CN108155350A - A kind of functionalization graphene composite material and its preparation method and application - Google Patents
A kind of functionalization graphene composite material and its preparation method and application Download PDFInfo
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- CN108155350A CN108155350A CN201611094474.2A CN201611094474A CN108155350A CN 108155350 A CN108155350 A CN 108155350A CN 201611094474 A CN201611094474 A CN 201611094474A CN 108155350 A CN108155350 A CN 108155350A
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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
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- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- 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
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- 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 present invention provides a kind of functionalization graphene composite materials, including graphene nanometer sheet, vertical-growth in the carbon nano pipe array of the graphene nano on piece, and by graphene nanometer sheet polyelectrolyte crosslinked together, by the way that π is pi-conjugated, one or more of chemical bond, hydrogen bond, Van der Waals force active force connect between the graphene nanometer sheet and the polyelectrolyte.The functionalization graphene composite material can be used as lithium battery system cathode protection materials; the effect of artificial SEI films can be functioned similarly to by being coated on the surface of lithium battery system negative electrode active material, improved the cyclical stability of cathode pole piece, extended battery；And the formation of Li dendrite can effectively be avoided by being coated on lithium anode surface, and then the phenomenon that prevent battery short circuit and coulombic efficiency from reducing.The present invention also provides the preparation method and application of the functionalization graphene composite material.
Description
Technical field
The present invention relates to technical field of lithium batteries, more particularly to a kind of functionalization graphene composite material and its preparation side
Method and application.
Background technology
With the research and development of lithium battery system, it is desirable to while battery energy density leap is obtained, ensure electricity
Pond has long circulating service life and high rate charge-discharge performance.Existing lithium battery lithium anode and negative electrode of lithium ion battery are lived
Volume expansion causes the unstable situation of material surface SEI films after property material is often accompanied by the embedding lithium of pole piece.Since SEI is repeatedly generated
With rupture, a large amount of losses of electrolyte and excessive irreversible capacity loss can be caused, significantly limits battery cycle life
Raising.Research thus about the protection of lithium battery system cathode is quite important to the raising of battery performance.
At present, someone is by the way that high-stability graphene material coats negative electrode active material, to improve cathode work
Property material surface SEI films stability, be effectively improved pole piece cycle.However for the highly expandeds negative electrode of lithium ion battery such as silicon activity
Material, such surface modification cannot meet the stability of material under its high level expansion state.Thus, it is necessary to designing one kind has
The artificial SEI protective layers of lithium battery system negative electrode active material of certain elasticity, to completely cut off the straight of negative electrode active material and electrolyte
Contact, and meet negative electrode active material under high embedding lithium expanded state, it is still completely coated in artificial SEI shells, is improved
The cyclical stability of material.Meanwhile the artificial SEI protective layers of the elasticity should have high conductivity and mechanical stability, avoid tradition
Elastomeric polymer cladding causes excessive pole piece internal resistance.
Invention content
In consideration of it, first aspect present invention provides a kind of functionalization graphene composite material, the functionalization graphene is compound
The surface that material is coated on lithium battery system negative electrode active material can function similarly to the effects of artificial SEI films, improve cathode
The cyclical stability of pole piece extends battery；And Li dendrite can effectively be avoided by being coated on lithium anode surface
The phenomenon that being formed, and then preventing battery short circuit and coulombic efficiency from reducing.
Specifically, in a first aspect, the present invention provides a kind of functionalization graphene composite material, including graphene nano
Piece, vertical-growth are crosslinked in the carbon nano pipe array of the graphene nano on piece and by the graphene nanometer sheet one
The polyelectrolyte risen, passes through π-pi-conjugated, chemical bond, hydrogen bond, Van der Waals between the graphene nanometer sheet and the polyelectrolyte
One or more of power active force connects.
Wherein, the graphene nanometer sheet forms graphene/carbon nano-tube three-dimensional structure with the carbon nano pipe array and answers
The mass ratio of conjunction object, the graphene/carbon nano-tube three-dimensional structure compound and the polyelectrolyte is 1-10:1.
The graphene nanometer sheet be single-layer or multi-layer graphene, thickness 5nm-500nm.
The height of the carbon nano pipe array is 500nm-4 μm.
The polyelectrolyte includes cationic polyelectrolyte, anionic polyelectrolyte, amphoteric polyelectrolyte and gathers
It is one or more in electrolyte composite.
More specifically, the polyelectrolyte includes protein, nucleic acid, natural gum, modified starch, modified cellulose, polypropylene
Acid, Sodium Polyacrylate, polyacrylamide, polymethylacrylic acid, polymaleic anhydride, poly-metaphosphoric acid, polyethylene glycol oxide, polyethylene
Amine, polyvinyl pyridine, polyvinylpyrrolidone, kayexalate, phthalic acid diethylene glycol diacrylate, poly- second
It is one or more in alkene sulfonic acid, polyethyleneimine, amino acid, natural acid and polydimethyl diallyl ammonium chloride.
