CN110518211A - A kind of carbon package metal fluoride and its preparation method and application - Google Patents
A kind of carbon package metal fluoride and its preparation method and application Download PDFInfo
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- CN110518211A CN110518211A CN201910809660.7A CN201910809660A CN110518211A CN 110518211 A CN110518211 A CN 110518211A CN 201910809660 A CN201910809660 A CN 201910809660A CN 110518211 A CN110518211 A CN 110518211A
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- 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
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/625—Carbon or graphite
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Abstract
The invention discloses a kind of carbon package metal fluorides and its preparation method and application, comprising the following steps: (1) organic fluorocompound is dissolved in organic solvent, obtains organic fluorocompound solution A;(2) by metal oxide dispersion in organic fluorocompound solution A, suspension B is obtained;(3) suspension B is filtered, after taking screening heating, drying dry, obtains the metal oxide C of organic fluorocompound package;(4) the metal oxide C for wrapping up organic fluorocompound after temperature reaction, obtains carbon and wraps up metal fluoride under protective gas atmosphere.A kind of preparation method of carbon package metal fluoride of the invention, by its preparation process using organic fluorocompound and metal oxide as reactant, pass through single step reaction, realize transformation of the metal oxide to metal fluoride, and it is externally formed with one layer of amorphous carbon layer, preparation process is simple, and preparation process will not introduce and generate the toxic gases such as fluorine gas, hydrogen fluoride.
Description
Technical field
The invention belongs to metal fluoride technical field, in particular to a kind of carbon package metal fluoride and preparation method thereof
And application.
Background technique
Metal fluoride is widely used as the lithium-rich manganese-based cladding material of lithium ion battery as the hot spot material studied now
Expect, the adsorbent material of polysulfide, catalyst and the fluorescent material of oversubscription subdomains of catalytic field etc. in lithium-sulfur cell.Carbon materials
Material is used as most common conductive material, is often used as conductive agent, conductive network skeleton, insulation material in battery research field
Expect carrier, positive or negative pole material clad etc..Cladding is carried out with oxide or fluoride of the carbon material to poorly conductive to repair
Decorations, can increase the electric conductivity of material, this kind of method of modifying is able to solve basic material while retaining original material performance
The defect of poorly conductive.
In recent years, the preparation method of metal fluoride is it has been reported that very much, such as plasma fluoride process, sol-gel
Method, oxidative decomposition process etc..Although these methods are widely used, but there are many problems, comprising: solidifying in colloidal sol-
HF gas can be generated in glue method, oxidative decomposition process uses pernicious gas F2As the source F, and plasma is fluorinated rule to equipment requirement
High, preparation condition is harsh, and the production cost is very high.
To sum up, a kind of preparation method of new metal fluoride is needed.
Summary of the invention
It is above-mentioned to solve the purpose of the present invention is to provide a kind of carbon package metal fluoride and its preparation method and application
Existing one or more technical problem.Preparation method of the invention can solve existing fluoride preparation process, and there are toxic gases
Harm and preparation process complexity problem;The present invention provides Fluorine source with organic fluorocompound, by one-step method, realizes oxidation
Conversion of the object to fluoride, and it is capable of forming a kind of clad structure of carbon packet fluoride.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of preparation method of carbon package metal fluoride of the invention, comprising the following steps:
(1) organic fluorocompound is dissolved in organic solvent, obtains organic fluorocompound solution A;
(2) by metal oxide dispersion in organic fluorocompound solution A, suspension B is obtained;
(3) suspension B is filtered, after taking screening heating, drying dry, obtains the metal oxide of organic fluorocompound package
C;
(4) the metal oxide C for wrapping up organic fluorocompound after temperature reaction, obtains carbon packet under protective gas atmosphere
Wrap up in metal fluoride.
A further improvement of the present invention is that the organic fluorocompound is Kynoar, polytetrafluoroethyl-ne in step (1)
One of alkene, fluorine-containing alkane, Fluorine containing olefine and fluorine-containing aromatic hydrocarbons are a variety of.
