CN110364687A - A kind of preparation method of fexible film electrode and prepared electrode and purposes - Google Patents
A kind of preparation method of fexible film electrode and prepared electrode and purposes Download PDFInfo
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- CN110364687A CN110364687A CN201910693346.7A CN201910693346A CN110364687A CN 110364687 A CN110364687 A CN 110364687A CN 201910693346 A CN201910693346 A CN 201910693346A CN 110364687 A CN110364687 A CN 110364687A
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- polyacrylic acid
- carboxymethyl cellulose
- fexible film
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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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/621—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
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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 invention discloses a kind of preparation methods of fexible film electrode, waterborne compound adhesive is prepared using graphene oxide, carboxymethyl cellulose and polyacrylic acid in water first, nano-silicon particle is being added, is aoxidizing sub- silicon particle isoreactivity particle, pass through vacuum filter and vacuum freeze drying, prepare flexible graphene oxide-carboxymethyl cellulose-polyacrylic acid-active particle laminated film, using liquid-phase reduction and Vacuum Heat polycondensation reaction, fexible film electrode is obtained.This method makees solvent with water and prepares bonding agent, and molecule cross-link effect can occur with bonding agent for conductive agent, and conductive effect is good, and the stabilization of electrode structure is still able to maintain after multiple circulations, and capacity attenuation is slow, and has good mechanical strength and flexibility.Prepared fexible film electrode can be used for lithium ion battery, capacitor or other energy storage system electrode fabrications.
Description
Technical field
The present invention relates to electrode material fields, and in particular to a kind of preparation method of fexible film electrode, prepared electricity
Pole and purposes.
Background technique
For the problems such as energy crisis, resource currently increasingly sharpened be exhausted and environmental pollution, development cleaning and renewable
The energy becomes the Major Strategic of Chinese society economic development, have been cited as in national medium & long term sci-tech development program outline emphasis and
The direction first developed.Lithium ion battery (LIBs) due to having high-energy density, long circulation life and the advantages such as environmental-friendly,
Main power source as portable energy-storing device has caused the extensive concern in worldwide.It is set to meet portable electronic
How the growing energy consumption demand such as standby, wearable flexible electronic devices, electric vehicle and hybrid electric vehicle, further realize lithium
While the high efficiency energy of ion battery is stored and converted, having both high security, low cost, advantages of environment protection becomes existing rank
The significant challenge that section faces.
The storage lithium performance of lithium ion battery is heavily dependent on the performance of positive and negative electrode, currently, in lithium ion battery
Research and development during, researcher is more to be concentrated on energy in anode and cathode active materials, to important component in electrode ---
Binder and conductive agent do not cause enough attention.Currently, in commercial Li-ion battery production, due to its good electricity
Chemical stability, caking property and wider electrochemical stability window, Kynoar (Poly (vinylidene fluoride),
PVDF) it is widely used as the binder of positive and negative electrode.However, the price of PVDF binder valuableness increases the life of lithium ion battery
Produce cost；It is also needed in application process simultaneously using toxic volatile organic solvent N-Methyl pyrrolidone (NMP) as slurry
Expect dispersing agent, not only pollutes environment, but also endanger operator's health.In addition, its production technology requires strictly, to be easy to ambient humidity
It is reacted with lithium metal and generates stable LiF6, exothermic reaction occurs.In order to overcome disadvantage mentioned above existing for PVDF binder, base
In the demand that ecological friendly, low cost, enhancing electrode storage lithium performance and solvent recycle etc., Recent study person are mentioned
The method for replacing oiliness binder PVDF with the binder of water-based system is gone out.Aqueous binders not only can avoid making for NMP
With, and have many advantages, such as that low cost, easily acquisition, environmental-friendly and use are safe.Moreover, with water simply as dispersion
Agent is more easy come the process for making electrode, has become the perfect adhesion agent of the lithium ion battery of safety and environmental protection.In recent years
Come, during the polymeric binder of active development substitution PVDF, a large amount of work, which focuses on design and exploitation, has spy
The novel aqueous polymeric binder of different molecular composition and structure.
The chain of the straight chains such as current common PVDF, carboxymethyl cellulose (CMC), polyacrylic acid (PAA) bonding agent molecule with
It can only be attached by the weaker physical crosslinking mode of binding force (such as Van der Waals force, hydrogen bond) between chain, by shorter time
After several continuous circulations, inevitably irreversible sliding can occur with active material particle, so that active material and conductive additive
Electrical connectivity is lost between collector, causes the degeneration of electrode structure stability and the rapid decay of capacity.Meanwhile conductive agent
There is no caking property between active material, during charge/discharge, conductive agent is easily detached from active material, to lose
Electrical connectivity causes the interruption in electron-transport path.In addition, conventional binders lack enough mechanical strengths, silicon cannot be born
The large volume variation that the electrode materials such as base, tinbase and oxide-base occur in de-/process of intercalation, accelerates the machine of electrode material
Tool fracture and removing, lead to the loss of electrical conductance path.