The functionalization graphene composite material that first aspect present invention provides, based on graphene nanometer sheet, in graphite
Alkene nanometer sheet surface vertical-growth has a carbon nano pipe array, and resilient, crosslinked is realized by polyelectrolyte between graphene nanometer sheet,
The functionalization graphene composite material can be used as lithium battery system cathode protection materials, be coated on negative electrode active material surface or gold
Belong to cathode of lithium surface, wherein, graphene and carbon nanotube can be that electrode integrally provides efficiently quickly electronics conduction, gather electrolysis
Matter can be Li+Diffusion provides transmission channels, and is acted on using " bridge formation " of the polyelectrolyte between graphene nano lamella, can
Make the negative electrode active material being wrapped by when the expansion of embedding lithium occurs, though occur between graphene nanometer sheet and piece it is opposite slide but
Remain to be tightly linked into compact film so that the negative electrode active material being wrapped by not with electrolyte contacts, even if recurring structure
It collapses and dusting, is also still completely wrapped in functionalization graphene composite material protective layer, without losing and conductive network
Effectively electrical contact, so as to improve the cyclical stability of electrode entirety.
Second aspect, the present invention provides a kind of preparation methods of functionalization graphene composite material, include the following steps：
Preparing surface vertical-growth using chemical vapour deposition technique has the graphene nanometer sheet of carbon nano pipe array, obtains stone
Black alkene/carbon nanotube three-dimensional structure compound；
Dispersion liquid will be obtained in the graphene/carbon nano-tube three-dimensional structure compound ultrasonic disperse to water, it will be described point
Dispersion liquid is mixed 0.5-3 hours with polyelectrolyte aqueous solution, and then through centrifuging, washing, gained precipitation is function graphite
Alkene composite material.
In the present invention, the preparation process of the graphene/carbon nano-tube three-dimensional structure compound is specially：
Metallic catalyst is taken, by the metallic catalyst equably splash to substrate, and the substrate is placed in level
Then the quartz ampoule is placed in tube furnace and heats by the center of quartz ampoule again；
Argon gas and hydrogen are passed through into the tube furnace, after in-furnace temperature rises to 500 DEG C -1000 DEG C, introduces reaction gas
Body C2H410min-100min is reacted, with vertical-growth carbon nano pipe array on the substrate；
Air-flow is become into argon gas and is heated to 500 DEG C -1000 DEG C, reaction gas CH is introduced to the tube furnace4Reaction
10min-100min, with horizontal graphene nanometer sheet is generated between the carbon nano pipe array of vertical-growth to get to graphene/
Carbon nanotube three-dimensional structure compound crude product；
After reaction, tube body is cooled down, takes out the crude product, and by the crude product with 1mol/L-10mol/L's
5h-24h is handled at 50 DEG C -150 DEG C of HCl/water solution, then is handled at 50 DEG C -150 DEG C of the HF aqueous solutions of 1mol/L-10mol/L
5h-24h obtains the graphene/carbon nano-tube three-dimensional structure compound.
Specifically, the metallic catalyst includes Cu, Al, Fe, Mo, Co, Ni, Ti, V, Cr, Mn, Zn, Ag, Pt, Au, Hg
One or more of catalyst and the multimetal reforming catalyst that is made of above two or two or more components.
The flow of the argon gas is 150mL/min, and the flow of the hydrogen is 100-200mL/min, the C2H4Flow
For 10-100mL/min；The CH4Flow be 100-200mL/min.
In addition the present invention also provides a kind of lithium battery system negative materials, including negative electrode active material and are coated on described
The functionalization graphene composite material on negative electrode active material surface, the lithium battery system negative material have nucleocapsid, institute
Functionalization graphene composite material is stated as the functionalization graphene composite material described in first aspect present invention, the lithium battery body
Be negative material be lithium ion battery negative material or lithium polymer battery negative material.The functionalization graphene composite material
Connected between the negative electrode active material by one or more of π-pi-conjugated, chemical bond, hydrogen bond, Van der Waals force active force
It connects.
Wherein, the mass ratio of the functionalization graphene composite material and the negative electrode active material is 1:1-100.
The present invention also provides a kind of lithium battery system cathode pole pieces, including collector and are supported on the collector
Negative material, the negative material is the above-mentioned lithium battery system negative material of the present invention, the lithium battery system cathode pole
Piece is lithium ion battery negative electrode or lithium polymer battery cathode pole piece.
The present invention also provides a kind of lithium an- ode pole pieces, including metal lithium sheet and are arranged on the lithium metal piece table
The protective layer in face, the material of the protective layer is the functionalization graphene composite material described in first aspect present invention.
Wherein, the functionalization graphene composite material and the mass ratio of the metal lithium sheet are 1:1-100.
And the present invention also provides a kind of battery, the battery includes above-mentioned lithium battery system cathode pole piece or lithium gold
Belong to cathode pole piece.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
Or can be through the embodiment of the present invention implementation and know.
Description of the drawings
Fig. 1 is the structure diagram of lithium ion battery negative material that the embodiment of the present invention 1 is prepared；
Fig. 2 is the charge-discharge performance test chart of lithium-ion button battery that the embodiment of the present invention 1 is prepared；
Fig. 3 is the charge-discharge performance test chart for the lithium metal battery that the embodiment of the present invention 2 prepares gained.
Specific embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise of principle of the embodiment of the present invention is not departed from, several improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
An embodiment of the present invention provides a kind of functionalization graphene composite material, including graphene nanometer sheet, vertical-growth
In the carbon nano pipe array of the graphene nano on piece and by the graphene nanometer sheet poly- electrolysis crosslinked together
Matter passes through one kind in π-pi-conjugated, chemical bond, hydrogen bond, Van der Waals force between the graphene nanometer sheet and the polyelectrolyte
Or several active force connections.
