Background technology
Ultracapacitor has become as a kind of novel green energy storage device and solves the energy that the world is faced, resource
One of with the most potential electrochemical energy storage device of significant problems such as environment.World-renowned technical journal《It explores》Magazine once will
Ultracapacitor is classified as one of seven big scientific discovery of the world, it is believed that it is a revolutionary development in energy storage field, and will
Replace accumulator in certain fields.Exploitation have high-energy density, high power density and the ultracapacitor of long-life national defence,
There is very wide application prospect in the fields such as aerospace, auto industry, consumer electronics, telecommunications, electric power and railway, right
In mitigating environmental pollution, the sustainable development of human society is promoted to have far-reaching influence.
Currently, with the continuous improvement of living standards, people are to wearable and portable electronic product(Such as Flexible Displays
Device, e-book, tablet computer, ultra-thin smart handset etc.)Demand it is growing day by day, however for driving the electricity of these electronic products
Source(Flexible super capacitor)Development it is still unsound, influence and constrain the scale of mass production of product to a certain extent.Cause
This, develops ultracapacitor controllable preparation new strategy, and exploitation has flexibility, lightweight, low cost and high-performance(High-energy density,
High power density and excellent cycling stability)Ultracapacitor increasingly show its market potential be worth, become current
The emphasis and hot spot of energy storage research field.
Can electrode material be one of the key factor that determines performance of the supercapacitor quality and mass produce.It is passing
It unites in ultracapacitor, electrode material is usually bonded on a conductive collector.Collector generally uses electric conductivity good
Metal material(Such as nickel foam, stainless (steel) wire, titanium foil).But metal material matter itself is hard, yield strength is high, fatiguability damage
And quality is heavy(Density is big).This external cause long period of soaking is easy to corrode in the electrolytic solution, to influence the use scope of electrode
And the service life.Therefore, use they as flexible light weight ultracapacitor collector have the shortcomings that it is very big.Make a general survey of various materials
Material, graphite paper is because it is with good electric conductivity, excellent mechanical performance and flexibility and slim and graceful quality(Density is small),
As preparing the preferred material of flexible super capacitor capacitance collector.
Graphene, after being found from 2004, because its unique two-dimensional structure and excellent physicochemical characteristic are considered as one
The highly desirable electrode material of kind.And it is mild with preparation condition, can prepare on a large scale and the graphene of excellent mechanical strength
Paper is even more to show huge application potential in flexible super capacitor field.But in graphene paper, between graphene film
π-π interactions and Van der Waals force would generally make them that serious reunion and stacking occur, and cause the specific surface area of graphene paper
Become smaller, compact structure can hinder the diffusion of electrolyte, cause its capacitive property unsatisfactory.This defect greatly hinders
Its application in terms of high-performance flexible electrode of super capacitor.In order to overcome this defect, researchers to propose in graphite
Hole is introduced between alkene nanometer sheet or is isolated between graphene film(Be added carbon black, carbon nano-fiber, carbon nanotube,
Transition metal oxide and conducting polymer are done " gasket ").The study found that the introducing of these holes and " gasket " can have
Effect prevents the stacking between graphene nanometer sheet, and the diffusion for increasing its specific surface area, promoting electrolyte, electrode shows excellent
Speed characteristic.The introducing of especially active fake capacitance material is even more to improve the specific capacity and energy density of electrode.However, it is necessary to
, it is noted that the flexibility and electric conductivity of the combination electrode prepared by these methods are but greatly diminished, reality cannot be satisfied
Border production requirement.
