CN107871850A - A kind of silicon/graphene composite film electrode and preparation method thereof and lithium ion battery - Google Patents
A kind of silicon/graphene composite film electrode and preparation method thereof and lithium ion battery Download PDFInfo
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- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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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- 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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- 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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of silicon/graphene composite film electrode, silicon/graphene composite film on the collector is formed including collector and by electrostatic self-assembled, silicon/the graphene composite film includes at least one layer of silicon membrane layer of alternately laminated setting and at least one layer of graphene film layer, the silicon membrane layer by electrostatic attraction be incorporated on the collector or the graphene film layer on, the graphene layer is incorporated on the collector or on the silicon membrane layer by electrostatic attraction.The electrode has high structural stability, and electrode structure caused by can effectively alleviating silicon materials expansion destroys, and improves battery cycle life, and have height ratio capacity and high rate capability.Present invention also offers the preparation method of the electrode and the lithium ion battery including the electrode.
Description
Technical field
The present invention relates to battery electrode preparing technical field, more particularly to a kind of silicon/graphene composite film electrode and
Its preparation method and lithium ion battery.
Background technology
Lithium ion battery has open-circuit voltage height compared with traditional secondary cell, energy density is big, service life is long, certainly
Discharge the advantages such as small, memory-less effect, be widely used in mobile electronic device and electric automobile field.
At present, the lithium ion battery negative material of commercialization is mainly the carbon-based materials such as graphite, its discharge capacity base
Originally in 350mAh/g or so, can not meet the needs of following lithium ion battery is to high-energy-density.And silicon materials are with known
Maximum embedding lithium capacity (4212mAh/g), contributes to the lifting of battery energy density, and studied scholar is considered the ideal of a new generation
Negative material.But the enormousness that silicon is shown during embedding lithium/de- lithium is repeated changes (＞ 300%), causes material easy
Broken and efflorescence occurs, loses good electrical connection and lithium ion transmission channels and causes the rapid decay of capacity.
One of existing effective way for solving the problems, such as silicon cycling stability difference is that silicon and other negative materials is compound.Stone
Black alkene as a kind of New Two Dimensional nano material, have high conductivity, high-specific surface area, high-mechanical property and be widely used in
Energy storage field research.In recent years, graphene and the compound report as lithium ion battery negative material of silicon are of common occurrence.But
It is due to that graphene and chemistry of silicones stability are higher, is hardly formed stronger adhesion and causes compound uneven and silicon grain swollen
The situation that swollen rear and graphene conductive network departs from, does not solve the problems, such as silicon cycling stability difference fundamentally.Therefore, open
Send out high mechanical properties a kind of and the 3 SiC 2/graphite alkene composite negative pole material of long circulation life be field of lithium ion battery technical barrier.
The content of the invention
In consideration of it, first aspect present invention provides a kind of silicon/graphene composite film electrode, the electrode has high structure
Stability, electrode structure caused by can effectively alleviating silicon materials expansion destroy, and improve battery cycle life, and be advantageous to electronics
Quick transmission with ion is to improve battery charge efficiency.
Specifically, in a first aspect, the invention provides a kind of silicon/graphene composite film electrode, including collector and logical
Cross electrostatic self-assembled and form silicon/graphene composite film on the collector, the silicon/graphene composite film includes handing over
Pass through electrostatic attraction knot at least one layer of silicon membrane layer and at least one layer of graphene film layer, the silicon membrane layer being stacked
Close on the collector or on the graphene film layer, the graphene layer is incorporated in the collector by electrostatic attraction
On upper or described silicon membrane layer.
In the present invention, the 1-20 layers silicon membrane layer of the silicon/graphene composite film including alternately laminated setting and
The 1-20 layers graphene film layer.
The outermost layer of the silicon/graphene composite film is graphene film layer.
There is loose porous structure inside the silicon/graphene composite film.
Alternatively, the collector carries negative electrical charge, and the silicon membrane layer carries positive charge or negative electrical charge, the graphene
Film layer carries positive charge or negative electrical charge.
The silicon materials surface modification of the silicon membrane layer has cationic polyelectrolyte, the graphite of the graphene film layer
Alkene surface modification has anionic polyelectrolyte.
The cationic polyelectrolyte includes the polymer with basic ionizable group, the basic ionizable group
Including amino, imino group.Specifically, it can be diallyl dimethyl ammoniumchloride.
The anionic polyelectrolyte includes carrying after carrying carboxyl, the polymer of alkoxy or phenol epoxide or ionization
Carbanion, bicarbonate ion, phosphate anion, silicic acid foundation ion, the polymer of sulphion.Specifically, Ke Yishi
Polyacrylic acid.
The thickness of the silicon membrane layer is 500nm-2 μm.
The thickness of the graphene film layer is 500nm-2 μm.
The quality accounting of silicon membrane layer is 5%-90% in the silicon/graphene composite film, still optionally further for
5%-30%.
Wherein, the silicon materials of the silicon membrane layer are silicon nano, silicon nanofiber, silicon nanorod, nano-tube, silicon
One or more in nanoneedle and silicon nanoporous microballoon.
The average grain diameter of the silicon nano is 10nm-900nm, is optionally 300nm-500nm；The silicon Nanowire
Dimension, silicon nanorod, a diameter of 5nm-900nm of the average transverse of nano-tube or silicon nanoneedle, are optionally 100nm-500nm；
The average grain diameter of the silicon nanoporous microballoon is 10nm-900nm, is optionally 500nm-800nm.