A further improvement of the present invention is that the organic solvent is N-Methyl pyrrolidone, dimethyl in step (1)
One of sulfoxide, N,N-dimethylformamide, dimethyl acetamide and triethyl phosphate are a variety of.
A further improvement of the present invention is that the dry step of heating, drying specifically includes in step (3): 60 DEG C~90
It is dry under DEG C constant-temperature vacuum environment.
A further improvement of the present invention is that protective gas atmosphere in step (4) specifically: nitrogen atmosphere, argon atmosphere
Or ammonia atmosphere.
A further improvement of the present invention is that being specifically included the step of temperature reaction in step (4): with 1 DEG C/min~15
DEG C/heating rate of min is heated to 650 DEG C~950 DEG C, it is cooled to room temperature after keeping the temperature 60min~180min, obtains carbon package gold
Belong to fluoride.
A further improvement of the present invention is that every 0.12g~0.3g organic fluorocompound is right in step (1) and step (2)
Answer 2ml~4ml organic solvent, corresponding 0.06g~0.15g metal oxide.
A further improvement of the present invention is that in step (2), metal oxide materials are as follows: Al2O3、SiO2、La2O3、
GeO2、TiO2、ZrO2、V2O5、MoO3、Cr2O3、MnO2、Fe2O3、Fe3O4、Co2O3、CuO、Nb2O5、RuO2、In2O3、SnO2、
Sb2O3、NiO、Sb2O5、Ga2O3、Tl2O3、PbO、Bi2O3、Ta2O5、WO2、ZnO、WO3、Bi2O3And CeO2One of or it is a variety of.
A kind of carbon of the invention wraps up metal fluoride, is made of preparation method of the invention, is externally formed with one
Layer amorphous carbon layer.
A kind of application of carbon package metal fluoride of the invention, is coated on lithium-sulfur cell diaphragm.
Compared with prior art, the invention has the following advantages:
A kind of preparation method of carbon package metal fluoride of the invention, utilizes organic fluorocompound and gold by its preparation process
Belong to oxide as reactant and transformation of the metal oxide to metal fluoride is realized by single step reaction, and is externally formed with
One layer of amorphous carbon layer, preparation process is simple, and preparation process will not introduce and generate the toxic gases such as fluorine gas, hydrogen fluoride.
Specifically advantage includes:
One, preparation method of the invention, using organic fluorocompound and metal oxide as reactant, with traditional oxidation
F is needed in decomposition method2Compared as the source F, the reactant of the method for the present invention more safely, be easy to get;
Two, reaction efficiency of the invention is higher, prepares carbon package metal pentafluoride species material with conventional method, needs with existing
Then some metal fluorides are coated as reactant with traditional carbon coating method.The carbon-coated means of tradition are usual
Hydro-thermal, polymerization, carbonization treatment are carried out using glucose, dopamine etc. as carbon source;Another means are with PVD on the surface of material
Deposited carbon layer, common carbon coating method are coated on basic material, and the ingredient and property of material itself can't be changed
Matter.The present invention, directly as reactant, first can will prepare metal fluorine with metal oxide in conventional method with metal oxide
Compound, then realized in single step reaction with the complicated processes of carbon-clad metal fluoride, so that the preparation efficiency of material mentions significantly
It is high;
Three, the present invention does not have a large amount of HF gases during the preparation process and generates, instead compared with traditional sol-gel method
Answer process safer, the corrosion to equipment, the harm of environment all falls below minimum;
Four, the present invention is compared with traditional plasma fluoride process, and the requirement to preparation condition and consersion unit is low, and work
Skill is simply easy to implement.
In the present invention, 650 DEG C~950 DEG C are heated to 1 DEG C/min~15 DEG C/min heating rate, heat preservation 60min~
It is cooled to room temperature after 180min, obtains carbon package metal fluoride;Suitable heating rate carry out reaction can sufficiently, close
Suitable holding temperature can guarantee that reaction is carried out by the process that we design, will not generate side reaction.When suitable heat preservation
Between, it can ensure that reaction can be properly completed.