How conductive agent and bonding agent are selected, make them that can more preferably carry out molecule cross-link each other and enhances leading for conductive agent
Electrical property, while being conducive to preferably coat electrode material, enhance the mechanical strength and flexibility of prepared electrode, it is promoted
The recyclability and service life of battery are this field phase practical problems to be solved.
Summary of the invention
It is an object of the present invention to provide a kind of preparation method of fexible film electrode, this method does solvent preparation with water
Bonding agent, and molecule cross-link effect can occur with bonding agent for conductive agent, and conductive effect is good, remains to protect after multiple circulations
The stabilization of electrode structure is held, capacity attenuation is slow, and has good mechanical strength and flexibility.
To achieve the goals above, the present invention adopts the following technical scheme that:
A kind of preparation method of fexible film electrode, it is characterised in that include the following steps:
(a) graphene oxide and carboxymethyl cellulose are dispersed in water respectively, obtain graphene oxide dispersion and carboxymethyl
Polyacrylic acid and the carboxymethyl cellulose dispersion liquid are added in the graphene oxide dispersion by cellulose dispersion liquid,
The raw molecule cross-link of uniform hybrid concurrency, obtains aqueous composite caking agent, wherein the mass percentage content of graphene oxide be 10 ~
35%, the mass percentage content of carboxymethyl cellulose is 5 ~ 10%, and the mass percentage content of polyacrylic acid is 55 ~ 85%, oxidation
The sum of mass percentage content of graphene, carboxymethyl cellulose and polyacrylic acid is 100%；
(b) active particle is added in the aqueous composite caking agent, it is made to be uniformly dispersed, obtain active particle mixed liquor,
The active particle is silicon nano or aoxidizes sub- silicon particle, and the mass percentage content of the active particle is 60 ~ 90%,
The sum of mass percentage content of the graphene oxide, carboxymethyl cellulose and polyacrylic acid be 10 ~ 40%, active particle with
The sum of mass percentage content of graphene oxide, carboxymethyl cellulose and polyacrylic acid is 100%；
(c) vacuum filter and vacuum freeze drying are carried out to the active particle mixed liquor, prepares flexible graphene oxide-carboxylic
Methylcellulose-polyacrylic acid-active particle laminated film；
(d) it is by the flexible graphene oxide-carboxymethyl cellulose-polyacrylic acid-active particle laminated film liquid-phase reduction
Flexible graphene-carboxymethyl cellulose-polyacrylic acid-active particle laminated film；
(e) Flexible graphene-carboxymethyl cellulose-polyacrylic acid-active particle laminated film impregnated in water, washed
And be freeze-dried, Vacuum Heat polycondensation reaction is then carried out, fexible film electrode is obtained after reaction.
Preferably, the carboxymethyl cellulose is Japanese Daicel DAICEL CMC2200, viscosity (1% 25 DEG C of aqueous solution@
It 60rpm) is 1500 ~ 3000 mPas, pH value (1% 25 DEG C of aqueous solution@) is 6.0 ~ 8.5, degree of substitution minimum 0.8, polypropylene
Acid is 45 ~ 55% aqueous solution of mass percent concentration, the average molecular weight 2800 ~ 3200 of polyacrylic acid.
Preferably, the silicon nano purity is not less than 99.9%, and partial size is 20 ~ 100 nanometers；It is flat to aoxidize sub- silicon particle
Equal partial size is 3.5 ~ 5 microns.
Preferably, it is restored in the step (d) using liquid-phase reduction agent, the liquid-phase reduction agent is hydrazine hydrate or boron
Sodium hydride aqueous solution.
Preferably, the fexible film electrode that the step (e) obtains with a thickness of 5 ~ 200 microns.
Preferably, the temperature of the Vacuum Heat polycondensation reaction of the step (e) is 120-180 DEG C, and the time is 1-6 h, vacuum
Degree is not higher than 0.1MPa.
The above method takes water as a solvent, easy to operate and environmentally protective, is easy to large area and prepares fexible film electrode.Pass through
Bonding action occurs for this method, graphene oxide and carboxymethyl cellulose (CMC), polyacrylic acid (PAA), in graphene oxide quilt
Bonded portion still keeps good connection after being reduced to graphene, and is finally polymerize again by vacuum thermal polycondensation, this has
Effect enhances the binding force of the graphene and carboxymethyl cellulose, polyacrylic acid as conductive agent, enhances conductive agent and electrode
Active material aoxidizes the continuous and effective contact of sub- silicon, silicon nano, avoids between previous electrode active material and conductive agent
Incidental irreversible sliding improves the structural stability, mechanical strength and cycle performance of electrode, avoids battery capacity
Too fast decaying.
It is a further object to provide a kind of fexible film electrode, which is prepared using the above method,
Stratiform network structure is presented on the whole, improves electron transmission and the ion diffusion of electrode interior, while binder is covered on work
Property material surface, reduce the oxidation of nano-active material, can not only inhibit electrolyte surface of active material deposition send out
Raw irreversible reaction, and can effectively alleviate volume expansion of material during charge/discharge, improve the circulation of battery
Service life and high rate performance.
