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 PDFInfo
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0036—Magnets 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
- H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
- H01F1/0054—Coated nanoparticles, e.g. nanoparticles coated with organic surfactant
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets 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
- H01F1/10—Magnets 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
- H01F1/11—Magnets 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
- H01F1/112—Magnets 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets 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
- H01F1/34—Magnets 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
- H01F1/36—Magnets 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus 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
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
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)
| 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 |
| 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)
| 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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