The collector is metal foil, coated metal paper tinsel, alloy, stainless steel, silicon chip, conductive carbon, electro-conductive glass, conduction
One kind in fiber cloth and graphene-based substrate.
Silicon/graphene composite film electrode that first aspect present invention provides, has height ratio capacity, and silicon membrane layer and stone
Black alkene film layer is combined on a current collector by electrostatic attraction, between silicon materials are intactly coated on graphene layer, electrode knot
Structure stability is strong；High conductivity graphene network can provide efficient quick electron transmission simultaneously, make electrode have high power forthright
Energy；In addition, between interlayer between the high degree of flexibility and pore structure and silicon membrane layer and graphene film layer of graphene film
Gap can provide enough cushion spaces for the expansion of silicon, so that electrode obtains higher cyclical stability.
Second aspect, the invention provides a kind of preparation method of silicon/graphene composite film electrode, including following step
Suddenly：
Collector is provided, the collector is subjected to negative electricity processing, obtains electronegative collector；
Silicon materials are provided, the silicon materials are subjected to electric charge processing, obtain electrically charged silicon materials dispersion liquid；
Graphene is provided, the graphene is subjected to electric charge processing, obtains the stone with the silicon materials oppositely charged
Black alkene dispersion liquid；
The electronegative collector is alternately immersed in the electrically charged silicon materials dispersion liquid and described and silicon materials
In the graphene dispersing solution of oppositely charged, deposit thin films of silicon layer on the electronegative collector is acted on by electrostatic attraction
With graphene film layer, silicon/graphene composite film is finally self-assembly of, that is, obtains silicon/graphene composite film electrode, institute
Stating silicon/graphene composite film includes at least one layer of silicon membrane layer of alternately laminated setting and at least one layer of graphene film layer.
Wherein, it is by the concrete operations of collector progress negative electricity processing：Soaked using the alcohol water mixed solution of alkali
The collector.The alkali includes LiOH, NaOH, KOH, RbOH, CsOH, FrOH, Ca (OH)2、Sr(OH)2、Ba(OH)2、Ra
(OH)2、HgOH、TiOH、AgOH·NH3With the one or more in choline.
Wherein, it is by the concrete operations of silicon materials progress electric charge processing：The silicon materials are scattered in certain dense
Ultrasonic disperse in the cationic polyelectrolyte aqueous solution of degree, obtain positively charged silicon materials dispersion liquid.
By the graphene carry out electric charge processing concrete operations be：Using anionic polyelectrolyte to peeling off state
Graphene film carries out surface modification, obtains negatively charged graphene dispersing solution.
The preparation method for silicon/graphene composite film electrode that second aspect of the present invention provides, first pass through electric chargeization processing
So that nano silicon material and graphite olefinic constituent carry opposite charges, then by negatively charged collector electrostatic precipitation in situ obtain
To the membrane electrode structure of layer assembly, the process route is simple, and the electrode specific capacity being prepared is high, Stability Analysis of Structures, circulation
Performance is good, is provided simultaneously with high rate capability.
In addition, third aspect present invention provides a kind of lithium ion battery, it is above-mentioned that the lithium ion battery includes the present invention
Silicon/graphene composite film electrode described in first aspect.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
, or can be known by the implementation of the embodiment of the present invention.
Brief description of the drawings
Fig. 1 is the structural representation of silicon/graphene composite film electrode in the embodiment of the invention；
Fig. 2 is the electrostatic self-assembled deposition process schematic diagram of silicon/graphene composite film in the embodiment of the present invention 1；
Fig. 3 is filling first using silicon/button cell made from graphene composite film electrode of the embodiment of the present invention 2
Electricity/discharge curve；
Fig. 4 is to be surveyed using the cycle performance of full battery made from silicon/graphene composite film electrode of the embodiment of the present invention 2
Test result.
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, on the premise of principle of the embodiment of the present invention is not departed from, some 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.
The embodiments of the invention provide a kind of silicon/graphene composite film electrode, including collector and by electrostatic from group
Dress forms silicon/graphene composite film on the collector, and the silicon/graphene composite film includes alternately laminated setting
At least one layer of silicon membrane layer and at least one layer of graphene film layer, the silicon membrane layer collection is incorporated in by electrostatic attraction
On fluid or on the graphene film layer, the graphene layer is incorporated in by electrostatic attraction on the collector or the silicon
In film layer.
The silicon of the embodiment of the present invention/graphene composite film electrode, due to comprising high power capacity silicon materials, thus with higher
Specific capacity.The silicon of the embodiment of the present invention/graphene composite film electrode, change the physics synthesis side of traditional silicon carbon complex
Method, silicon membrane layer and graphene film layer are combined on a current collector by stronger electrostatic attraction, therefore electrode structure is stable
Property is strong；And alternately laminated set of two kinds of film layers is in interlayer sandwich-like structure, nano silicon material is completely coated on graphene
In conductive network, graphene layer can provide enough cushion spaces for the volumetric expansion of silicon, ensure its reexpansion shrink after still
It is wrapped in graphene conductive network, effective electrical contact with electrode will not be lost；Graphene can also improve electrode entirety
Electric conductivity, effectively improve the high rate performance of electrode；The interlaminal toughness and pore structure and silicon membrane layer and stone of other graphene
Interlayer spacings between black alkene film layer can provide enough cushion spaces for the expansion of silicon, so that electrode obtains higher follow
Ring stability.
The silicon of the embodiment of the present invention/graphene composite film electrode, silicon/graphene composite film on a current collector it is in situ into
Film, the use of conductive additive and binding agent is avoided, improves electrode capacity.