In the present invention, every 0.12g~0.3g organic fluorocompound, corresponding 2ml~4ml organic solvent, corresponding 0.06g~
0.15g metal oxide.It is tested if not in this proportional region, it is possible that two kinds of situations.1. organic fluorocompound
Excessively, the carbon covered metal fluoride carbon-coating eventually formed is too thick, influences the property of metal fluoride.2. organic fluorocompound is very few,
Not only carbon-coating is too thin for the carbon covered metal fluoride eventually formed, and metal pentafluoride cannot be completely transformed by also resulting in metal oxide
Object.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below to embodiment or existing
Attached drawing needed in technical description does simple introduction;It should be evident that the accompanying drawings in the following description is of the invention
Some embodiments to those skilled in the art without creative efforts, can also be according to this
A little attached drawings obtain other attached drawings.
Fig. 1 is a kind of operating process schematic diagram of the preparation method of carbon package metal fluoride of the embodiment of the present invention;
Fig. 2 is the TEM schematic diagram of ceria in the embodiment of the present invention;
Fig. 3 is the Elemental redistribution schematic diagram of ceria in the embodiment of the present invention;
Fig. 4 is in the embodiment of the present invention, and carbon wraps up the TEM schematic diagram of cerous fluoride;
Fig. 5 is in the embodiment of the present invention, and carbon wraps up the Elemental redistribution schematic diagram of cerous fluoride;
Fig. 6 is the XRD schematic diagram that organic fluorocompound package lanthanum sesquioxide is carbonized and is not carbonized in the embodiment of the present invention;
Fig. 7 is to illustrate in the embodiment of the present invention by comparing with the battery performance without diagram modification for diagram modification
Figure.
Specific embodiment
To keep the purpose, technical effect and technical solution of the embodiment of the present invention clearer, implement below with reference to the present invention
Attached drawing in example, technical scheme in the embodiment of the invention is clearly and completely described;Obviously, described embodiment
It is a part of the embodiment of the present invention.Based on embodiment disclosed by the invention, those of ordinary skill in the art are not making creation
Property labour under the premise of other embodiments obtained, all should belong to the scope of protection of the invention.
Referring to Fig. 1, a kind of preparation method of carbon package metal fluoride of the embodiment of the present invention, specific preparation process
Include:
One, prepare mixture solution: taking appropriate organic fluorocompound in vial, organic solvent is added and matches until completely dissolved
The organic fluorocompound solution of 0.01g/ml~0.5g/ml is made.Suitable metal oxide samples are weighed, organic fluorocompound is poured into
It is stirred in solution, ultrasound oxidizes metal object and is thoroughly dispersed in organic fluorocompound solution, acquisition suspension.
Two, dry composite sample: above-mentioned suspension is simply filtered, and then filtered screening sample is put into
Vacuum oven, composite sample heating, drying after dried after dry with 60 DEG C~90 DEG C constant-temperature vacuums are that is, fluorine-containing organic
The metal oxide of object package.
Three, carbonization treatment: the composite sample after drying is put into tube furnace, and in ammonia, nitrogen or argon atmosphere
Under, 650 DEG C~950 DEG C are heated to 1 DEG C/min~15 DEG C/min heating rate, is cooled to after keeping the temperature 60min~180min
Room temperature, the sample after being carbonized, i.e. carbon wrap up metal fluoride.
Wherein, the organic fluorocompound is Kynoar, polytetrafluoroethylene (PTFE), fluorine-containing alkane, Fluorine containing olefine and fluorine-containing
Aromatic hydrocarbons etc. has F, and C element and at high temperature F can be with the mixtures of O one of the organic matter replaced or its different proportion.
The organic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide, n,N-Dimethylformamide, dimethyl acetamide
With the mixture of one of triethyl phosphate or its different proportion.
In step 1, every 0.12g~0.3g organic fluorocompound, corresponding 2ml~4ml organic solvent, corresponding 0.06g~
0.15g metal oxide.