Functionalization graphene composite material provided in an embodiment of the present invention is received based on graphene nanometer sheet in graphene
Rice piece surface vertical-growth carbon nano pipe array passes through polyelectrolyte between graphene nanometer sheet and realizes resilient, crosslinked, the function
Graphite alkene composite material can be used as lithium battery system cathode protection materials, be coated on the table of lithium battery system negative electrode active material
Face is coated on lithium anode surface.In the functionalization graphene composite structure, growth has vertical carbon nanotube array
Graphene nanometer sheet it is interlaced, can be that electrode integrally provide efficient quick conductive network, contribute to battery high rate performance
Raising；Polyelectrolyte is ionic with leading, and can be used as Li+The transmission channels of negative electrode active material are diffused into, ensure that
The fast ionic transmission efficiency of system；Polyelectrolyte has film forming and caking property simultaneously, plays graphene nano lamella and piece
Interlayer, functionalization graphene composite material and " bridge formation " effect being wrapped by between negative electrode active material, work as negative electrode active material
When embedding lithium expansion occurs, using the opposite resilient, crosslinked slided with polyelectrolyte between graphene nanometer sheet, ensure that cathode is lived
Property material be completely wrapped in functionalization graphene composite material film layer, be not exposed in electrolyte, though cathode live
Property material dusting will not lose effective electrical contact with conductive network, thus play stable SEI films, improve pole piece coulomb effect
Rate, the effect for reducing irreversible capacity loss.Meanwhile graphene nanometer sheet has stronger fracture toughness and mechanical strength, protects
Structural stability of the material in cyclic process is demonstrate,proved；When the functionalization graphene composite material is protected applied to lithium anode
When, the film which forms can improve the uniformity of lithium anode surface ion dispersion, effectively avoid lithium
The generation of dendrite, meanwhile, the polyelectrolyte in structure can also improve the interface fusion between lithium metal and electrolyte.
In embodiment of the present invention, the graphene nanometer sheet forms graphene/carbon nanometer with the carbon nano pipe array
Pipe three-dimensional structure compound, the mass ratio of the graphene/carbon nano-tube three-dimensional structure compound and the polyelectrolyte are
1-10:1.Still optionally further, the mass ratio is 3-6:1.
The graphene nanometer sheet be single-layer or multi-layer graphene, thickness 5nm-500nm.Still optionally further, thickness
For 50nm-200nm.
The height of the carbon nano pipe array is 500nm-4 μm.Still optionally further, the height of array is 1 μm -3 μm.
In embodiment of the present invention, the polyelectrolyte includes cationic polyelectrolyte, anionic polyelectrolyte, two
It is one or more in property type polyelectrolyte and polyelectrolyte complex.Polyelectrolyte can be provided quick by its charged ion
Ion-electron transmission channels.The specific connection mode of polyelectrolyte and graphene nanometer sheet depends on the specific knot of polyelectrolyte
Structure can be connected by one or more of π-pi-conjugated, chemical bond, hydrogen bond, Van der Waals force active force according to different structure
It connects.
In embodiment of the present invention, the polyelectrolyte includes protein, nucleic acid, natural gum, modified starch, modified fibre
Element, polyacrylic acid, Sodium Polyacrylate, polyacrylamide, polymethylacrylic acid, polymaleic anhydride, poly-metaphosphoric acid, polyoxyethylene
Alkene, polyvinylamine, polyvinyl pyridine, polyvinylpyrrolidone, kayexalate, O-phthalic acid diethylene glycol dipropyl alkene
One kind in acid esters, polyvinyl sulfonic acid, polyethyleneimine, amino acid, natural acid and polydimethyl diallyl ammonium chloride or
It is a variety of.
Functionalization graphene composite material provided in an embodiment of the present invention, based on graphene nanometer sheet, in graphene
Nanometer sheet surface vertical-growth has a carbon nano pipe array, and resilient, crosslinked is realized by polyelectrolyte between graphene nanometer sheet, should
Functionalization graphene composite material can be used as lithium battery system cathode protection materials, be coated on negative electrode active material surface or modification
In lithium anode surface, the cyclical stability of electrode entirety is improved.
Correspondingly, the embodiment of the present invention additionally provides a kind of preparation method of functionalization graphene composite material, including with
Lower step：
S10, the graphene nanometer sheet for being had carbon nano pipe array using chemical vapour deposition technique preparation surface vertical-growth, are obtained
To graphene/carbon nano-tube three-dimensional structure compound；
S20, dispersion liquid will be obtained in the graphene/carbon nano-tube three-dimensional structure compound ultrasonic disperse to water, by institute
It states dispersion liquid to be mixed 0.5-3 hours with polyelectrolyte aqueous solution, then through centrifuging, washing, gained precipitation is functionalization
Graphene composite material.