In embodiment of the present invention, the silicon/graphene composite film can include one or more layers silicon membrane layer, and
Including one or more layers graphene film layer.Can be specifically include alternately laminated setting the 1-20 layers silicon membrane layer and
The 1-20 layers graphene film layer.More specifically can be the 3-15 layers silicon membrane layer and 3- for including alternately laminated setting
15 layers of graphene film layer.In embodiment of the present invention, the number of plies of silicon membrane layer and graphene film layer can with equal,
Can be with unequal.
In embodiment of the present invention, in the silicon/graphene composite film, with the collector directly in conjunction with innermost layer
Can be silicon membrane layer or graphene film layer.
In the preferred embodiment for the present invention, the outermost layer of the silicon/graphene composite film is graphene film layer.It is compound
Outermost layer is graphene film layer in membrane electrode, can effectively avoid silicon from being contacted with the direct of electrolyte, be advantageous to stablize SEI
Film, the irreversible capacity loss of electrode material is reduced, and then improve electrode cycle life.
Alternatively, in embodiment of the present invention, the collector carries negative electrical charge, the silicon membrane layer with positive charge or
Negative electrical charge, the graphene film layer carry positive charge or negative electrical charge.In the embodiment of the invention, the silicon membrane layer
Cationic polyelectrolyte is modified with, the graphene film layer is modified with anionic polyelectrolyte.The cationic poly
Electrolyte includes the polymer with basic ionizable group, and the basic ionizable group includes amino, imino group.Specifically
Ground, can be diallyl dimethyl ammoniumchloride.The anionic polyelectrolyte includes carrying carboxyl, alkoxy or phenol oxygen
With carbanion, bicarbonate ion, phosphate anion, silicic acid foundation ion, sulphion after the polymer of base or ionization
Polymer.Specifically, it can be polyacrylic acid.In the embodiment, alternating layer successively is included with silicon/graphene composite film
Exemplified by the folded 3 layers of silicon membrane layer set and 3 layer graphene film layers, the structure of silicon/graphene composite film electrode is：Afflux
Body/silicon membrane layer/graphene film layer/silicon membrane layer/graphene film layer/silicon membrane layer/graphene film layer, concrete structure
As shown in figure 1, in figure, 10 be collector, and 11,13 and 15 be silicon membrane layer, and 12,14 and 16 be graphene film layer, due to silicon
Film layer and collector, and opposite charges is carried between graphene film layer, therefore stronger electrostatic attraction can be formed.
In embodiment of the present invention, there is loose porous structure inside the silicon/graphene composite film.This is loose more
The structure in hole is due to the interlayer spacings band between the interlayer pore structure and silicon membrane layer and graphene film layer of graphene
Come.
In embodiment of the present invention, the thickness of the silicon membrane layer is 500nm-2 μm, is optionally 800nm-1.5 μm, is fitted
The thickness range of conjunction can realize the preferable cyclical stability of silicon membrane layer, avoid the nano-silicon of undue agglomeration in charge and discharge process
Middle volume reexpansion/film layer pulverizing problem caused by contraction.
In embodiment of the present invention, the thickness of the graphene film layer is 500nm-2 μm, is optionally 800nm-1.5 μ
M, in suitable thickness range, graphene nanometer sheet can realize the loose porous network structure being cross-linked with each other, thin as silicon
The embedding lithium expansion of film layer provides cushion space.
In embodiment of the present invention, the quality accounting of silicon membrane layer is 5%-90% in the silicon/graphene composite film,
It is still optionally further 5%-30%, 10%-50%.In the silicon/graphene composite film using grapheme material as main body with
Structural framework, silicon are that electrode capacity contributes component, and the suitable quality accounting of the silicon can realize the overall Gao Rong of electrode simultaneously
Amount and preferable cyclical stability.
In embodiment of the present invention, the material of the silicon membrane layer is silicon nano, silicon nanofiber, silicon nanorod,
One or more in nano-tube, silicon nanoneedle and silicon nanoporous microballoon.The average grain diameter of wherein described silicon nano
For 10nm-900nm, 300nm-500nm is optionally；The silicon nanofiber, silicon nanorod, nano-tube or silicon nanoneedle
The a diameter of 5nm-900nm of average transverse, is optionally 100nm-500nm；The average grain diameter of the silicon nanoporous microballoon is
10nm-900nm, it is optionally 500nm-800nm.
In embodiment of the present invention, the collector can be metal foil, coated metal paper tinsel, alloy, stainless steel, silicon
Any one in piece, conductive carbon, electro-conductive glass, conductive fibre fabric and graphene-based substrate, the afflux body thickness is 5 μm-
10μm。
In embodiment of the present invention, the gross thickness of silicon/graphene composite film electrode is at 8 μm -30 μm.
The silicon of the above-mentioned offer of the embodiment of the present invention/graphene composite film electrode, has a height ratio capacity, and silicon membrane layer and
Graphene film layer is combined on a current collector by electrostatic attraction, between silicon materials are intactly coated on graphene layer, electrode
Structural stability is strong；Graphene can provide efficient quick electron transmission simultaneously, electrode is had high rate capability；In addition, stone
Interlayer spacings between the high degree of flexibility and pore structure and silicon membrane layer and graphene film layer of black alkene piece can be silicon
Expansion provides enough cushion spaces, so that electrode obtains higher cyclical stability.