In recent years, other than graphene to be prepared into the flexible paper-like electrode of two-dimentional macroscopic view, more and more researcher's notes
It has anticipated and self assembly or the importance with three-dimensional macro structure of template structure is passed through by graphene nanometer sheet.Due to combining
The good characteristic of the three-dimensional porous hierarchical structure of carbon material, these are with micropore, mesoporous and macroporous network structure three-dimensional macro
Big specific surface area, slim and graceful quality and quick electrons/ions transmission path may be implemented in structure.By three-dimensional stone flexible
Mertenyl macrostructure is used for flexible super capacitor, it can play the part of the dual role of electrode material and current collector.But mesh
It is preceding studies have shown that the three-dimensional macro structure of graphene structure there is also scarce in terms of making flexible super capacitor electrode
It falls into.Faint connection between graphene film makes its electric conductivity and flexibility poor, to influence the performance as flexible electrode.
Therefore, realize graphene film between it is full cross-linked be flexible electrode commercial application one of challenge.
Polyaniline is recognized due to its high theoretical capacity, low cost, easily prepared, flexibility and advantages of environment protection
To be the fake capacitance material of the most flexible super capacitor of application potential.But low conductivity and polymer long-chain is not
Stability constrains the acquisition of polyaniline high electrochemical performance.In order to improve the electric conductivity and stability of polyaniline electrode, gather
Aniline/graphene composite nanostructure is often used to build large-scale energy storage system.In addition, in order to realize large capacity
The practical application of ultracapacitor(Such as hybrid vehicle), improving the load capacity of polyaniline is very important.But it is high
Load capacity frequently results in low specific capacity and low energy density, this is because thick polyaniline compact reactor lamination makes electrolyte
Ion is difficult or also cannot can not just participate in electrochemical energy storage within the faster time close to redox active centre at all.
Therefore, if good dispersion can be prepared and with the nano-scale polyaniline electroactive material of abundant hierarchical porous structure, electricity
Chemical energy storage ability can undoubtedly be largely increased, to reach industrial requirement.
In conclusion graphite paper plays irreplaceable role in terms of preparing flexible super capacitor electrode, and structure
Build the hot issue that graphene three-dimensional macro structure is even more an exploitation high-performance flexible electrode material for super capacitor.These three
The interconnected structure that the macrostructure of dimension is provided, only electronics is not transferred to collector rapidly and provides conductive channel,
And shorten the distance that electrolyte ion is diffused into electrode interior surface.
Invention content
The object of the present invention is to provide a kind of graphite paper/carbon nanotube-graphene/polyaniline flexible compound electrodes of preparing
Method, using graphite paper as substrate, graphene and carbon nanotube intersection using electrophoretic deposition by high dispersive in milk power solution
Stacking is constructed on its surface, and loose nano-powder is realized in succession through vacuum high-temperature carbonization treatment, prepares that activated carbon is crosslinked to be had
Three dimensions be connected network structure graphite paper/carbon nanotube-graphene, finally use microwave radiation technology polymerization obtain graphite paper/
Carbon nanotube-graphene/polyaniline flexible electrode has high chemical property and mechanical performance, solves background technology and exists
The above problem.
A method of graphite paper/carbon nanotube-graphene/polyaniline flexible compound electrode is prepared, is comprised the following steps:
By graphene and carbon nanotube high dispersive in milk power solution, it is configured to stable suspension, using electrophoretic deposition
Method is constructed graphene and carbon nanotube are cross layered on its surface, and by electrophoresis, milk powder package is received coated in graphene and carbon
On mitron;
Loose nano-powder is realized through vacuum high-temperature carbonization treatment in succession, prepares being led with three dimensions for activated carbon bonding
Graphite paper/carbon nanotube-graphene of open network structure;
Finally microwave radiation technology polymerization is used to obtain graphite paper/carbon nanotube-graphene/polyaniline flexible electrode.