In embodiment of the present invention, in step S10, the preparation of the graphene/carbon nano-tube three-dimensional structure compound
Journey is specially：
S11, metallic catalyst is taken, by the metallic catalyst equably splash to substrate, and the substrate is placed in
Then the quartz ampoule is placed in tube furnace and heats by the center of horizontal quartz tube again；
S12, argon gas and hydrogen are passed through into the tube furnace, after in-furnace temperature rises to 500 DEG C -1000 DEG C, introduced anti-
Answer gas C2H410min-100min is reacted, with vertical-growth carbon nano pipe array on the substrate；
S13, air-flow is become to argon gas and is heated to 500 DEG C -1000 DEG C, reaction gas CH is introduced to the tube furnace4Instead
10min-100min is answered, to generate horizontal graphene nanometer sheet between the carbon nano pipe array of vertical-growth to get to graphite
Alkene/carbon nanotube three-dimensional structure compound crude product；
S14, after reaction cools down tube body, takes out the crude product, and by the crude product 1mol/L-10mol/L
50 DEG C -150 DEG C of HCl/water solution at handle 5h-24h, then at 50 DEG C -150 DEG C of the HF aqueous solutions of 1mol/L-10mol/L
5h-24h is managed, obtains the graphene/carbon nano-tube three-dimensional structure compound.
In embodiment of the present invention, in step S11, the metallic catalyst include Cu, Al, Fe, Mo, Co, Ni, Ti, V,
One in Cr, Mn, Zn, Ag, Pt, Au, Hg catalyst and the multimetal reforming catalyst being made of above two or two or more components
Kind is several.Optionally, substrate can be aluminium oxide porcelain boat etc..
In embodiment of the present invention, in step S12, the flow of the argon gas is 150mL/min, and the flow of the hydrogen is
100mL/min-200mL/min, the C2H4Flow be 10mL/min-100mL/min.Still optionally further, the hydrogen
Flow is 120mL/min-160mL/min, the C2H4Flow be 50mL/min-80mL/min.Optionally, in-furnace temperature is treated
After rising to 600 DEG C -900 DEG C, reaction gas C is introduced2H4。
In embodiment of the present invention, in step S13, the flow of the argon gas is 150mL/min, the CH4Flow be
100mL/min-200mL/min.Still optionally further, the CH4Flow be 120mL/min-160mL/min.Optionally, add
Heat introduces reaction gas CH to after 600 DEG C -900 DEG C4。
In embodiment of the present invention, in step S20, the graphene/carbon nano-tube three-dimensional structure in the dispersion liquid is compound
The mass ratio of object and the polyelectrolyte in the polyelectrolyte aqueous solution is 1-10:1.Still optionally further, the mass ratio
For 3-6:1.The concentration of the dispersion liquid can be 1mg/mL-2.5mg/mL；The concentration of the polyelectrolyte aqueous solution can be
0.05g/L-0.2g/L.The washing is carried out using deionized water.
The preparation method of functionalization graphene composite material provided in an embodiment of the present invention, it is simple for process, conducive to industrialization
Production.
Functionalization graphene composite material provided in an embodiment of the present invention can be used for lithium ion battery, lithium polymer battery powder
The surface protection of body negative electrode active material is particularly suitable for solving the problems, such as the embedding lithium volume expansion of negative electrode active material.It is corresponding
Ground, an embodiment of the present invention provides a kind of lithium battery system negative materials, including negative electrode active material and are coated on the cathode
The functionalization graphene composite material of surface of active material, the lithium battery system negative material have nucleocapsid, the work(
Can graphite alkene composite material be the above-mentioned functionalization graphene composite material provided of the embodiment of the present invention, the lithium battery system
Negative material is lithium ion battery negative material or lithium polymer battery negative material.The functionalization graphene composite material with
It is connected between the negative electrode active material by one or more of π-pi-conjugated, chemical bond, hydrogen bond, Van der Waals force active force.
In embodiment of the present invention, the mass ratio of the functionalization graphene composite material and the negative electrode active material is
1:1-100.Further mass ratio is 1:1-25 or 1:30-80.
In embodiment of the present invention, liquid phase method, solid phase method, electrochemistry may be used in the functionalization graphene composite material
One or more of method, sputtering method, spray drying process method is modified on the negative electrode active material surface.The above method
Concrete operations parameter can be set as the case may be.
Lithium battery system negative material provided in an embodiment of the present invention, by coating functionalization on negative electrode active material surface
Graphene composite material, the shell that the functionalization graphene composite material is formed play negative electrode active material surface artificial SEI
The poly- electrolysis at graphene film layer surface and edge is slided and modified to the effect of film, opposite using high tenacity graphene film interlayer
The resilient, crosslinked effect of matter layer, it is ensured that negative electrode active material kernel is still completely coated on functionalization graphene upon inflation
Inside composite material shell, and it is avoided to cause excessive irreversible capacity loss with contacting repeatedly for electrolyte.
The embodiment of the present invention additionally provides a kind of lithium battery system cathode pole piece, including collector and is supported on the collection
Negative material on fluid, the negative material is the above-mentioned lithium battery system negative material provided of the embodiment of the present invention, described
Lithium battery system cathode pole piece is lithium ion battery negative electrode or lithium polymer battery cathode pole piece.