Above-mentioned fexible film electrode can be used for lithium ion battery, capacitor or other energy storage system electrode fabrications.
The present invention is based on organic and inorganics micro-, nanometer hierarchical layer assembly structure and interfacial interaction, with lamellar graphite alkene
For skeleton structure, carboxymethyl cellulose enhances its adhesive property, and introducing polyacrylic acid not only can be with graphene, carboxymethyl cellulose
Molecule cross-link occurs for plain strand, while-COOH group is evenly distributed in polyacrylic acid, and can in three dimensions and electricity
Chemically active material particle is connected by chemical bond (hydrogen bond or covalent bond), the binding force of enhancing and active material；Polyacrylic acid
Success will follow is embedded into the channel of graphene oxide interlayer for molecule and carboxymethyl cellulose molecule, can shape between graphene oxide
At greater number of hydrogen bond, carboxymethyl cellulose plays the role of connecting graphene oxide layer and polyacrylic acid molecule, makes layer
Between active force further increase.Thermal polycondensation reaction can occur under vacuum conditions for polyacrylic acid molecule and carboxymethyl cellulose, increase
Add its power that be combined with each other.Due to the unique molecular structure of carboxymethyl cellulose, horizontally also hydrogen bond can be formed with polyacrylic acid,
Make material that there is better tensile strength.Meanwhile it is higher than crystallinity with the higher polypropylene acid layer of graphene crosslinkable amorphous degree
PVDF be easier to be covered on surface of active material, form a kind of difunctional conformal coating similar to SEI film, be similar to one
The polarity hydrogen bond action of the hydroxyl of the carboxyl and surface of active material of a little binders.This conformal coating similar to SEI film is not
It can only inhibit electrolyte that irreversible reaction occurs in the deposition in surface of active material, and can effectively alleviate material and exist
Volume expansion during charge/discharge provides three-dimensional continuous electrical conductance path, is conducive to maintain electrode in charge/discharge
The integrality of structure in journey and cyclic process it is reversible.
The present invention passes through polyacrylic acid and graphene oxide and carboxymethyl cellulose using graphene oxide as inorganic reinforcement
Element generation is covalently cross-linked, constructs graphene/carboxymethyl cellulose/polyacrylic acid aqueous binders, while can also make binder
Mutual key continuous cropping occurs between each component and active material to use, realizes the integrated electrochemistry of strong, tough, high electronics and ion transmission
The preparation of energy storage composite and flexible membrane electrode.In addition, composite structure is more after liquid phase chemical reduction for graphene oxide
Completely, therefore there is good electrochemical energy storage performance.
The invention has the following advantages:
(1) present invention uses water soluble polymer derivative --- and carboxymethyl cellulose is raw material, and the raw material sources are extensive, cost
It is cheap.And carboxymethyl cellulose has biodegradability, and green non-pollution.
(2) presoma of the graphene oxide that the present invention uses as binder conduction agent material is applied to aqueous bonding
Agent system.Graphene oxide can form stable suspension in water.Meanwhile graphene platelet is kept in the micron-scale, this has
Conducive to its long-range electric conductivity；There is the conductive film of formation ductility certain active materials can be inhibited to a certain extent in charge and discharge
Biggish volume change in electric process is conducive to the high rate performance for improving battery, extends the service life of battery.The present invention passes through
Graphene is added and substitutes business conductive carbon material, solves infiltration of the business conductive carbon material under water-based system in a way
Property it is poor, the shortcomings that difficult dispersion easy to reunite.
(3) it introduces carboxymethyl cellulose and polyacrylic acid evenly spreads to silicon particle surface, shape during vacuum filtration
At effectively covering and protecting, reduce the oxidation of nano-silicon；It can play the role of stable silicon particle simultaneously.
(4) binder and conductive additive that the present invention additionally uses in avoiding traditional electrode preparation process.Therefore,
This method is expected to become traditional one most suitable alternative techniques of coating arts techniques, and improves the boundary between electrolyte
Face performance, to improve the coulombic efficiency of electrode material and the cyclical stability of battery and high rate performance.
(5) the technology of the present invention is environmentally protective, scheme is simple, easy to operate, reproducible, widely applicable, be high-capacity lithium ion battery from
The research of sub- battery provides effective approach.
Detailed description of the invention
Fig. 1 is the photo of nano silicon-based fexible film electrode prepared by the embodiment of the present invention 3；
Fig. 2 is the XRD spectrum of nano silicon-based fexible film electrode prepared by the embodiment of the present invention 3；
Fig. 3 to Fig. 6 be the embodiment of the present invention 3 prepare nano silicon-based fexible film electrode different multiplying under SEM scheme；
Fig. 7 is the cyclic voltammetry curve of nano silicon-based fexible film electrode prepared by the embodiment of the present invention 3；
Fig. 8 is the charging and discharging curve of nano silicon-based fexible film electrode prepared by the embodiment of the present invention 3.