In this composite material, excellent flexibility, electric conductivity and the chemical stability of graphite paper are the mechanical performance of electrode
It provides safeguard with electrochemical stability.Loose nano-powder is realized through vacuum high-temperature carbonization treatment in succession, prepares activated carbon crosslinking
Graphite paper/carbon nanotube-graphene, greatly strengthen the three-dimensional macro knot built between graphite paper, carbon nanotube, graphene
The electric conductivity and mechanical performance of structure.Wherein, on the one hand carbon nanotube acts as " gasket " between graphene film, improves it and compares table
Area utilization;On the other hand conductive " bridge " is acted as, segregate graphene film is effectively crosslinked by activated carbon, realizes electricity
Son transmission unremitting in the electrodes.Using microwave radiation technology situ aggregation method uniform load nano polyaniline synthetic graphite paper/carbon
Nanotube-graphene alkene/polyaniline flexible compound electrode.In this journey, good dispersion and the nanometer with abundant hierarchical porous structure
Size polyaniline electroactive material can not only further fix the structure of composite material, increase its flexibility, and for carrying
The specific capacity of high composite material, multiplying power property and cyclical stability are also most important.Therefore, the crosslinked three dimensions of activated carbon is led
Graphite paper/carbon nanotube-graphene/polyaniline flexible electrode of open network structure will be with high chemical property and mechanicalness
Energy.
This patent innovative point:
(1)Using flexibility, the high and cheap graphite paper of good, excellent electric conductivity, thermal stability and chemical stability is made
For substrate, guarantee is provided for the good composite and flexible electrode of processing machinery function admirable, electrochemical stability;
(2)Based on the selection of active carbon matrix precursor, design and prepare activated carbon bonding have three dimensions be connected network
Graphite paper/carbon nanotube-graphene of structure is realized full cross-linked between graphite paper, carbon nanotube, graphene film;
(3)To with the uniform negative of high-specific surface area, high electronic conductivity, abundant three-dimensional multistage duct and nano polyaniline
Structure/interface/chemical property mechanism of action of graphite paper/carbon nanotube of load-graphene/polyaniline flexible compound material electrode
Research obtains the high-performance for reaching commercial requirements, inexpensive flexible electrode.
Advantageous effect of the present invention:
(1)Using flexibility, good, excellent electric conductivity, thermal stability and the high graphite paper of chemical stability are as substrate
The mechanical performance and electrochemical stability of this project research combination electrode provide guarantee.It solves in traditional electrode preparation process
In, it is collector usually to select nickel foam, stainless (steel) wire, titanium foil, and not only flexibility is poor and is soaked in aqueous solution electricity for a long time
Xie Zhizhong is easy to be corroded, the problem of seriously affecting electrode use scope and service life;Meanwhile the price of graphite paper is relatively just
Preferably, be conducive to practical popularization and application;
(2)Using electrophoretic deposition is by graphene of the high dispersive in milk power solution and carbon nanotube is cross layered constructs
Graphite paper surface(Milk powder package is coated on graphene and carbon nanotube), loose nano powder is realized through vacuum high-temperature carbonization treatment
Body in succession, prepares the crosslinked graphite paper/carbon nanotube-graphene of activated carbon, formed graphite paper, carbon nanotube, graphene film it
Between it is full cross-linked, both prevented folded poly- effective connection further through activated carbon of graphene film, and realized electronics in the electrodes continuously
Disconnected transmission;
(3)It is multiple using uniform load nano polyaniline synthetic graphite paper/carbon nanotube-graphene/polyaniline flexibility in situ
Composite electrode is realized in the controllable uniform load polyaniline of nano combined layer surface, further increases specific capacitance, in-situ consolidation level hole
Structure realizes the fexible film of height ratio capacity.Study the influence between composite structure/interface/chemical property and its work
With mechanism, to obtain providing fundamental basis for high performance flexible compound electrode.