Functionalization graphene composite material provided in an embodiment of the present invention can also be used for lithium metal battery, lithium-sulfur cell, lithium
The lithium an- ode protection using lithium metal as cathode such as air cell.Since metal lithium electrode surface has in charging process
Huge volume expansion, and the SEI films of its surface self-assembling formation are more crisp, and defect can be caused after Li expansions cause SEI films to be broken
Locate the growth of Li dendrite, cause battery short circuit and relatively low coulombic efficiency.And by the above-mentioned function graphite of the embodiment of the present invention
Alkene composite material is coated on metallic lithium surface, can stablize SEI film layers, effectively solve the above problems.
Correspondingly, an embodiment of the present invention provides a kind of lithium an- ode pole pieces, including metal lithium sheet and are arranged on institute
The protective layer on lithium metal piece surface is stated, the material of the protective layer is the above-mentioned functionalization graphene composite wood of the embodiment of the present invention
Material.Pass through π-pi-conjugated, chemical bond, hydrogen bond, Van der Waals force between the functionalization graphene composite material and the metal lithium sheet
One or more of active force connection.
In embodiment of the present invention, the mass ratio of the functionalization graphene composite material and the metal lithium sheet is 1:1-
100.Further mass ratio is 1:20-50 or 1:50-100.
The lithium an- ode pole piece can be used following manner and be prepared：Functionalization graphene composite material is scattered in
In NMP organic solvents, mixed slurry is obtained, gained mixed slurry is then coated on metal lithium sheet electrode surface, vacuum 50-65
DEG C be dried overnight to get.
In addition, the embodiment of the present invention additionally provides a kind of battery, the battery includes above-mentioned lithium battery system cathode pole
Piece or lithium an- ode pole piece.Wherein, it is lithium ion battery or lighium polymer electricity including the lithium battery system cathode pole piece
Pond；And it is lithium metal battery, lithium-air battery or lithium-sulfur cell including the lithium an- ode pole piece.The embodiment of the present invention carries
The battery of confession has good cyclical stability.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.Wherein, the embodiment of the present invention is unlimited
Due to following specific embodiment.In the range of constant principal right, implementation can be suitably changed.
Embodiment 1
A kind of preparation method of functionalization graphene composite material, includes the following steps：
S101：It is compound that graphene/carbon nano-tube three-dimensional structure is prepared using metal Fe/Mo as chemical vapor deposition (CVD)
Porcelain boat by the uniform splash to porcelain boat of Fe/Mo catalyst, and is placed in the center of horizontal quartz tube by the catalysts of object,
It is heated in tube furnace；
S102：Ar (150mL/min) and H is passed through in tube furnace2(120mL/min) after temperature rises to 750 DEG C, draws
Enter reaction gas C2H4(60mL/min) reacts 30min to generate the carbon nanotube of vertical arrangement (CNT) array；
S103：Air-flow is become into Ar (150mL/min), and be heated to 950 DEG C, changes reaction gas as CH4(120mL/min),
Logical 30min is answered with generating horizontal graphene nanometer sheet between vertical CNT array to get to graphene/carbon nano-tube three-dimensional structure
Close object crude product；
S104：After reaction, tube body is cooled down under conditions of Ar streams are persistently led to, by gained graphene/carbon nano-tube three
Handle 12h at 80 DEG C of HCl (6.0mol/L) aqueous solution of dimension structural composites crude product, then with HF (6.0mol/L) aqueous solution 80
12h is handled at DEG C, to remove catalytic component in product, obtains graphene/carbon nano-tube three-dimensional structure compound (CNT/CNs)；
S105：By above-mentioned gained graphene/carbon nano-tube three-dimensional structure compound ultrasonic disperse in 200mL deionized waters
Form the suspension of a concentration of 1mg/mL；It is stirred again with the kayexalate of a concentration of 0.1g/L of 50mL (PSS) aqueous solution
Mix 30min；Through being centrifuged repeatedly washing, supernatant liquor is removed, must be precipitated Ji Wei functionalization graphene composite material (CNT/CNs/
PSS ternary complexes).
The preparation of lithium ion battery negative material
Lithium ion battery silicon-carbon compound powder body material is surface modified using functionalization graphene composite material：It will
Silicon-carbon cathode composite materials powder granule presses 10 with CNT/CNs/PSS:1 mass ratio is scattered in deionized water, and mixing is super
It after sound 2h, being filtered under diminished pressure and removes water, obtain the silicon-carbon compound that filter cake is CNT/CNs/PSS claddings, 60 DEG C of vacuum is dried overnight,
Obtain lithium ion battery negative material product.
Fig. 1 is the structure diagram of lithium ion battery negative material that the embodiment of the present invention 1 is prepared.In figure, 10 are
Silicon-carbon cathode composite materials kernel, 20 be functionalization graphene composite material (CNT/CNs/PSS ternary complexes) shell,
201 represent graphene nanometer sheet, and 202 represent carbon nanotube, and 203 represent polyelectrolyte.
It is prepared by lithium ion battery
Button cell makes:By the above-mentioned lithium ion battery negative material being prepared according to negative material:Conductive black:
Butadiene-styrene rubber=80:10:10 ratio is coated on copper foil current collector surface after being stirred evenly using deionized water as dispersant；Very
After sky is dry, slice is weighed, in the environment of glove box high-purity argon gas using metal lithium sheet as to electrode assembling into button cell.Its
In, diaphragm Celgard2400, electrolyte is 1M LiPF6/EC+PC+DEC+EMC (volume ratios 1:0.3:1:1) solution.Electrification
It is 0.02-1.5V to learn test charging/discharging voltage window, and environmental testing temperature is 25 ± 2 DEG C.