Specific embodiment
In order to further illustrate the present invention, with reference to the accompanying drawing and specific embodiment the present invention is carried out it is further detailed
Explanation.
1 fexible film method for making its electrode 1 of embodiment
(1) it weighs 10 mg of graphene oxide in the balance first, is placed in 20 ml deionized waters, persistently stirs 30 min, then
60 min are ultrasonically treated, uniform graphene oxide dispersion is obtained；Weigh 5 mg of carboxymethyl cellulose, be placed in 10 ml go from
In sub- water, stirring ultrasound is made into uniform carboxymethyl cellulose dispersion liquid；By the polyacrylic acid solution containing 85mg polyacrylic acid
0.2ml is slowly added into above-mentioned graphene oxide dispersion, and 30 min of room temperature magnetic agitation is then sonicated 30 min；So
Above-mentioned carboxymethyl cellulose dispersion liquid is added in graphene oxide dispersion again afterwards, stirring is ultrasonic to uniform.Above-mentioned stirring
In ultrasonic procedure, carboxyl and epoxy group of the polyacrylic acid with graphene oxide and on carboxymethyl cellulose surface occur covalently to hand over
Connection, generates aqueous compound binding agent.
(2) 150 mg silicon nanos are added in above-mentioned aqueous compound binding agent, are surpassed again after 30 min of magnetic agitation
Sound disperses 30 min and obtains uniform active particle mixed liquor；
(3) use the miillpore filter of 0.22 μm of micropore in vacuum resulting active particle mixed liquor using vacuum assisted filtration
It is filtered in Suction filtration device；Filtered product is cleaned using 100 ~ 300 milliliters of deionized water later；Then will
Filter membrane is put into refrigerator freezing.After freezing 5h, it is freeze-dried 8h using vacuum freeze drier, obtains flexible graphene oxide-carboxylic
Methylcellulose-polyacrylic acid-nano-silicon laminated film.
(4) the above-mentioned laminated film after drying is placed in surface plate, hydrazine hydrate solution reduction is then added, stands 6h,
Obtain Flexible graphene-carboxymethyl cellulose-polyacrylic acid-nano-silicon laminated film.
(5) compound film sheet obtained by step (4) is taken out, is cleaned for several times with deionized water；After cleaning, it is immediately placed in ice
Case freezes 5 hours；It is placed again into vacuum freeze drier, is freeze-dried 8h, then the Vacuum Heat polycondensation reaction at 120 DEG C
6h reacts locating pressure and is not higher than 0.1Mpa, that is, obtains nano silicon-based fexible film electrode.
2 fexible film method for making its electrode 2 of embodiment
(1) it weighs 35 mg of graphene oxide in the balance first, is placed in 50 ml deionized waters, persistently stirs 30 min, then
60 min are ultrasonically treated, uniform graphene oxide dispersion is obtained；Weigh 10 mg of carboxymethyl cellulose, be placed in 10 ml go from
In sub- water, stirring ultrasound is made into uniform carboxymethyl cellulose dispersion liquid；By the polyacrylic acid solution containing 55mg polyacrylic acid
0.13ml is slowly added into above-mentioned graphene oxide dispersion, and 30 min of room temperature magnetic agitation is then sonicated 30 min；So
Above-mentioned carboxymethyl cellulose dispersion liquid is added in graphene oxide dispersion again afterwards, stirring is ultrasonic to uniform.Above-mentioned stirring
In ultrasonic procedure, carboxyl and epoxy group of the polyacrylic acid with graphene oxide and on carboxymethyl cellulose surface occur covalently to hand over
Connection, generates aqueous compound binding agent.
(2) 900 mg nano-silicons are added in above-mentioned aqueous compound binding agent, ultrasound is divided again after 30 min of magnetic agitation
It dissipates 30 min and obtains uniform active particle mixed liquor；
(3) use the miillpore filter of 0.22 μm of micropore in vacuum resulting active particle mixed liquor using vacuum assisted filtration
It is filtered in Suction filtration device；Filtered product is cleaned using 100 ~ 300 milliliters of deionized water later；Then will
Filter membrane is put into refrigerator freezing.After freezing 5h, it is freeze-dried 8h using vacuum freeze drier, obtains flexible graphene oxide-carboxylic
Methylcellulose-polyacrylic acid-nano-silicon laminated film.
(4) the above-mentioned laminated film after drying is placed in surface plate, sodium borohydride aqueous solution reduction is then added, stands
6h obtains Flexible graphene-carboxymethyl cellulose-polyacrylic acid-nano-silicon laminated film.
(5) compound film sheet obtained by step (4) is taken out, is cleaned for several times with deionized water；After cleaning, it is immediately placed in ice
Case freezes 5 hours；It is placed again into vacuum freeze drier, is freeze-dried 8h, then the Vacuum Heat polycondensation reaction at 180 DEG C
1h reacts locating pressure and is not higher than 0.1Mpa, that is, obtains nano silicon-based fexible film electrode.
