CN110395723A - A kind of method of fuse salt strategy preparation High-performance graphene - Google Patents

A kind of method of fuse salt strategy preparation High-performance graphene Download PDF

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Publication number
CN110395723A
CN110395723A CN201910788105.0A CN201910788105A CN110395723A CN 110395723 A CN110395723 A CN 110395723A CN 201910788105 A CN201910788105 A CN 201910788105A CN 110395723 A CN110395723 A CN 110395723A
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salt
graphene
mixed metal
fuse salt
agaric
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CN201910788105.0A
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CN110395723B (en
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杨震宇
李超
孙成华
陈德良
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Dongguan University of Technology
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Dongguan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of methods of fuse salt strategy preparation High-performance graphene, firstly, leaching a large amount of mixed metal solions using the superabsorbency of dried fungus, drying is stand-by；Then leaching salt agaric and mixed metal salt, the lift-off processing in the equipment high temperature fuse salt atmosphere such as tube furnace are weighed according to the ratio；It the separation processes such as most washed, dried afterwards to respectively obtain graphene and the mixed metal salt used can be continued cycling through.Advantage is: using a large amount of metal ions are leached inside the superabsorbency of agaric, being advantageously implemented the full and uniform removing of fuse salt from inside to outside, obtains High-performance graphene；It is the production cost that raw material advantageously reduces graphene using biomass, reduces the dependence to fossil energy raw material；Metal melting salt may be reused through separation, and this preparation process being simple and efficient is introduced without poisonous and harmful chemicals, meets Green Chemical Engineering Process.