Correspondingly, the embodiments of the invention provide a kind of preparation method of silicon/graphene composite film electrode, including it is following
Step：
S10, collector is provided, the collector is subjected to negative electricity processing, obtains electronegative collector；
S20, silicon materials are provided, the silicon materials are subjected to electric charge processing, obtain electrically charged silicon materials dispersion liquid；
S30, graphene is provided, the graphene is subjected to electric charge processing, obtained and the silicon materials oppositely charged
Graphene dispersing solution；
S40, the electronegative collector is alternately immersed in the electrically charged silicon materials dispersion liquid and described and silicon
In the graphene dispersing solution of material oppositely charged, it is thin that deposition silicon on the electronegative collector is acted on by electrostatic attraction
Film layer and graphene film layer, are finally self-assembly of silicon/graphene composite film, that is, obtain silicon/graphene composite film electricity
Pole, at least one layer of silicon membrane layer and at least one layer of graphene of the silicon/graphene composite film including alternately laminated setting are thin
Film layer.
In embodiment of the present invention, in S10, the concrete operations that the collector is carried out to negative electricity processing are：Using alkali
Alcohol water mixed solution soak the collector.Wherein, the alkali can be LiOH, NaOH, KOH, RbOH, CsOH, FrOH, Ca
(OH)2、Sr(OH)2、Ba(OH)2、Ra(OH)2、HgOH、TiOH、AgOH·NH3With the one or more in choline, the mixing
In solution, the volume ratio of alcohol and water can be 1:0.2-5, the alcohol can be ethanol.The collector can be metal foil, band
It is any in coating metal paper tinsel, alloy, stainless steel, silicon chip, conductive carbon, electro-conductive glass, conductive fibre fabric and graphene-based substrate
It is a kind of.Certainly, also collector can be processed into positively charged form using other modes.
In embodiment of the present invention, in S20, it can be positive chargeization processing that the silicon materials are carried out into electric chargeization processing,
Can also be negative electrical chargeization processing, the concrete operations of wherein positive chargeization processing can be：The silicon materials are scattered in necessarily
Ultrasonic disperse in the cation type polymer electrolyte aqueous solution of concentration, obtain positively charged silicon materials dispersion liquid, the sun
Ionic polyelectrolyte includes the polymer with basic ionizable group, and the basic ionizable group includes amino, imido
Base, can be diallyl dimethyl ammoniumchloride specifically.The concentration of the described cationic polyelectrolyte aqueous solution is
5wt%-80wt%.
The silicon materials are silicon nano, silicon nanofiber, silicon nanorod, nano-tube, silicon nanoneedle and silicon nanometer
One or more in porous microsphere.The average grain diameter of wherein described silicon nano is 10nm-900nm, is optionally
300nm-500nm；The silicon nanofiber, silicon nanorod, a diameter of 5nm- of the average transverse of nano-tube or silicon nanoneedle
900nm, it is optionally 100nm-500nm；The average grain diameter of the silicon nanoporous microballoon is 10nm-900nm, is optionally
500nm-800nm。
In embodiment of the present invention, in S30, it can be positive chargeization processing that the graphene is carried out into electric chargeization processing,
Can also be negative electrical chargeization processing, the concrete operations of wherein negative electrical chargeization processing can be：Using anionic polyelectrolyte pair
The graphene film for peeling off state carries out surface modification, obtains negatively charged graphene dispersing solution.The graphene is received for graphene
Rice piece.The anionic polyelectrolyte includes carrying carbonic acid after carrying carboxyl, the polymer of alkoxy or phenol epoxide or ionization
Radical ion, bicarbonate ion, phosphate anion, silicic acid foundation ion, the polymer of sulphion.Specifically, can be poly- third
Olefin(e) acid.
In embodiment of the present invention, in S40, the electronegative collector is alternately immersed in the electrically charged silicon material
5-30min is soaked respectively in material dispersion liquid and the described and graphene dispersing solution of silicon materials oppositely charged.
In the embodiment of the invention, the preparation method of the silicon/graphene composite film electrode includes following step
Suddenly：
S110, by collector carry out negative electrical charge processing：The ethanol that collector is soaked in 1wt%-10wt% alkali is water-soluble
Liquid (ethanol, water volume ratio 1:5-30min in 0.2-5), then with milli-Q water, obtain electronegative collector；
S120, by silicon materials carry out positive charge processing：By 500mg nano silicones material and a certain amount of polydiene dimethylamine
Ammonium chloride (PDDA) aqueous dispersion is in 80mL-200mL deionized waters, ultrasonic disperse 5-60min, PDDA in dispersion liquid
Mass fraction is 5wt%-80wt%.Removal supernatant liquor is then centrifuged repeatedly in deionized water does not modify silicon to remove
The unnecessary PDDA of material surface, the Si-PDDA dispersion liquids with positive electricity are obtained, are then diluted to 100mL- with deionized water
1000mL；
S130, by graphene film carry out negative electrical charge processing：Graphene nanometer sheet (GNs) is scattered in deionized water, made
It is placed in into the GNs dispersion liquids 200mL that concentration is 1g/L-10g/L in three-necked flask, then adds 1g-10g polyacrylic acid
(PAA) 5min-60min, is stirred；Lead to the protective gas 5min-60min such as nitrogen into flask again to remove oxygen in bottle, then lead to
0.5g/L-2.5g/L (NH is added dropwise in inflow-rate of water turbine injector4)2S2O8Solution 80mL, stirring in 40 DEG C -80 DEG C of oil bath
Lower heating 12-48 hours, after heating, the dilution of 100mL-500mL deionized waters, ultrasonic disperse 0.5-2 are added into system
Hour, then washing is centrifuged, product is obtained, finally product is scattered in 100mL-800mL deionized waters, is obtained with negative electricity
GNs-PAA dispersion liquids；
S140, silicon/graphene composite film electrostatic self-assembled deposition：Step a:By the electronegative collector immersion in surface
The 5min-30min in Si-PDDA dispersion liquids, nano-silicon is set to deposit to collection by the electrostatic attraction between powered PDDA and collector
In fluid substrate, the silicon membrane layer of densification is formed；Step b:Collector is soaked in 5min- in GNs-PAA dispersion liquids again
30min, electronegative GNs is attracted on the silicon membrane layer of positively charged, form graphene film layer；
S150, n above-mentioned steps a, b are alternately repeated, obtained with multi-layer compound structure (Si-PDDA/GNs-PAA)n's
Silicon/graphene composite film.