3 fexible film method for making its electrode 3 of embodiment
(1) it weighs 25 mg of graphene oxide in the balance first, is placed in 20 ml deionized waters, persistently stirs 30 min, then
60 min are ultrasonically treated, uniform graphene oxide dispersion is obtained；Weigh 8 mg of carboxymethyl cellulose, be placed in 10 ml go from
In sub- water, stirring ultrasound is made into uniform carboxymethyl cellulose dispersion liquid；By the polyacrylic acid solution containing 67mg polyacrylic acid
0.16ml is slowly added into above-mentioned graphene oxide dispersion, and 30 min of room temperature magnetic agitation is then sonicated 30 min；So
Above-mentioned carboxymethyl cellulose dispersion liquid is added in graphene oxide dispersion again afterwards, stirring is ultrasonic to uniform.Above-mentioned stirring
In ultrasonic procedure, carboxyl and epoxy group of the polyacrylic acid with graphene oxide and on carboxymethyl cellulose surface occur covalently to hand over
Connection, generates aqueous compound binding agent.
(2) 240 mg nano-silicons are added in above-mentioned aqueous compound binding agent, ultrasound is divided again after 30 min of magnetic agitation
It dissipates 30 min and obtains uniform active particle mixed liquor；
(3) use the miillpore filter of 0.22 μm of micropore in vacuum resulting active particle mixed liquor using vacuum assisted filtration
It is filtered in Suction filtration device；Filtered product is cleaned using 100 ~ 300 milliliters of deionized water later；Then will
Filter membrane is put into refrigerator freezing.After freezing 5h, it is freeze-dried 8h using vacuum freeze drier, obtains flexible graphene oxide-carboxylic
Methylcellulose-polyacrylic acid-nano-silicon laminated film.
(4) the above-mentioned laminated film after drying is placed in surface plate, hydrazine hydrate solution reduction is then added, stands 6h,
Obtain Flexible graphene-carboxymethyl cellulose-polyacrylic acid-nano-silicon laminated film.
(5) compound film sheet obtained by step (4) is taken out, is cleaned for several times with deionized water；After cleaning, it is immediately placed in ice
Case freezes 5 hours；It is placed again into vacuum freeze drier, is freeze-dried 8h, then the Vacuum Heat polycondensation reaction at 160 DEG C
4h reacts locating pressure and is not higher than 0.1Mpa, that is, obtains nano silicon-based fexible film electrode.
4 fexible film method for making its electrode 4 of embodiment
(1) it weighs 10 mg of graphene oxide in the balance first, is placed in 20 ml deionized waters, persistently stirs 30 min, then
60 min are ultrasonically treated, uniform graphene oxide dispersion is obtained；Weigh 5 mg of carboxymethyl cellulose, be placed in 10 ml go from
In sub- water, stirring ultrasound is made into uniform carboxymethyl cellulose dispersion liquid；By the polyacrylic acid solution containing 85mg polyacrylic acid
0.2ml is slowly added into above-mentioned graphene oxide dispersion, and 30 min of room temperature magnetic agitation is then sonicated 30 min；So
Above-mentioned carboxymethyl cellulose dispersion liquid is added in graphene oxide dispersion again afterwards, stirring is ultrasonic to uniform.Above-mentioned stirring
In ultrasonic procedure, carboxyl and epoxy group of the polyacrylic acid with graphene oxide and on carboxymethyl cellulose surface occur covalently to hand over
Connection, generates aqueous compound binding agent.
(2) 150 mg sub- silicon is aoxidized to be added in above-mentioned aqueous compound binding agent, it is ultrasonic again after 30 min of magnetic agitation
Disperse 30 min and obtains uniform active particle mixed liquor；
(3) use the miillpore filter of 0.22 μm of micropore in vacuum resulting active particle mixed liquor using vacuum assisted filtration
It is filtered in Suction filtration device；Filtered product is cleaned using 100 ~ 300 milliliters of deionized water later；Then will
Filter membrane is put into refrigerator freezing.After freezing 5h, it is freeze-dried 8h using vacuum freeze drier, obtains flexible graphene oxide-carboxylic
Methylcellulose-polyacrylic acid-oxidation Asia silicon laminated film.
(4) the above-mentioned laminated film after drying is placed in surface plate, hydrazine hydrate solution reduction is then added, stands 6h,
Obtain Flexible graphene-carboxymethyl cellulose-polyacrylic acid-oxidation Asia silicon laminated film.
(5) compound film sheet obtained by step (4) is taken out, is cleaned for several times with deionized water；After cleaning, it is immediately placed in ice
Case freezes 5 hours；It is placed again into vacuum freeze drier, is freeze-dried 8h, then the Vacuum Heat polycondensation reaction at 120 DEG C
6h reacts locating pressure and is not higher than 0.1Mpa, that is, obtains and aoxidize sub- silicon substrate fexible film electrode.