Description

A kind of method of fuse salt strategy preparation High-performance graphene
Technical field
The present invention relates to the sides of electrochemical technology field more particularly to a kind of fuse salt strategy preparation High-performance graphene Method.
Background technique
Graphene can be rated as super material, and theoretically it is with many excellent performances.Such as superior electron mobility, electronics fortune Scanning frequency degree is the 1/300 of the light velocity, and measured value of experiment is 1.5 × l05 cm2/ V s is equivalent to monocrystalline silicon electron mobility about 100 Times, it is 2 times of generally acknowledged preferred materials ladder indium at present；Low resistance, highly conductive, electric conductivity is 100 times of copper, flexible good, It is the ideal material for preparing conductive film electrode；High mechanical strength, Young's modulus are lT Pa；Specific surface area theory is reachable 2600m2/g；These superior functions impart graphene and are widely applied basis.Especially friendly process preparation is inexpensive, high-quality The research and development of amount graphene will have product to the progress and innovation in the fields such as the energy, material, catalysis, electronics and optical device The far-reaching influence of pole.
The method for commonly preparing graphene has: mechanical micro- stripping method, oxidation-reduction method and chemical vapour deposition technique (CVD) Deng.Wherein, not only easy but also efficient method is oxidation-reduction method.This method obtains stone by the operation preparation that initial oxidation restores Black alkene.However, either chemical reduction method or other methods prepares graphene and all has certain limitation, such as environment It is unfriendly, energy consumption is high, product is not readily separated etc., be unfavorable for graphene industrialized development.
The present invention provides a kind of method of fuse salt strategy preparation High-performance graphene, high using biomass agaric as raw material The full and uniform removing from inside to outside of warm fuse salt, preparation process is simple, efficient and pollution-free, is expected to realization scale and prepares high property Graphene and it can be promoted in the extensive use in the fields such as energy storage.
Summary of the invention
In order to solve the deficiency of existing High-performance graphene preparation method, it is an object of that present invention to provide a kind of fuse salts The method of strategy preparation High-performance graphene, preparation process are simple, efficient and pollution-free.
The technical solution adopted by the present invention is that: a kind of method of fuse salt strategy preparation High-performance graphene, feature exist In specific step is as follows:
(1) mixed metal solion is leached using dried fungus, drying is stand-by；
(2) leaching salt agaric and mixed metal salt are weighed according to the ratio, are shelled in the equipment high temperature fuse salt atmosphere such as tube furnace From processing；
(3) it washed, dry separation graphene and mixed metal salt；Obtain High-performance graphene product of the present invention.
In step (1), dried fungus leaches the concentration 1-5mol/L of solution metal ion；Solvent is water.
In step (2), the mass ratio for soaking salt agaric and mixed metal salt is 1:10 to 1:50.
In step (2), two or more of mixed metal salt for the chloride of sodium K-Mg-Ca aluminium element and in hydroxide.
In step (2), the mass ratio of preferably a kind of leaching salt agaric and mixed metal salt (NaCl/KCl) are 1:30, are obtained High-performance graphene product, graphene number of plies be 5 layers or so.For lithium ion battery negative material, current density 10A g-1 Lower acquisition 331mAh g-1High capacity output, current density 1A g-1Lower circulation 1000 times without capacity attenuation.
The positive effect of the present invention is as follows: being the production cost that raw material advantageously reduces graphene using biomass, reduces Dependence to fossil energy raw material；Metal melting salt may be reused through separation, and this preparation process being simple and efficient No poisonous and harmful chemicals introduces, and meets Green Chemical Engineering Process；The graphene of preparation is used for lithium ion battery negative material, electric current Density 10A g-1Lower acquisition 331mAh g-1High capacity output, current density 1A g-1Lower circulation 1000 times without capacity attenuation.
Detailed description of the invention
Fig. 1 is that fuse salt strategy prepares graphene schematic diagram.
Fig. 2 is SEM the and AFM phenogram that graphene sample is prepared in embodiment.
Specific embodiment
The present invention is such to work and implementation, and a kind of method of fuse salt strategy preparation High-performance graphene is special Sign is that specific step is as follows:
(1) mixed metal solion is leached using dried fungus, drying is stand-by；
(2) leaching salt agaric and mixed metal salt are weighed according to the ratio, are shelled in the equipment high temperature fuse salt atmosphere such as tube furnace From processing；
(3) it washed, dry separation graphene and mixed metal salt；Obtain High-performance graphene product of the present invention.
The innovation of the invention consists in that: liquid is presented in the fuse salt high temperature used, these are by from molecular ionic liquid Quantity, ratio can regulate and control dried fungus wellability or wetability in fuse salt atmosphere, improve peeling effect, using fuse salt Strategy, which prepares high-quality graphene for the direct removing of biomass agaric, has novelty；Utilize the super-strong moisture absorbing of dried fungus Property, it first passes through and leaches a large amount of fuse salts inside biological cell, then by being realized in high-temperature fusion salt atmosphere from inside to outside uniformly Biomass agaric is removed on ground, improves the uniformity of graphene product Micro-sheet Structure and size, and regulation prepares high performance graphite Alkene product has apparent innovative in this field.
The following examples are a further detailed description of the invention.
Embodiment 1
Dried fungus (50g) leaches NaCl/KCl solution 2mol/L, and drying is stand-by；1:10 weighs above-mentioned system in mass ratio Standby leaching salt agaric and NaCl/KCl, the lift-off processing in the equipment high temperature fuse salt atmosphere such as tube furnace；It washed, dried point From graphene and NaCl/KCl salt-mixture；High-performance graphene product of the present invention is obtained, graphene number of plies is 9 layers or so. NaCl/KCl salt-mixture is recycled and is continued with.The graphene of preparation is used for lithium ion battery negative material, current density 10A g-1Lower acquisition 206mAh g-1Volume output, current density 1A g-1Lower 1000 capacity of circulation keep 91%.
Embodiment 2
Dried fungus (50g) leaches NaCl/KCl solution 2mol/L, and drying is stand-by；1:30 weighs above-mentioned system in mass ratio Standby leaching salt agaric and NaCl/KCl, the lift-off processing in the equipment high temperature fuse salt atmosphere such as tube furnace；It washed, dried point From graphene and NaCl/KCl salt-mixture；High-performance graphene product of the present invention is obtained, graphene number of plies is 5 layers or so. NaCl/KCl salt-mixture is recycled and is continued with.The graphene of preparation is used for lithium ion battery negative material, current density 10A g-1Lower acquisition 331mAh g-1Volume output, current density 1A g-1Lower circulation 1000 times without capacity attenuation.
Embodiment 3
Dried fungus (50g) leaches Ca2Cl/KCl solution 2mol/L, drying are stand-by；1:30 weighs above-mentioned in mass ratio The leaching salt agaric of preparation and CaCl2/ KCl, the lift-off processing in the equipment high temperature fuse salt atmosphere such as tube furnace；It washed, done Dry separation graphene and NaCl/KCl salt-mixture；High-performance graphene product of the present invention is obtained, graphene number of plies is 5 layers of left side It is right.NaCl/KCl salt-mixture is recycled and is continued with.
Embodiment 4
Dried fungus (50g) leaches CaCl2/ KCl solution 2mol/L, drying are stand-by；1:50 weighs above-mentioned in mass ratio The leaching salt agaric of preparation and CaCl2/ KCl, the lift-off processing in the equipment high temperature fuse salt atmosphere such as tube furnace；It washed, done Dry separation graphene and NaCl/KCl salt-mixture；High-performance graphene product of the present invention is obtained, graphene number of plies is 4 layers of left side It is right.
Embodiment 5
Dried fungus (50g) leaches NaCl/KCl solution 2mol/L, and drying is stand-by；1:50 weighs above-mentioned system in mass ratio Standby leaching salt agaric and NaCl/KCl, the lift-off processing in the equipment high temperature fuse salt atmosphere such as tube furnace；It washed, dried point From graphene and NaCl/KCl salt-mixture；High-performance graphene product of the present invention is obtained, graphene number of plies is 4 layers or so. NaCl/KCl salt-mixture is recycled and is continued with.The graphene of preparation is used for lithium ion battery negative material, current density 10A g-1Lower acquisition 325mAh g-1Volume output, current density 1A g-1Lower 1000 capacity of circulation keep 95% or more.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (4)