The preparation method of the silicon of the above-mentioned offer of the embodiment of the present invention/graphene composite film electrode, is first passed through at electric charge
Reason causes nano silicon material to carry opposite charges with graphite olefinic constituent, then passes through the electrostatic precipitation in situ on negatively charged collector
The membrane electrode structure of layer assembly is obtained, the process route is simple, and the electrode specific capacity being prepared is high, Stability Analysis of Structures, follows
Ring performance is good, is provided simultaneously with high rate capability.
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, can be suitably carry out change implementation.
Embodiment 1
A kind of preparation method of silicon/graphene composite film electrode, comprises the following steps：
S10, by collector carry out negative electrical charge processing：The foam copper current collector that purification process is crossed is immersed in 2wt%Ca
(OH)2(volume ratio of second alcohol and water is 1 to ethanol water:3) immersion 20min in, then washed repeatedly with ultra-pure water, obtain surface band
There is the foam copper current collector of negative electrical charge；
S20, by silicon materials carry out positive charge processing：Weigh 100mg nano silicon particles (D50 200-300nm) and with
100mg PDDA are scattered in 500mL deionized waters altogether, ultrasonic disperse 30min；After dispersion liquid is centrifuged with deionized water repeatedly
Washing precipitate, to remove unnecessary PDDA, the product after washing is scattered in deionized water, is configured to 100mL with just
The Si-PDDA dispersion liquids of electric charge；
S30, by graphene film carry out negative electrical charge processing：The graphene nanometer sheet reduced and after mechanical stripping is scattered in
In ionized water, the GNs dispersion liquids 200mL that concentration is 10g/L is made and is placed in three-necked flask, adds 20g PAA, stirring
60min.Nitrogen is continually fed into flask again to remove oxygen in bottle, 10g/L is added dropwise by flow injector after 20min
(NH4)2S2O8Solution 80mL, heat 12 hours under stirring in 80 DEG C of oil bath, after heating, added into system
Ultrasonic disperse 1 hour after the dilution of 50mL deionized waters, then centrifugal treating and washed repeatedly with deionized water, obtain product.Finally
Product is scattered in 200mL deionized waters, obtains the GNs-PAA dispersion liquids with negative electricity；
S40, silicon/graphene composite film electrostatic self-assembled deposition：The electronegative collector in surface is soaked in Si-
15min in PDDA dispersion liquids, silicon nanoparticle is set to be deposited to by the electrostatic attraction between powered PDDA and collector on collector,
Form fine and close silicon membrane layer；Collector is soaked in 20min in GNs-PAA dispersion liquids again, is attracted to electronegative GNs
On the silicon membrane layer of positively charged, graphene film layer is formed, cycle alternation repeats above-mentioned Si-PDDA and GNs-PAA deposition steps
Rapid 3 times, must be deposited in copper foil current collector has multi-layer compound structure (Si-PDDA/GNs-PAA)3Silicon/graphene it is compound
Film, that is, obtain silicon/graphene composite film electrode.The electrode can use directly as the negative pole of lithium ion battery.
Fig. 2 is the electrostatic self-assembled deposition process schematic diagram of silicon/graphene composite film in the embodiment of the present invention, in figure
10 ' be the copper foil current collector that surface carries negative electrical charge, and 20 represent the silicon grain Si-PDDA of PDDA modifications, and 30 represent PAA modifications
Graphene film GNs-PAA.
Embodiment 2
A kind of preparation method of silicon/graphene composite film electrode, comprises the following steps：
S10, by collector carry out negative electrical charge processing：The copper foil current collector that purification process is crossed is immersed in 1wt%KOH ethanol
(volume ratio of second alcohol and water is 2 to the aqueous solution:3) immersion 5min in, then washed repeatedly with ultra-pure water, obtain surface and carry negative electrical charge
Copper foil current collector；
S20, by silicon materials carry out positive charge processing：Weigh 500mg nano silicon particles (D50 500nm) and and 40mg
PDDA is scattered in 200mL deionized waters altogether, ultrasonic disperse 30min；It is heavy to be washed repeatedly with deionized water after dispersion liquid is centrifuged
Starch, to remove unnecessary PDDA, the product after washing is scattered in deionized water, is configured to 500mL and carries positive charge
Si-PDDA dispersion liquids；
S30, by graphene film carry out negative electrical charge processing：The graphene nanometer sheet reduced and after mechanical stripping is scattered in
In ionized water, the GNs dispersion liquids 200mL that concentration is 2g/L is made and is placed in three-necked flask, adds 5g PAA, stirs 20min.