5 fexible film method for making its electrode 5 of embodiment
(1) it weighs 35 mg of graphene oxide in the balance first, is placed in 50 ml deionized waters, persistently stirs 30 min, then
60 min are ultrasonically treated, uniform graphene oxide dispersion is obtained；Weigh 10 mg of carboxymethyl cellulose, be placed in 10 ml go from
In sub- water, stirring ultrasound is made into uniform carboxymethyl cellulose dispersion liquid；By the polyacrylic acid solution containing 55mg polyacrylic acid
0.13ml is slowly added into above-mentioned graphene oxide dispersion, and 30 min of room temperature magnetic agitation is then sonicated 30 min；So
Above-mentioned carboxymethyl cellulose dispersion liquid is added in graphene oxide dispersion again afterwards, stirring is ultrasonic to uniform.Above-mentioned stirring
In ultrasonic procedure, carboxyl and epoxy group of the polyacrylic acid with graphene oxide and on carboxymethyl cellulose surface occur covalently to hand over
Connection, generates aqueous compound binding agent.
(2) 900 mg sub- silicon is aoxidized to be added in above-mentioned aqueous compound binding agent, it is ultrasonic again after 30 min of magnetic agitation
Disperse 30 min and obtains uniform active particle mixed liquor；
(3) use the miillpore filter of 0.22 μm of micropore in vacuum resulting active particle mixed liquor using vacuum assisted filtration
It is filtered in Suction filtration device；Filtered product is cleaned using 100 ~ 300 milliliters of deionized water later；Then will
Filter membrane is put into refrigerator freezing.After freezing 5h, it is freeze-dried 8h using vacuum freeze drier, obtains flexible graphene oxide-carboxylic
Methylcellulose-polyacrylic acid-oxidation Asia silicon laminated film.
(4) the above-mentioned laminated film after drying is placed in surface plate, sodium borohydride aqueous solution reduction is then added, stands
6h obtains Flexible graphene-carboxymethyl cellulose-polyacrylic acid-oxidation Asia silicon laminated film.
(5) compound film sheet obtained by step (4) is taken out, is cleaned for several times with deionized water；After cleaning, it is immediately placed in ice
Case freezes 5 hours；It is placed again into vacuum freeze drier, is freeze-dried 8h, then the Vacuum Heat polycondensation reaction at 180 DEG C
1h reacts locating pressure and is not higher than 0.1Mpa, that is, obtains and aoxidize sub- silicon substrate fexible film electrode.
6 fexible film method for making its electrode 6 of embodiment
(1) it weighs 25 mg of graphene oxide in the balance first, is placed in 20 ml deionized waters, persistently stirs 30 min, then
60 min are ultrasonically treated, uniform graphene oxide dispersion is obtained；Weigh 8 mg of carboxymethyl cellulose, be placed in 10 ml go from
In sub- water, stirring ultrasound is made into uniform carboxymethyl cellulose dispersion liquid；By the polyacrylic acid solution containing 67mg polyacrylic acid
0.16ml is slowly added into above-mentioned graphene oxide dispersion, and 30 min of room temperature magnetic agitation is then sonicated 30 min；So
Above-mentioned carboxymethyl cellulose dispersion liquid is added in graphene oxide dispersion again afterwards, stirring is ultrasonic to uniform.Above-mentioned stirring
In ultrasonic procedure, carboxyl and epoxy group of the polyacrylic acid with graphene oxide and on carboxymethyl cellulose surface occur covalently to hand over
Connection, generates aqueous compound binding agent.
(2) 240 mg sub- silicon is aoxidized to be added in above-mentioned aqueous compound binding agent, it is ultrasonic again after 30 min of magnetic agitation
Disperse 30 min and obtains uniform active particle mixed liquor；
(3) use the miillpore filter of 0.22 μm of micropore in vacuum resulting active particle mixed liquor using vacuum assisted filtration
It is filtered in Suction filtration device；Filtered product is cleaned using 100 ~ 300 milliliters of deionized water later；Then will
Filter membrane is put into refrigerator freezing.After freezing 5h, it is freeze-dried 8h using vacuum freeze drier, obtains flexible graphene oxide-carboxylic
Methylcellulose-polyacrylic acid-oxidation Asia silicon laminated film.
(4) the above-mentioned laminated film after drying is placed in surface plate, hydrazine hydrate solution reduction is then added, stands 6h,
Obtain Flexible graphene-carboxymethyl cellulose-polyacrylic acid-oxidation Asia silicon laminated film.
(5) compound film sheet obtained by step (4) is taken out, is cleaned for several times with deionized water；After cleaning, it is immediately placed in ice
Case freezes 5 hours；It is placed again into vacuum freeze drier, is freeze-dried 8h, then the Vacuum Heat polycondensation reaction at 160 DEG C
4h reacts locating pressure and is not higher than 0.1Mpa, that is, obtains and aoxidize sub- silicon substrate fexible film electrode.
Carboxymethyl cellulose can be using Japanese Daicel DAICEL CMC2200, viscosity (1% 25 DEG C of aqueous solution@
It 60rpm) is 1500 ~ 3000 mPas, pH value (1% 25 DEG C of aqueous solution@) is 6.0 ~ 8.5, degree of substitution minimum 0.8.