Full battery makes：Using 4.4V high voltages cobalt acid lithium as positive electrode, according to active material:Conductive black:PVDF=
80:10:10 ratio is scattered in nmp solvent and coated on aluminium foil surface, as anode pole piece after vacuum drying, with above-mentioned silicon-carbon
For composite material pole piece as cathode, electrolyte is 1M LiPF6/EC+PC+DEC+EMC (volume ratios 1:0.3:1:1), diaphragm PP/
PE/PP three-layer membranes (thickness is 16 μm), assemble in glove box and help battery；Full battery electrochemical tests charge and discharge window
2.75-4.4V, environmental testing temperature are 25 ± 2 DEG C.
Embodiment 2
A kind of preparation method of functionalization graphene composite material, includes the following steps：
S201：The catalysts of graphene/carbon nano-tube three-dimensional structure compound are prepared using metal Co as CVD, it will
In the uniform splash to porcelain boat of Co catalyst, and porcelain boat is placed in the center of horizontal quartz tube, is heated in tube furnace；
S202：Ar (150mL/min) and H is passed through in tube furnace2(180mL/min) after temperature rises to 600 DEG C, draws
Enter reaction gas C2H4(80mL/min) 20min is to generate the CNT array of vertical arrangement；
S203：Air-flow is become into Ar (150mL/min) and is heated to 1050 DEG C, introducing reaction gas CH4(150mL/min)
20min between vertical CNT array to generate horizontal graphene nanometer sheet；
S204：After reaction, tube body is cooled down under conditions of Ar streams are persistently led to, by gained graphene/carbon nano-tube three
Handle 15h at 60 DEG C of HCl (8.0mol/L) aqueous solution of dimension structural composites crude product, then with HF (8.0mol/L) aqueous solution 60
15h is handled at DEG C, to remove catalytic component in product, obtains graphene/carbon nano-tube three-dimensional structure compound (CNT/CNs).
S205：Graphene/carbon nano-tube three-dimensional structure compound ultrasonic disperse is formed into concentration in 200mL deionized waters
Suspension for 2.5mg/mL；Again with the phthalic acid diethylene glycol diacrylate of a concentration of 0.08g/L of 100mL (PDDA)
Aqueous solution is stirred 60min；Again through being centrifuged repeatedly washing, supernatant liquor is removed, must be precipitated compound Ji Wei functionalization graphene
Material (CNT/CNs/PDDA ternary complexes)；
The preparation of lithium an- ode pole piece
Lithium battery lithium anode is surface modified using functionalization graphene composite material：By CNT/CNs/PDDA
It is scattered in NMP organic solvents, obtains mixed slurry, gained mixed slurry is coated on metal lithium electrode table in a manner of spin coating
Face is dried overnight at 60 DEG C of vacuum, obtains the lithium an- ode pole piece of functionalization graphene composite material modification；Wherein metal lithium sheet
Mass ratio with CNT/CNs/PDDA protective layers is 10:1.
The preparation of lithium metal battery
By α-MnO2Powder is according to active material:Conductive black:Butadiene-styrene rubber=80:10:It is molten that 10 ratio is scattered in NMP
Agent is coated with being dried in vacuo after aluminium foil, is sliced and weighs；With α-MnO in glove box2Pole piece is as anode, using functionalization
Metal lithium sheet after the protection of graphene composite material surface modification is as cathode, 1M LiPF6/EC+PC+DEC+EMC (volume ratios 1:
0.3:1:1) it is electrolyte, Celgard2400 is assembled into lithium metal battery for diaphragm；Electro-chemical test operating voltage is 2.75-
3.3V, environmental testing temperature are 25 ± 2 DEG C.
Embodiment 3
A kind of preparation method of functionalization graphene composite material, includes the following steps：
S301：Graphene/carbon nano-tube three-dimensional structure compound is prepared using Ni metal as chemical vapor deposition (CVD)
Porcelain boat by the uniform splash to porcelain boat of Cu catalyst, and is placed in the center of horizontal quartz tube, in tube furnace by catalysts
Heating；
S302：Ar (180mL/min) and H is passed through in tube furnace2(120mL/min) after temperature rises to 600 DEG C, draws
Enter reaction gas C2H4(80mL/min) reacts 15min to generate the carbon nanotube of vertical arrangement (CNT) array；
S303：Air-flow is become into Ar (100mL/min), and be heated to 1000 DEG C, changes reaction gas as CH4(150mL/min),
Logical 20min is answered with generating horizontal graphene nanometer sheet between vertical CNT array to get to graphene/carbon nano-tube three-dimensional structure
Close object crude product；
S304：After reaction, tube body is cooled down under conditions of Ar streams are persistently led to, by gained graphene/carbon nano-tube three
Handle 12h at 80 DEG C of HCl (6.0mol/L) aqueous solution of dimension structural composites crude product, then with HF (6.0mol/L) aqueous solution 80
12h is handled at DEG C, to remove catalytic component in product, obtains graphene/carbon nano-tube three-dimensional structure compound (CNT/CNs)；
S305：By above-mentioned gained graphene/carbon nano-tube three-dimensional structure compound ultrasonic disperse in 200mL deionized waters
Form the suspension of a concentration of 1mg/mL；The polyvinyl sulfonic acid aqueous solution with a concentration of 0.2g/L of 50mL is stirred 30min again；
Through being centrifuged repeatedly washing, supernatant liquor is removed, must be precipitated Ji Wei functionalization graphene composite material (CNT/CNs/ polyvinyl sulfonic acids
Ternary complex).