Nitrogen is continually fed into flask again to remove oxygen in bottle, is added dropwise 1.25g/L's by flow injector after 20min
(NH4)2S2O8Solution 80mL, heated 48 hours under stirring in 60 DEG C of oil bath, after heating, 200mL is added into system
Ultrasonic disperse 1 hour after deionized water dilution, then centrifugal treating and washed repeatedly with deionized water, obtain product.Finally will production
Thing is scattered in 500mL deionized waters, obtains the GNs-PAA dispersion liquids with negative electricity；
S40, silicon/graphene composite film electrostatic self-assembled deposition：The electronegative collector in surface is soaked in Si-
10min in PDDA dispersion liquids, silicon nanoparticle is set to be deposited to by the electrostatic attraction between powered PDDA and collector on collector,
Form fine and close silicon membrane layer；Collector is soaked in 10min in GNs-PAA dispersion liquids again, is attracted to electronegative GNs
On the silicon membrane layer of positively charged, graphene film layer is formed, cycle alternation repeats above-mentioned Si-PDDA and GNs-PAA deposition steps
Rapid 10 times, must be deposited in copper foil current collector has multi-layer compound structure (Si-PDDA/GNs-PAA)10Silicon/graphene it is multiple
Film is closed, that is, obtains silicon/graphene composite film electrode.The electrode can use directly as the negative pole of lithium ion battery.
The making of button cell：The silicon that above-described embodiment is prepared/graphene composite film electrode is through 120 DEG C of vacuum
Negative pole is used as after drying, in the environment of glove box high-purity argon gas, using metal lithium sheet as to electrode assembling into button cell.Its
In, barrier film Celgard2400, electrolyte 1MLiPF6/ 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 high voltage 4.4V cobalt acid lithiums as positive pole, the silicon/graphene being prepared with above-described embodiment is multiple
Membrane electrode is closed as negative pole, electrolyte is 1M LiPF6/EC+PC+DEC+EMC (volume ratios 1:0.3:1:1), barrier film PP/
PE/PP three-layer membranes (thickness is 16 μm), are fabricated to 4Ah or so soft-package battery, are born for test silicon graphene composite film
The full battery performance of pole.Electro-chemical test discharge and recharge window is 2.75-4.4V.
Embodiment 3
A kind of preparation method of silicon/graphene composite film electrode, comprises the following steps：
S10, by collector carry out negative electrical charge processing：The foam copper current collector that purification process is crossed is immersed in 1wt%NaOH
(volume ratio of second alcohol and water is 2 to ethanol water:3) immersion 5min in, then washed repeatedly with ultra-pure water, obtain surface and carry negative electricity
The foam copper current collector of lotus；
S20, by silicon materials carry out positive charge processing：Weigh 200mg nano silicon particles (D50 200-300nm) and with
60mg PDDA are scattered in 200mL deionized waters altogether, ultrasonic disperse 60min；Washed repeatedly with deionized water after dispersion liquid is centrifuged
Sediment is washed, to remove unnecessary PDDA, the product after washing is scattered in deionized water, 200mL is configured to and carries positive electricity
The Si-PDDA dispersion liquids of lotus；
S30, by graphene film carry out negative electrical charge processing：The graphene nanometer sheet reduced and after mechanical stripping is scattered in
In ionized water, the GNs dispersion liquids 200mL that concentration is 5g/L is made and is placed in three-necked flask, adds 10g PAA, stirring
40min.Nitrogen is continually fed into flask again to remove oxygen in bottle, 2g/L is added dropwise by flow injector after 20min
(NH4)2S2O8Solution 80mL, heat 24 hours under stirring in 80 DEG C of oil bath, after heating, added into system
Ultrasonic disperse 2 hours after the dilution of 100mL deionized waters, then centrifugal treating and washed repeatedly with deionized water, obtain product.Finally
Product is scattered in 500mL deionized waters, obtains the GNs-PAA dispersion liquids with negative electricity；
S40, silicon/graphene composite film electrostatic self-assembled deposition：The electronegative collector in surface is soaked in Si-
5min in PDDA dispersion liquids, silicon nanoparticle is set to be deposited to by the electrostatic attraction between powered PDDA and collector on collector,
Form fine and close silicon membrane layer；Collector is soaked in 10min in GNs-PAA dispersion liquids again, is attracted to electronegative GNs
On the silicon membrane layer of positively charged, graphene film layer is formed, cycle alternation repeats above-mentioned Si-PDDA and GNs-PAA deposition steps
Rapid 20 times, must be deposited in copper foil current collector has multi-layer compound structure (Si-PDDA/GNs-PAA)20Silicon/graphene it is multiple
Film is closed, that is, obtains silicon/graphene composite film electrode.The electrode can use directly as the negative pole of lithium ion battery.