Metal oxide materials described in step 1 are as follows: Al2O3、SiO2、La2O3、GeO2、TiO2、ZrO2、V2O5、MoO3、
Cr2O3、MnO2、Fe2O3、Fe3O4、Co2O3、CuO、Nb2O5、RuO2、In2O3、SnO2、Sb2O3、NiO、Sb2O5、Ga2O3、Tl2O3、
PbO、Bi2O3、Ta2O5、WO2、ZnO、WO3、Bi2O3、CeO2One of or different proportion mixture.
To sum up, the preparation method of one of present invention carbon package metal fluoride, is had by its preparation process using fluorine-containing
Machine object and metal oxide will not introduce and generate F in preparation process as reactant2, the toxic gases such as HF.In carbonisation
In, the product that carbon wraps up metal fluoride is directly obtained by single step reaction, greatly improves the preparation efficiency of material.
It has the effect that
One, a kind of preparation method of carbon package metal fluoride of the present invention, is made using organic fluorocompound and metal oxide
To need F in reactant, with traditional oxidative decomposition process2It is compared as the source F, the reactant of the method for the present invention is safer, easy
.
Two, reaction efficiency of the invention is higher, prepares carbon package metal pentafluoride species material with conventional method, needs with existing
Then some metal fluorides are coated as reactant with traditional carbon coating method.The present invention is straight with metal oxide
It connects as reactant, first can will prepare metal fluoride with metal oxide in conventional method, then be fluorinated with carbon-clad metal
The complicated processes of object are realized in single step reaction, so that the preparation efficiency of material greatly improves.It is pointed out that current carbon packet
The means covered usually carry out hydro-thermal, polymerization, carbonization treatment using glucose, dopamine etc. as carbon source;Another means are to use PVD
In the surface deposited carbon layer of material, common carbon coating method is to be coated on basic material, can't change material sheet
The ingredient and property of body.
Three, the present invention does not have a large amount of HF gases during the preparation process and generates, instead compared with traditional sol-gel method
Answer process safer, the corrosion to equipment, the harm of environment all falls below minimum.
Four, the present invention is compared with traditional plasma fluoride process, and the requirement to preparation condition and consersion unit is low, and work
Skill is simply easy to implement.
Embodiment 1:
A kind of preparation method of carbon package metal fluoride of the embodiment of the present invention, specifically includes the following steps:
One, prepare mixture solution: taking appropriate organic fluorocompound in vial, organic solvent is added and matches until completely dissolved
The organic fluorocompound solution of 0.01g/ml~1g/ml is made.Suitable metal oxide samples are weighed, it is molten to pour into organic fluorocompound
It is stirred in liquid, ultrasound oxidizes metal object and is thoroughly dispersed in organic fluorocompound solution.
Wherein, organic fluorocompound is the Kynoar of 0.12g, and organic solvent is the N-Methyl pyrrolidone of 2ml, metal
Oxide is the Al of 0.06g2O3。
Two, dry composite sample: above-mentioned suspension is simply filtered, and filtered sample is then put into vacuum
Drying box, composite sample heating, drying after dried after dry with 60 DEG C of constant-temperature vacuums, the i.e. gold of organic fluorocompound package
Belong to oxide.
Three, carbonization treatment: the composite sample after drying is put into tube furnace, and under nitrogen or argon atmosphere, with 1
DEG C/heating rate of min is heated to 650 DEG C, it is cooled to room temperature after keeping the temperature 60min, the sample after be carbonized, i.e. carbon package are golden
Belong to fluoride.
Embodiment 2
In the embodiment of the present invention, the difference with embodiment 1 is only that:
One, during preparation mixture solution: the Kynoar and polytetrafluoroethylene (PTFE) mixing that organic fluorocompound is 0.3g
Object, organic solvent are the N-Methyl pyrrolidone and dimethyl sulfoxide mixture of 4ml, and metal oxide is the Al of 0.15g2O3With
Fe3O4Mixture.
Two, dry with 90 DEG C of constant-temperature vacuums in dry composite sample.
Three, during carbonization treatment, 950 DEG C is heated to the heating rate of 15 DEG C/min, is cooled to after keeping the temperature 180min
Room temperature, the sample after being carbonized.