Embodiment 4
A kind of preparation method of functionalization graphene composite material, includes the following steps：
S401：Graphene/carbon nano-tube three-dimensional structure compound is prepared using metal Al as chemical vapor deposition (CVD)
Porcelain boat by the uniform splash to porcelain boat of Al catalyst, and is placed in the center of horizontal quartz tube, in tube furnace by catalysts
Heating；
S402：Ar (200mL/min) and H is passed through in tube furnace2(150mL/min) after temperature rises to 800 DEG C, draws
Enter reaction gas C2H4(50mL/min) reacts 20min to generate the carbon nanotube of vertical arrangement (CNT) array；
S403：Air-flow is become into Ar (100mL/min), and be heated to 800 DEG C, changes reaction gas as CH4(120mL/min),
Logical 40min is answered with generating horizontal graphene nanometer sheet between vertical CNT array to get to graphene/carbon nano-tube three-dimensional structure
Close object crude product；
S404：After reaction, tube body is cooled down under conditions of Ar streams are persistently led to, by gained graphene/carbon nano-tube three
Handle 12h at 80 DEG C of HCl (6.0mol/L) aqueous solution of dimension structural composites crude product, then with HF (6.0mol/L) aqueous solution 80
12h is handled at DEG C, to remove catalytic component in product, obtains graphene/carbon nano-tube three-dimensional structure compound (CNT/CNs)；
S405：By above-mentioned gained graphene/carbon nano-tube three-dimensional structure compound ultrasonic disperse in 200mL deionized waters
Form the suspension of a concentration of 1mg/mL；The aq. polyethyleneimine with a concentration of 0.1g/L of 50mL is stirred 30min again；
Through being centrifuged repeatedly washing, supernatant liquor is removed, must be precipitated Ji Wei functionalization graphene composite material (CNT/CNs/ polyethyleneimines
Ternary complex).
Effect example
Advantageous effect to be brought to technical solution of the embodiment of the present invention provides powerful support for, and provides following performance and surveys
Examination：
The embodiment of the present invention 1 is prepared to the charge and discharge cycles under the lithium-ion button battery progress 0.2C current densities of gained
Performance test, test result are as shown in Figure 2.The results show that the button cell has excellent cycle performance, this is because this hair
Bright embodiment using functionalization graphene composite material as protection materials, to lithium ion battery silicon-carbon compound powder body material into
Row surface coats, and can effectively inhibit the silicium cathode material surface that enormousness expansion is brought in embedding lithium/de- lithium cycle is repeated
SEI films rupture, and so as to greatly reduce irreversible capacity loss of the electrode in cyclic process, improve battery cycle life.
The lithium metal battery that the embodiment of the present invention 2 is prepared to gained carries out cycle performance test, test result such as Fig. 3 institutes
Show.After 100 weeks are recycled under 2C current densities, the battery short circuit phenomenon caused by lithium dendrite growth does not occur for battery, and
Cycle performance is excellent.Illustrate that functionalization graphene composite material prepared by the embodiment of the present invention is protected suitable for lithium an- ode,
And lithium battery cycle performance is contributed to be promoted.
It should be noted that according to the above description the announcement of book and with illustrate, those skilled in the art in the invention also
The above embodiment can be changed and be changed.Therefore, the invention is not limited in specific realities disclosed and described above
Mode is applied, some equivalent modifications and change to the present invention should also be as within the scope of the claims of the present invention.This
Outside, although having used some specific terms in this specification, these terms merely for convenience of description, not to the present invention
Form any restrictions.
Claims (16)
1. a kind of functionalization graphene composite material, which is characterized in that including graphene nanometer sheet, vertical-growth in the graphite
Carbon nano pipe array in alkene nanometer sheet and by graphene nanometer sheet polyelectrolyte crosslinked together, the graphite
Pass through the effect of one or more of π-pi-conjugated, chemical bond, hydrogen bond, Van der Waals force between alkene nanometer sheet and the polyelectrolyte
Power connects.
2. functionalization graphene composite material as described in claim 1, which is characterized in that the graphene nanometer sheet with it is described
Carbon nano pipe array forms graphene/carbon nano-tube three-dimensional structure compound, and the graphene/carbon nano-tube three-dimensional structure is compound
The mass ratio of object and the polyelectrolyte is 1-10:1.
3. functionalization graphene composite material as described in claim 1, which is characterized in that the graphene nanometer sheet is individual layer
Or multi-layer graphene, thickness 5nm-500nm.
4. functionalization graphene composite material as described in claim 1, which is characterized in that the height of the carbon nano pipe array
It is 500nm-4 μm.
5. functionalization graphene composite material as described in claim 1, which is characterized in that the polyelectrolyte includes cation
It is one or more in type polyelectrolyte, anionic polyelectrolyte, amphoteric polyelectrolyte and polyelectrolyte complex.