Embodiment 4
A kind of preparation method of silicon/graphene composite film electrode, comprises the following steps：
S10, by collector carry out negative electrical charge processing：The foam copper current collector that purification process is crossed is immersed in 2wt%Ca
(OH)2(volume ratio of second alcohol and water is 1 to ethanol water:3) immersion 20min in, then washed repeatedly with ultra-pure water, obtain surface band
There is the foam copper current collector of negative electrical charge；
S20, by silicon materials carry out positive charge processing：Weigh 100mg nano silicon particles (D50 200-300nm) and with
100mg PDDA are scattered in 500mL deionized waters altogether, ultrasonic disperse 30min；After dispersion liquid is centrifuged with deionized water repeatedly
Washing precipitate, to remove unnecessary PDDA, the product after washing is scattered in deionized water, is configured to 100mL with just
The Si-PDDA dispersion liquids of electric charge；
S30, by graphene film carry out negative electrical charge processing：The graphene nanometer sheet reduced and after mechanical stripping is scattered in
In ionized water, the GNs dispersion liquids 200mL that concentration is 10g/L is made and is placed in three-necked flask, adds 20g PAA, stirring
60min.Nitrogen is continually fed into flask again to remove oxygen in bottle, 10g/L is added dropwise by flow injector after 20min
(NH4)2S2O8Solution 80mL, heat 12 hours under stirring in 80 DEG C of oil bath, after heating, added into system
Ultrasonic disperse 1 hour after the dilution of 50mL deionized waters, then centrifugal treating and washed repeatedly with deionized water, obtain product.Finally
Product is scattered in 200mL deionized waters, obtains the GNs-PAA dispersion liquids with negative electricity；
S40, silicon/graphene composite film electrostatic self-assembled deposition：The electronegative collector in surface is soaked in Si-
15min in PDDA dispersion liquids, silicon nanoparticle is set to be deposited to by the electrostatic attraction between powered PDDA and collector on collector,
Form fine and close silicon membrane layer；Collector is soaked in 20min in GNs-PAA dispersion liquids again, is attracted to electronegative GNs
On the silicon membrane layer of positively charged, graphene film layer is formed, cycle alternation repeats above-mentioned Si-PDDA and GNs-PAA deposition steps
Rapid 5 times, must be deposited in copper foil current collector has multi-layer compound structure (Si-PDDA/GNs-PAA)5Silicon/graphene it is compound
Film, that is, obtain silicon/graphene composite film electrode.The electrode can use directly as the negative pole of lithium ion battery.
Effect example
Beneficial effect to be brought to technical scheme of the embodiment of the present invention provides powerful support for, and spy provides following performance and surveyed
Examination：
Fig. 3 is filling first using silicon/button cell made from graphene composite film electrode of the embodiment of the present invention 2
Electricity/discharge curve；Can know from figure, to should the discharge capacity first of silicon/graphene composite film electrode be 721mAh/
g.The capacity of the composite film electrode, which plays, is far above conventional graphite cathode pole piece, and this comes from high theoretical capacity nanometer in system
The contribution of silicon materials.Meanwhile discharge curve shows relatively low discharge platform voltage, illustrate that the composite film electrode is advantageous to
The voltage increase of full battery system.
Fig. 4 is to be surveyed using the cycle performance of full battery made from silicon/graphene composite film electrode of the embodiment of the present invention 2
Test result.It can be seen that full battery can keep first circle discharge capacity after 100 circle charge/discharge cycles
More than 90%, illustrate that the battery system has preferably cyclical stability, disclosure satisfy that practical application request.This be due to silicon/
In graphene composite film, using the high mechanical properties porous graphene that inside is interweaved as skeleton, the dispersiveness of silicon is improved,
Cushion space is provided for its expansion.The structure can effectively alleviate the stress that the embedding lithium expansion of silicon nanoparticle is brought, and ensure film layer
Structural stability in electrochemistry cyclic process.The silicon of the embodiment of the present invention/graphene composite film electrode efficiently solves
The stable circulation sex chromosome mosaicism of silicium cathode materials application in lithium ion battery.
The silicon of the above-mentioned offer of the embodiment of the present invention/graphene composite film electrode and preparation method thereof, passes through silicon and graphite
Xenogenesis charge attraction between the component of alkene two, realize that the electrostatic LBL self-assembly of silicon/graphene composite film on electric charge collector sinks
Product.The silicon/graphene composite film electrode can be directly used for lithium ion battery assembling, it is not necessary to conductive additive and binding agent
Use, avoid stirred in electrode fabrication material, coating etc. complexity preceding process, and on collector active material silicon carbon ratio
Example, quality, film thickness etc. can be controlled by sedimentation time, be advantageous to electrode capacity raising；The silicon/graphene composite film electrode
The physics synthetic method of traditional silicon carbon complex is changed, by the powered modification in the surface of polymer, realizes silicon and graphene group
Stronger electrostatical binding power, improves structural stability of the electrode in electrochemistry cyclic process between point；Wherein, graphene conduct
A kind of high intensity two-dimensional nanostructure, a loose porous high conductivity network can be provided for laminated film, on the one hand promoted
Enter the efficient transmission of electronics in electrode, on the other hand improve the unit area load capacity of silicon and provide enough bufferings for its expansion
Space, ensure that its reexpansion is still wrapped in graphene conductive network after shrinking, will not lose and be connect with effective electricity of electrode
Touch；In addition, outermost layer is graphene film layer in silicon/graphene composite film electrode, silicon and electrolyte can be effectively avoided
Directly contact, be advantageous to stablize SEI films, reduce the irreversible capacity loss of electrode material, and then improve electrode cycle life；And
PDDA can play the effect for being equal to binding agent with PAA resilient, crosslinked, have inhibition to the volumetric expansion under the embedding lithium state of silicon,
So as to improve the cycle life of silicon materials.
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
Above-mentioned embodiment can be changed and changed.Therefore, the invention is not limited in disclosed and described above specific real
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 (20)
1. a kind of silicon/graphene composite film electrode, it is characterised in that formed including collector and by electrostatic self-assembled in institute
Silicon/graphene composite film on collector is stated, the silicon/graphene composite film includes at least one layer of alternately laminated setting
Silicon membrane layer and at least one layer of graphene film layer, the silicon membrane layer is incorporated in by electrostatic attraction on the collector or institute
State on graphene film layer, the graphene layer is incorporated on the collector or on the silicon membrane layer by electrostatic attraction.