Embodiment 3
In the embodiment of the present invention, the difference with embodiment 1 is only that:
One, during preparation mixture solution: organic fluorocompound is the polytetrafluoroethylene (PTFE) and Fluorine containing olefine mixture of 0.2g,
Organic solvent is the dimethyl acetamide and dimethyl sulfoxide mixture of 3.5ml, and metal oxide is the WO of 0.10g3And Sb2O3
Mixture.
Two, dry with 70 DEG C of constant-temperature vacuums in dry composite sample.
Three, during carbonization treatment, 850 DEG C is heated to the heating rate of 10 DEG C/min, is cooled to after keeping the temperature 120min
Room temperature, the sample after being carbonized.
Embodiment 4
A kind of preparation method of carbon package metal fluoride of the embodiment of the present invention, specifically includes the following steps:
One, prepare mixture solution: taking appropriate organic fluorocompound in vial, organic solvent is added and matches until completely dissolved
The organic fluorocompound solution of 0.01g/ml~1g/ml is made.Suitable metal oxide samples are weighed, it is molten to pour into organic fluorocompound
It is stirred in liquid, ultrasound oxidizes metal object and is thoroughly dispersed in organic fluorocompound solution.
Two, dry composite sample: above-mentioned suspension is simply filtered, and filtered sample is then put into vacuum
Drying box, dry with 60~90 DEG C of constant-temperature vacuums, the composite sample after being dried after heating, drying, i.e. organic fluorocompound wrap up
Metal oxide.
Three, carbonization treatment: the composite sample after drying is put into tube furnace, and under ammonia atmosphere, with 1 DEG C/min~
The heating rate of 15 DEG C/min is heated to 650~950 DEG C, is cooled to room temperature after keeping the temperature 60min~180min, is carbonized and nitrogen
Sample after doping, i.e. nitrogen-doped carbon wrap up metal fluoride.
Through the foregoing embodiment it is found that the preparation method of carbon package metal fluoride of the invention, has preparation efficiency height,
The features such as preparation process is environmentally protective.Using organic fluorocompound as Fluorine source, in preparation process, will not introduce or generate fluorine gas,
The toxic gases such as hydrogen fluoride.The preparation method can realize that metal oxide turns to metal fluoride by single step reaction
Become, and is externally formed with one layer of amorphous carbon layer simultaneously.
Using following experimental verification invention effects: a kind of preparation method of carbon package metal fluoride of the present invention, material
Synthesis uses Hefei section crystalline substance tube furnace (OTF-1200X).The method of verifying carbon package metal fluoride is to be transmitted using Flied emission
Electron microscope (JEOL JEM-F200 (HR)) observes the pattern of material, structure.Element distribution analysis is carried out using EDS.
Test what the ceria used was bar-like it can be seen from the TEM photo of Fig. 2, and lattice fringe is obvious.
The distribution diagram of element photo of Fig. 3 can be seen that Ce elements and oxygen element is all generally evenly distributed in clava, and
Without other miscellaneous elemental compositions, the rodlike ceria purity for illustrating that experiment uses is very high.
Fig. 4 is by the TEM photo after the ceria carbonization treatment of Kynoar package, it can be seen that gathers inclined fluorine
Ethylene has turned to amorphous carbon (being amorphous carbon between two dotted lines), and ceria is completely transformed into cerous fluoride.
The distribution diagram of element of Fig. 5 can be seen that Ce elements, and fluorine element is distributed in white lighted region, indicate the light
Particle indicates that cerium fluoride, carbon are distributed in all samples region, indicates that cerium fluoride is to be wrapped up and be distributed in amorphous carbon
Portion.
It being can analyze out by the XRD diagram piece of Fig. 6, the organic fluorocompound without carbonization treatment wraps up lanthanum sesquioxide sample,
Its peak position and the lanthanum sesquioxide PDF card of standard coincide, and can illustrate to contain lanthanum sesquioxide in this state sample.Carbonization
The lanthanum sesquioxide sample of the organic fluorocompound package of processing, its peak position and the lanthanum trifluoride of standard coincide, and can illustrate this
Lanthanum sesquioxide in state sample has been completely transformed into lanthanum trifluoride.
