable phase nano magnetic composite materials of graphene coated according to claim 1, it is characterised in that described to receive The phase of rice magnetic-particle is α-Fe, the γ-Fe of iron phase, and γ-Fe (N), γ '-Fe4N、ε-Fe3N、α”-Fe16N2The iron nitrogen of phase One or more in compound.
3. the preparation method of the variable phase nano magnetic composite materials of graphene coated described in claim 1 or 2, its feature exists In comprising the following steps:
(1) after the reaction cavity of continuous and multiple plasma generation device carries out inert gas purge, filled with inert gas Full whole reaction cavity, completely cuts off air;
(2) after plasma electrical source excites the inert gas plasma stream stablized, by being input into reactant gas source shape Into hybrid plasma stream, then by ferrocene powder thermal evaporation, in current-carrying gas form by ferrocene steam feeding plasma Heart district domain;
(3) plasma enthalpy high and chemical activation effect are utilized, after ferrocene to be pyrolyzed rapidly concurrent biochemical reaction, is being waited Gas ions flame stream afterbody is grown up by forming core and obtains nano magnetic particle and in particle surface coated graphite alkene;
(4) reaction chamber is dropped into room temperature, the as composite granule that collection is obtained, graphene coated under the conditions of inert gas shielding Nano magnetic particle composite.
4. preparation method according to claim 3, it is characterised in that using ferrocene (C10H10Fe) as source of iron and carbon Source, the evaporation fluidized bed temperature setting of ferrocene powder is 100~400 DEG C;The current-carrying gas is argon gas, nitrogen, one kind of ammonia Or it is various.
5. preparation method according to claim 3, it is characterised in that described plasma stream is inductive coupled plasma One kind in body stream, capacitively coupled plasma stream, microwave coupling plasma jet, by inert gas and reactant gas source mixing shape Into the molar ratio of reactant gas source and inert gas is 0~5:1;Described inert gas is in argon gas, helium, neon Plant or various, reactant gas source is one or more in hydrogen, nitrogen, ammonia.
6. preparation method according to claim 3, it is characterised in that by adjusting reactant gas source, inert gas and current-carrying The flow of gas controls the nitrogenous ratio of plasma, so as to control the phase of nano magnetic particle to constitute so that nano-magnetic The phase of grain is α-Fe, γ-Fe, γ-Fe (N), γ '-Fe4N、ε-Fe3N、α”-Fe16N2In one or more.
7. preparation method according to claim 6, it is characterised in that the plasma it is nitrogenous than for 0 when, gained is multiple The phase of the nano magnetic particle in condensation material for iron phase α-Fe, γ-Fe in one or two.
8. preparation method according to claim 6, it is characterised in that the plasma it is nitrogenous than for 5~80% when, The phase of the nano magnetic particle in gained composite is γ-Fe (N), γ '-Fe4N、ε-Fe3One or more in N.
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Cited By (8)

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CN107127335A (en) * 2017-05-18 2017-09-05 山东大学 A kind of preparation method of hud typed carbon-encapsulated iron nano composite material
CN107895653A (en) * 2017-10-27 2018-04-10 西安理工大学 Method that microwave prepares cigarette filter/graphene composite material and application thereof
CN108110231A (en) * 2017-12-05 2018-06-01 银隆新能源股份有限公司 A kind of carbon coating Fe4N nanocomposites, preparation method and applications
CN108659790A (en) * 2018-04-26 2018-10-16 南通大学 A kind of preparation method of the composite wave-suction material of magnetic-particle intercalation porous graphene
CN109215913A (en) * 2017-07-04 2019-01-15 中国科学院金属研究所 A method of preparing carbon package iron-nitride and its composite magnetic nano material
CN110575814A (en) * 2019-08-27 2019-12-17 中国科学院合肥物质科学研究院 Graphene-coated metal-based environment functional material and preparation method and application thereof
CN111724954A (en) * 2020-02-07 2020-09-29 宴晶科技(北京)有限公司 Graphene oxide magnetic bead, antibody-coupled graphene oxide magnetic bead, preparation methods of graphene oxide magnetic bead and antibody-coupled graphene oxide magnetic bead and application of graphene oxide magnetic bead in cell sorting
CN113231633A (en) * 2021-04-06 2021-08-10 北京碳垣新材料科技有限公司 Graphene copper-based composite powder and preparation method thereof

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107127335A (en) * 2017-05-18 2017-09-05 山东大学 A kind of preparation method of hud typed carbon-encapsulated iron nano composite material
CN107127335B (en) * 2017-05-18 2019-04-02 山东大学 A kind of preparation method of hud typed carbon-encapsulated iron nanocomposite
CN109215913A (en) * 2017-07-04 2019-01-15 中国科学院金属研究所 A method of preparing carbon package iron-nitride and its composite magnetic nano material
CN109215913B (en) * 2017-07-04 2021-03-02 中国科学院金属研究所 Method for preparing carbon-coated iron nitride and composite magnetic nano material thereof
CN107895653A (en) * 2017-10-27 2018-04-10 西安理工大学 Method that microwave prepares cigarette filter/graphene composite material and application thereof
CN108110231A (en) * 2017-12-05 2018-06-01 银隆新能源股份有限公司 A kind of carbon coating Fe4N nanocomposites, preparation method and applications
CN108110231B (en) * 2017-12-05 2020-05-19 银隆新能源股份有限公司 Carbon-coated Fe4N nano composite material, preparation method and application thereof
CN108659790A (en) * 2018-04-26 2018-10-16 南通大学 A kind of preparation method of the composite wave-suction material of magnetic-particle intercalation porous graphene
CN110575814A (en) * 2019-08-27 2019-12-17 中国科学院合肥物质科学研究院 Graphene-coated metal-based environment functional material and preparation method and application thereof
CN111724954A (en) * 2020-02-07 2020-09-29 宴晶科技(北京)有限公司 Graphene oxide magnetic bead, antibody-coupled graphene oxide magnetic bead, preparation methods of graphene oxide magnetic bead and antibody-coupled graphene oxide magnetic bead and application of graphene oxide magnetic bead in cell sorting
CN111724954B (en) * 2020-02-07 2023-01-20 宴晶科技(北京)有限公司 Graphene oxide magnetic bead, antibody-coupled graphene oxide magnetic bead and application of graphene oxide magnetic bead in cell sorting
CN113231633A (en) * 2021-04-06 2021-08-10 北京碳垣新材料科技有限公司 Graphene copper-based composite powder and preparation method thereof

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