1. a kind of method of fuse salt strategy preparation High-performance graphene, it is characterised in that specific step is as follows:
(1) mixed metal solion is leached using dried fungus, drying is stand-by；
(2) leaching salt agaric and mixed metal salt are weighed according to the ratio, in the equipment high temperature fuse salt atmosphere such as tube furnace at removing Reason；
(3) it washed, dry separation graphene and mixed metal salt；Obtain High-performance graphene product.
2. a kind of method of fuse salt strategy preparation High-performance graphene according to claim 1, it is characterised in that: step (1) in, dried fungus leaches the concentration 1-5mol/L of solution metal ion；Solvent is water.
3. a kind of method of fuse salt strategy preparation High-performance graphene according to claim 1, it is characterised in that: step (2) in, the mass ratio for soaking salt agaric and mixed metal salt is 1:10 to 1:50.
4. a kind of method of fuse salt strategy preparation High-performance graphene according to claim 1, it is characterised in that: step (2) in, two or more of mixed metal salt for the chloride of sodium K-Mg-Ca aluminium element and in hydroxide.
CN201910788105.0A 2019-08-26 2019-08-26 Method for preparing high-performance graphene by molten salt strategy Expired - Fee Related CN110395723B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114180560A (en) * 2021-12-21 2022-03-15 山西大学 Preparation method of coal-based graphene in molten salt system
CN115784290A (en) * 2022-11-08 2023-03-14 宜都兴发化工有限公司 Process for purifying phosphogypsum by molten salt leaching method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106744830A (en) * 2016-11-24 2017-05-31 华南理工大学 A kind of method that three-dimensional porous/two-dimensional slice Graphene is prepared for carbon source with biology

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106744830A (en) * 2016-11-24 2017-05-31 华南理工大学 A kind of method that three-dimensional porous/two-dimensional slice Graphene is prepared for carbon source with biology

Non-Patent Citations (2)

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Title
CUNJING WANG ETAL.: "Nitrogen-doped two-dimensional porous carbon sheets derived from clover biomass for high performance supercapacitors", 《JOURNAL OF POWER SOURCES》 *
XIANGJUN LU ET AL.: "Molten-salt strategy for fabrication of hierarchical porous N-doped carbon nanosheets towards high-performance supercapacitors", 《MATERIALS CHEMISTRY AND PHYSICS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114180560A (en) * 2021-12-21 2022-03-15 山西大学 Preparation method of coal-based graphene in molten salt system
CN115784290A (en) * 2022-11-08 2023-03-14 宜都兴发化工有限公司 Process for purifying phosphogypsum by molten salt leaching method
CN115784290B (en) * 2022-11-08 2024-03-12 宜都兴发化工有限公司 Process for purifying phosphogypsum by molten salt leaching method

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