It is invented and is applied using following experimental verifications:
In the present invention, the carbon of preparation is wrapped up into metal fluoride materials, is coated on lithium-sulfur cell diaphragm, in O2Content <
0.1ppm, H2In O content < 0.1ppm glove box environment, common PP diaphragm is replaced with modified diaphragm, is assembled into 2032
Button cell.On new prestige cell tester, the cycle performance of battery is tested.
By Fig. 7 it can easily be seen that carbon package cerous fluoride is coated on the diaphragm of lithium-sulfur cell, electricity can be significantly improved
The capacity in pond, also, battery is after by 100 charging and dischargings, the rate of decay of capacity also than pure diaphragm it is slow very much.
The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, although referring to above-described embodiment pair
The present invention is described in detail, those of ordinary skill in the art still can to a specific embodiment of the invention into
Row modification perhaps equivalent replacement these without departing from any modification of spirit and scope of the invention or equivalent replacement, applying
Within pending claims of the invention.
Claims (10)
1. a kind of preparation method of carbon package metal fluoride, which comprises the following steps:
(1) organic fluorocompound is dissolved in organic solvent, obtains organic fluorocompound solution A;
(2) by metal oxide dispersion in organic fluorocompound solution A, suspension B is obtained;
(3) suspension B is filtered, after taking screening heating, drying dry, obtains the metal oxide C of organic fluorocompound package;
(4) the metal oxide C for wrapping up organic fluorocompound after temperature reaction, obtains carbon package gold under protective gas atmosphere
Belong to fluoride.
2. a kind of preparation method of carbon package metal fluoride according to claim 1, which is characterized in that in step (1),
The organic fluorocompound is one of Kynoar, polytetrafluoroethylene (PTFE), fluorine-containing alkane, Fluorine containing olefine and fluorine-containing aromatic hydrocarbons or more
Kind.
3. a kind of preparation method of carbon package metal fluoride according to claim 1, which is characterized in that in step (1),
The organic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, dimethyl acetamide and tricresyl phosphate
One of ethyl ester is a variety of.
4. a kind of preparation method of carbon package metal fluoride according to claim 1, which is characterized in that in step (3)
The dry step of heating, drying specifically includes: dry under 60 DEG C~90 DEG C constant-temperature vacuum environment.
5. a kind of preparation method of carbon package metal fluoride according to claim 1, which is characterized in that in step (4)
Protective gas atmosphere specifically: nitrogen atmosphere, argon atmosphere or ammonia atmosphere.
6. a kind of preparation method of carbon package metal fluoride according to claim 1, which is characterized in that in step (4)
The step of temperature reaction, specifically includes: being heated to 650 DEG C~950 DEG C with 1 DEG C/min~15 DEG C/min heating rate, heat preservation
It is cooled to room temperature after 60min~180min, obtains carbon package metal fluoride.
7. a kind of preparation method of carbon package metal fluoride according to claim 1, which is characterized in that step (1) and
In step (2), every 0.12g~0.3g organic fluorocompound, corresponding 2ml~4ml organic solvent, corresponding 0.06g~0.15g metal oxygen
Compound.
8. a kind of preparation method of carbon package metal fluoride according to claim 1, which is characterized in that in step (2),
Metal oxide materials are as follows: Al2O3、SiO2、La2O3、GeO2、TiO2、ZrO2、V2O5、MoO3、Cr2O3、MnO2、Fe2O3、Fe3O4、
Co2O3、CuO、Nb2O5、RuO2、In2O3、SnO2、Sb2O3、NiO、Sb2O5、Ga2O3、Tl2O3、PbO、Bi2O3、Ta2O5、WO2、ZnO、
WO3、Bi2O3And CeO2One of or it is a variety of.
9. a kind of carbon wraps up metal fluoride, which is characterized in that use preparation method described in any item of the claim 1 to 8
Production, is externally formed with one layer of amorphous carbon layer.
10. a kind of application of carbon package metal fluoride as claimed in claim 9, which is characterized in that be coated on lithium-sulfur cell every
Film.
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