2. silicon as claimed in claim 1/graphene composite film electrode, it is characterised in that the silicon/graphene composite film
The 1-20 layers silicon membrane layer and the 1-20 layers graphene film layer including alternately laminated setting.
3. silicon as claimed in claim 1 or 2/graphene composite film electrode, it is characterised in that the silicon/graphene is compound
The outermost layer of film is graphene film layer.
4. silicon/graphene composite film electrode as described in claim any one of 1-3, it is characterised in that the silicon/graphene
There is loose porous structure inside laminated film.
5. silicon/graphene composite film electrode as described in claim any one of 1-4, it is characterised in that the collector band
There is negative electrical charge, the silicon membrane layer carries positive charge or negative electrical charge, and the graphene film layer carries positive charge or negative electrical charge.
6. silicon/graphene composite film electrode as described in claim any one of 1-5, it is characterised in that the silicon membrane layer
Silicon materials surface modification have cationic polyelectrolyte, the graphenic surface of the graphene film layer is modified with anionic
Polyelectrolyte.
7. silicon as claimed in claim 6/graphene composite film electrode, it is characterised in that the cationic polyelectrolyte
Including the polymer with basic ionizable group, the basic ionizable group includes amino, imino group；The anionic
Polyelectrolyte include with carboxyl, alkoxy or phenol epoxide polymer or ionization after with carbanion, bicarbonate radical from
Son, phosphate anion, silicic acid foundation ion, the polymer of sulphion.
8. silicon as claimed in claim 7/graphene composite film electrode, it is characterised in that the cationic polyelectrolyte
Including diallyl dimethyl ammoniumchloride；The anionic polyelectrolyte includes polyacrylic acid.
9. silicon/graphene composite film electrode as described in claim any one of 1-8, it is characterised in that the silicon membrane layer
Thickness be 500nm-2 μm.
10. silicon/graphene composite film electrode as described in claim any one of 1-9, it is characterised in that the graphene is thin
The thickness of film layer is 500nm-2 μm.
11. silicon/graphene composite film electrode as described in claim any one of 1-10, it is characterised in that the silicon/graphite
The quality accounting of silicon membrane layer is 5%-90% in alkene laminated film.
12. silicon/graphene composite film electrode as described in claim any one of 1-11, it is characterised in that the silicon thin film
The silicon materials of layer are silicon nano, silicon nanofiber, silicon nanorod, nano-tube, silicon nanoneedle and silicon nanoporous microballoon
In one or more.
13. silicon as claimed in claim 12/graphene composite film electrode, it is characterised in that the silicon nano is put down
Equal particle diameter is 10nm-900nm；The silicon nanofiber, silicon nanorod, the average transverse of nano-tube or silicon nanoneedle are a diameter of
5nm-900nm；The average grain diameter of the silicon nanoporous microballoon is 10nm-900nm.
14. silicon/graphene composite film electrode as described in claim any one of 1-13, it is characterised in that the collector
For metal foil, coated metal paper tinsel, alloy, stainless steel, silicon chip, conductive carbon, electro-conductive glass, conductive fibre fabric and graphene-based base
One kind in bottom.
15. the preparation method of a kind of silicon/graphene composite film electrode, it is characterised in that comprise the following steps：
Collector is provided, the collector is subjected to negative electricity processing, obtains electronegative collector；
Silicon materials are provided, the silicon materials are subjected to electric charge processing, obtain electrically charged silicon materials dispersion liquid；
Graphene is provided, the graphene is subjected to electric charge processing, obtains the graphene with the silicon materials oppositely charged
Dispersion liquid；
The electronegative collector is alternately immersed in the electrically charged silicon materials dispersion liquid and described with silicon materials band phase
In the graphene dispersing solution of counter charges, deposit thin films of silicon layer and stone on the electronegative collector are acted on by electrostatic attraction
Black alkene film layer, is finally self-assembly of silicon/graphene composite film, that is, obtains silicon/graphene composite film electrode, described
Silicon/graphene composite film includes at least one layer of silicon membrane layer of alternately laminated setting and at least one layer of graphene film layer.
16. the preparation method of silicon as claimed in claim 15/graphene composite film electrode, it is characterised in that by the collection
Fluid carry out negative electricity processing concrete operations be：The collector is soaked using the alcohol water mixed solution of alkali.
17. the preparation method of silicon as claimed in claim 16/graphene composite film electrode, it is characterised in that the alkali bag
Include LiOH, NaOH, KOH, RbOH, CsOH, FrOH, Ca (OH)2、Sr(OH)2、Ba(OH)2、Ra(OH)2、HgOH、TiOH、
AgOH·NH3With the one or more in choline.
18. the preparation method of silicon as claimed in claim 15/graphene composite film electrode, it is characterised in that by the silicon
Material carry out electric charge processing concrete operations be：The silicon materials are scattered in certain density cationic polyelectrolyte water
Ultrasonic disperse in solution, obtain positively charged silicon materials dispersion liquid.
19. the preparation method of silicon as claimed in claim 15/graphene composite film electrode, it is characterised in that by the stone
The concrete operations that black alkene carries out electric charge processing are：Surface is carried out to the graphene film for peeling off state using anionic polyelectrolyte
Modification, obtains negatively charged graphene dispersing solution.
20. a kind of lithium ion battery, it is characterised in that the lithium ion battery is included as described in claim any one of 1-14
Silicon/graphene composite film electrode.
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