Polyacrylic acid can use 45 ~ 55% aqueous solution of mass percent concentration, and the average molecular weight 2800 of polyacrylic acid ~
3200。
Silicon nano purity used is not less than 99.9%, and partial size is 20 ~ 100 nanometers；Aoxidize sub- silicon particle average grain diameter
It is 3.5 ~ 5 microns.
Fexible film electrode with a thickness of 5 ~ 200 microns.
7 compliance test result of embodiment
The using effect of prepared fexible film electrode is verified by taking embodiment 3 as an example, as shown in Figure 1, institute's fexible film is straight
Diameter is about 5cm, and gained fexible film electrode foil can be cut into the electrode slice that diameter is 12 mm, do not need to add any conduction
Additive and polymer adhesive can be directly used as the assembling that working electrode completes button cell.
Fig. 2 is the XRD spectrum of above-mentioned fexible film electrode, as shown in Figure 2, rGO-Si-CMC-PAA film (i.e. nano-silicon
Base fexible film electrode) characteristic peak of crystalline silicon (JCPDS No. 27-1402) and graphene is showed (positioned at 2θ=
19.58 ° (002) characteristic diffraction peak).The result shows that: raw material graphene oxide is located at 2 after liquid-phase reductionθ=10.1 °
(001) diffraction maximum disappears, and a large amount of oxygen-containing functional groups of surface of graphene oxide and interlayer are removed.Graphene oxide is reduced to
Graphene.Referring to the characteristic diffraction peak and pertinent literature of graphene, it is located at 2θ=19.58 ° (002) characteristic diffraction peak shows
PAA and CMC molecule enters the piece lamellar spacing of adjoining graphite alkene.
Fig. 3 to Fig. 6 is the SEM figure under different multiplying, and wherein Fig. 3 and 4 is respectively rGO-Si-CMC-PAA film in 90,000 Hes
The SEM figure of 200000 times of enlargement ratio lower surfaces, can be seen that the stone in prepared rGO-Si-CMC-PAA film by Fig. 3 and 4
Black alkene piece is interconnected to form the continuous nanoporous network structure of a three-dimensional, and this porous structure is by having loaded Si nanoparticle
What the two-dimensional graphene nanometer sheet of son was constituted.The Si nano particle diameter size range contained in film is about 50nm, Ji Husuo
Some Si nanoparticles are all embedded in and are evenly distributed in lamellar graphite alkene network, while nano silicon particles surface is by layer
Organic matter coated.Figures 5 and 6 are respectively the SEM for being respectively rGO-Si-CMC-PAA film in different enlargement ratio lower sections
Relative level shape is presented in figure, the most of graphene films for as can be seen from the figure forming film, interlayer there are many new holes,
The film shows the three-dimensional structure of a loose typical lamellar.Meanwhile silicon nano is attached on graphene, it is effectively anti-
Only its nanoparticle is reunited.Compared to closelypacked structure, the nanoporous network structure of this opening is conducive to active material
Coming into full contact between material and electrolyte, electrolyte ion is rapidly diffused into electrode active material surface/electrolyte solution circle
Face, and a large amount of electrochemical reaction active site is increased, the diffusion path of lithium ion is shortened, and active material is effectively relieved
Change in the enormousness of continuous charge/discharge process.
The production of battery: being to electrode, by volume by ethylene carbonate and dimethyl carbonate (EC/DMC) with lithium piece
1mol L is prepared for 1:1-1LiPF6Solution is electrolyte, 2400 microporous polypropylene membrane of Celgard as lithium ion battery every
Film assembles button cell (CR2025) and carries out cyclic voltammetric, constant current charge/discharge, ac impedance measurement, and voltage tester scope is
0.005-3.0V(vs. Li+/ Li), current density 200-1000mA/g.The frequency range that ac impedance measurement uses for
100m Hz-100 kHz, voltage amplitude are 5 mV.25 ± 0.5 DEG C of test temperature.
Fig. 7 is the cyclic voltammetry curve that prepared rGO-Si-CMC-PAA film is assembled button cell by cathode, by
It can be seen that the cyclic voltammetry curve for the first time and second and the very big difference of subsequent cyclic voltammetry curve presence of electrode in figure,
Second curve for being recycled to third circulation is almost overlapped, and shows to have occurred in first Cyclic Voltammetry irreversible
Excellent invertibity after reaction and first circulation.The irreversible capacity in circulation is attributable to the decomposition of organic electrolyte for the first time
With the generation in electrode/electrolyte interface SEI film.Electrode third and the peak intensity recycled later and Global integration region and second
A circulation almost approaches, but compared to first circulation is decreased obviously.These results indicate that the electricity of rGO-Si-CMC-PAA electrode
Chemical invertibity is gradually established after first circulation.
Fig. 8 is for rGO-Si-CMC-PAA electrode in 420 mA g-1Current density under initial 1st、2nd、3rd、5th、
200thThe constant current charge/discharge curve of a circulation.As can be seen from Figure, the coulomb effect of rGO-Si-CMC-PAA electrode second circulation
Rate is rapidly increased to 95.65%, and is maintained at 99% or more after subsequent several circulations, shows electrode shape after discharge process for the first time
At relatively stable SEI film.After 200 circulations and keep higher charge/discharge capacity.