6. functionalization graphene composite material as claimed in claim 5, which is characterized in that the polyelectrolyte includes albumen
Matter, nucleic acid, natural gum, modified starch, modified cellulose, polyacrylic acid, Sodium Polyacrylate, polyacrylamide, polymethylacrylic acid,
Polymaleic anhydride, poly-metaphosphoric acid, polyethylene glycol oxide, polyvinylamine, polyvinyl pyridine, polyvinylpyrrolidone, polystyrene sulphur
Sour sodium, phthalic acid diethylene glycol diacrylate, polyvinyl sulfonic acid, polyethyleneimine, amino acid, natural acid and poly- two
It is one or more in methyl diallyl ammonium chloride.
7. a kind of preparation method of functionalization graphene composite material, which is characterized in that include the following steps：
Preparing surface vertical-growth using chemical vapour deposition technique has the graphene nanometer sheet of carbon nano pipe array, obtains graphite
Alkene/carbon nanotube three-dimensional structure compound；
Dispersion liquid will be obtained in the graphene/carbon nano-tube three-dimensional structure compound ultrasonic disperse to water, by the dispersion liquid
It is mixed 0.5-3 hours with polyelectrolyte aqueous solution, then through centrifuging, washing, gained precipitation is that functionalization graphene is answered
Condensation material.
8. preparation method as claimed in claim 7, which is characterized in that the graphene/carbon nano-tube three-dimensional structure compound
Preparation process be specially：
Metallic catalyst is taken, by the metallic catalyst equably splash to substrate, and the substrate is placed in horizontal quartz
Then the quartz ampoule is placed in tube furnace and heats by the center of pipe again；
Argon gas and hydrogen are passed through into the tube furnace, after in-furnace temperature rises to 500 DEG C -1000 DEG C, introduces reaction gas C2H4
10min-100min is reacted, with vertical-growth carbon nano pipe array on the substrate；
Air-flow is become into argon gas and is heated to 500 DEG C -1000 DEG C, reaction gas CH is introduced to the tube furnace4React 10min-
100min, to generate horizontal graphene nanometer sheet between the carbon nano pipe array of vertical-growth to get to graphene/carbon nanometer
Pipe three-dimensional structure compound crude product；
After reaction, tube body is cooled down, takes out the crude product, and by the HCl/water of the crude product 1mol/L-10mol/L
5h-24h is handled at 50 DEG C -150 DEG C of solution, then 5h- is handled at 50 DEG C -150 DEG C of the HF aqueous solutions of 1mol/L-10mol/L
For 24 hours, the graphene/carbon nano-tube three-dimensional structure compound is obtained.
9. preparation method as claimed in claim 8, which is characterized in that the metallic catalyst include Cu, Al, Fe, Mo, Co,
Ni, Ti, V, Cr, Mn, Zn, Ag, Pt, Au, Hg catalyst and the more metal catalytics being made of above two or two or more components
One or more of agent.
10. preparation method as claimed in claim 8, which is characterized in that the flow of the argon gas be 150mL/min, the hydrogen
The flow of gas is 100mL/min-200mL/min, the C2H4Flow be 10mL/min-100mL/min；The CH4Flow
For 100mL/min-200mL/min.
11. a kind of lithium battery system negative material, which is characterized in that including negative electrode active material and be coated on the negative electrode active
The functionalization graphene composite material of material surface, the lithium battery system negative material have nucleocapsid, the functionalization
Graphene composite material is claim 1-6 any one of them functionalization graphene composite materials, and the lithium battery system is born
Pole material is lithium ion battery negative material or lithium polymer battery negative material.
12. lithium battery system negative material as claimed in claim 11, which is characterized in that the functionalization graphene composite wood
The mass ratio of material and the negative electrode active material is 1:1-100.
13. a kind of lithium battery system cathode pole piece, which is characterized in that including collector and be supported on negative on the collector
Pole material, the negative material are the lithium battery system negative material described in claim 11 or 12, and the lithium battery system is born
Pole pole piece is lithium ion battery negative electrode or lithium polymer battery cathode pole piece.
14. a kind of lithium an- ode pole piece, which is characterized in that including metal lithium sheet and be arranged on the metal lithium sheet surface
Protective layer, the material of the protective layer is claim 1-6 any one of them functionalization graphene composite materials.
15. lithium an- ode pole piece as claimed in claim 14, which is characterized in that the functionalization graphene composite material with
The mass ratio of the metal lithium sheet is 1:1-100.
16. a kind of battery, which is characterized in that the battery include lithium battery system cathode pole piece as claimed in claim 13 or
Lithium an- ode pole piece as claimed in claim 14.
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| CN109065948A (en) * | 2018-08-13 | 2018-12-21 | 湖南省长沙市第中学 | Solid lithium battery, solid polymer electrolyte membrane and preparation method thereof |
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| CN109065948A (en) * | 2018-08-13 | 2018-12-21 | 湖南省长沙市第中学 | Solid lithium battery, solid polymer electrolyte membrane and preparation method thereof |
| CN109378476A (en) * | 2018-09-27 | 2019-02-22 | 苏州大学 | Using the method for self assembly RGO film preparation lithium electrode protective layer |
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| CN115036646A (en) * | 2022-04-26 | 2022-09-09 | 青岛科技大学 | Nano composite material battery diaphragm, preparation method thereof and lithium battery |
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