The initial voltage and the voltage change situation after 15 days that table 1 is five batteries, prepared film is made seen from table 1
For electrode, battery is assembled into relatively stable voltage, and voltage drop is smaller, and inside battery is stablized.
It is above-mentioned experiments have shown that prepared nano silicon-based fexible film electrode of the invention suitable for lithium ion battery, capacitor or
Other energy storage system electrode fabrications, and there is excellent performance.Nano silicon-based fexible film electrode performance prepared by embodiment 1,2
It is close with the preparation of embodiment 3, lithium ion battery, capacitor or other energy storage system electrode fabrications can also be also used for.
When active particle is to aoxidize sub- silicon particle, experiments prove that the above-mentioned experimental performance of performance and silicon nano
Quite, it can be used for lithium ion battery, capacitor or other energy storage system electrode fabrications.
Claims (9)
1. a kind of preparation method of fexible film electrode, it is characterised in that include the following steps:
(a) graphene oxide and carboxymethyl cellulose are dispersed in water respectively, obtain graphene oxide dispersion and carboxymethyl
Polyacrylic acid and the carboxymethyl cellulose dispersion liquid are added in the graphene oxide dispersion by cellulose dispersion liquid,
The raw molecule cross-link of uniform hybrid concurrency, obtains aqueous composite caking agent, wherein the mass percentage content of graphene oxide be 10 ~
35%, the mass percentage content of carboxymethyl cellulose is 5 ~ 10%, and the mass percentage content of polyacrylic acid is 55 ~ 85%, oxidation
The sum of mass percentage content of graphene, carboxymethyl cellulose and polyacrylic acid is 100%；
(b) active particle is added in the aqueous composite caking agent, it is made to be uniformly dispersed, obtain active particle mixed liquor,
The active particle is silicon nano or aoxidizes sub- silicon particle, and the mass percentage content of the active particle is 60 ~ 90%,
The sum of mass percentage content of the graphene oxide, carboxymethyl cellulose and polyacrylic acid be 10 ~ 40%, active particle with
The sum of mass percentage content of graphene oxide, carboxymethyl cellulose and polyacrylic acid is 100%；
(c) vacuum filter and vacuum freeze drying are carried out to the active particle mixed liquor, prepares flexible graphene oxide-carboxylic
Methylcellulose-polyacrylic acid-active particle laminated film；
(d) it is by the flexible graphene oxide-carboxymethyl cellulose-polyacrylic acid-active particle laminated film liquid-phase reduction
Flexible graphene-carboxymethyl cellulose-polyacrylic acid-active particle laminated film；
(e) Flexible graphene-carboxymethyl cellulose-polyacrylic acid-active particle laminated film impregnated in water, washed
And be freeze-dried, Vacuum Heat polycondensation reaction is then carried out, fexible film electrode is obtained after reaction.
2. the preparation method of fexible film electrode according to claim 1, which is characterized in that the carboxymethyl cellulose is
Japanese Daicel DAICEL CMC2200, viscosity (1% 25 DEG C of aqueous solution@60rpm) are 1500 ~ 3000 mPas, pH value
(1% 25 DEG C of aqueous solution@) is 6.0 ~ 8.5, degree of substitution minimum 0.8, and polyacrylic acid is that mass percent concentration 45 ~ 55% is water-soluble
Liquid, the average molecular weight 2800 ~ 3200 of polyacrylic acid.
3. the preparation method of fexible film electrode according to claim 1, which is characterized in that the silicon nano purity
Not less than 99.9%, partial size is 20 ~ 100 nanometers；Aoxidizing sub- silicon particle average grain diameter is 3.5 ~ 5 microns.
4. the preparation method of fexible film electrode according to claim 1, which is characterized in that used in the step (d)
Liquid-phase reduction agent carries out liquid-phase reduction, and the liquid-phase reduction agent is hydrazine hydrate or sodium borohydride aqueous solution.
5. the preparation method of fexible film electrode according to claim 1, which is characterized in that the step (e) obtained
Fexible film electrode with a thickness of 5 ~ 200 microns.
6. the preparation method of fexible film electrode according to claim 1, which is characterized in that the vacuum of the step (e)
The temperature of thermal polycondensation reaction is 120-180 DEG C, and the time is 1-6 h, and vacuum degree is not higher than 0.1MPa.
7. a kind of fexible film electrode, which is characterized in that the fexible film electrode is using the system as described in claim 1 to 6
Preparation Method production.
8. fexible film electrode according to claim 7, which is characterized in that the fexible film electrode is presented on the whole
Multi-layered network structure, the active particle are coated by graphene, carboxymethyl cellulose and polyacrylic acid molecule.
9. the purposes of fexible film electrode according to claim 7, which is characterized in that the purposes be lithium ion battery or
The production of supercapacitor.
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