Specific implementation mode
The present invention is described further for following example:
A method of graphite paper/carbon nanotube-graphene/polyaniline flexible compound electrode is prepared, is comprised the following steps:
By graphene and carbon nanotube high dispersive in milk power solution, it is configured to stable suspension, using electrophoretic deposition
Method is constructed graphene and carbon nanotube are cross layered on its surface, and by electrophoresis, milk powder package is received coated in graphene and carbon
On mitron;
Loose nano-powder is realized through vacuum high-temperature carbonization treatment in succession, prepares being led with three dimensions for activated carbon bonding
Graphite paper/carbon nanotube-graphene of open network structure;
Finally microwave radiation technology polymerization is used to obtain graphite paper/carbon nanotube-graphene/polyaniline flexible electrode.
With reference to attached drawing, this patent embodiment technical solution is described in detail:
Referring to Fig.1, technological process is as shown in the figure.
Using electrophoretic deposition is by graphene of the high dispersive in milk power solution and carbon nanotube is cross layered constructs in stone
Black paper surface prepares the graphite that network structure is connected with three dimensions of activated carbon bonding after through vacuum high-temperature carbonization treatment
Then paper/carbon nanotube-graphene uses microwave radiation technology polymerization to obtain graphite paper/carbon nanotube-graphene/polyaniline flexible
Electrode.
Study the chemical property of flexible compound electrode(Energy density, speed characteristic, power density and cyclical stability).
The present invention uses flexible graphite paper for substrate, prepares the graphene of high dispersive and the suspension milk power solution of carbon nanotube
Carry out electrophoretic deposition;It using graphite paper as an electrode, is immersed in mixing suspension together with auxiliary electrode, keeps spacing;Two
Apply DC electric field between electrode, with carbon nanotube electrophoretic deposition occurs on graphite paper for graphene, forms nanoscale three-dimensional network
Structure;Then, graphite paper/carbon nanometer tube-graphene composite material is put into the micro- evaporation coating machine of vacuum, vacuumizes, is passed through
Nitrogen protection, heating, heat preservation, then cools to room temperature, and is washed to neutrality with dilute hydrochloric acid and deionized water, obtains activated carbon and bonds
With three dimensions conducting network structure graphite paper/carbon nanotube-graphene.
The concrete technology that polyaniline is deposited using microwave radiation technology polymerization is as follows:Aniline and acid are sufficiently mixed to obtain uniformly
Above-mentioned solution is placed in dropping funel by solution, and dropping funel is remained turned-off and connected below equipped with graphite paper/carbon nanometer
The filter flask of pipe-graphene composite material opens dropping funel switch, under pressure inducement, drop after filter flask forvacuum
Solution in liquid funnel is injected into the three-dimensional multistage of the micro-nano double scales of graphite paper/carbon nanometer tube-graphene composite material
In duct;By graphite paper/carbon nanometer tube-graphene composite material of above-mentioned processing be put into the acid solution of aniline and sulfuric acid into
Row microwave radiation deposits, and by controlling reaction temperature, concentration, control graphite paper/carbon nanotube-graphene surface loads polyaniline
Particle size, the uniformity and layer thickness, obtain controllable nano polyaniline layer.
Measure CV curve, ac impedance characteristic and constant current charge-discharge of the flexible compound electrode in neutral or acidic electrolysis bath
Curve, the influence of research different structure, composition, interfacial characteristics to combination electrode chemical property.Disclose graphite paper/carbon nanometer
Pipe-graphene/polyaniline combined electrode structure/interface/chemical property(High-energy density, high-rate characteristics, high power density
And excellent cycling stability)Between influence and its mechanism of action.
Common chemical property parameter calculates as described below.
A specific capacitances
Specific capacitance refers to the ability of capacitor storage charge, unit F/g.Using CHI660C electrochemical workstations three
CV tests are carried out in electrode system, by studying the area that electric current is surrounded with current potential in the curve.Then according to active on electrode
The quality of substance can calculate specific capacitance, i.e.,:
Specific capacitance, energy density, power density can also be calculated according to constant current charge-discharge curve, i.e.,:
B electrode impedances
Ac impedance measurement is carried out on CHI660C electrochemical workstations, electrochemical impedance spectroscopy is Electrochemical Measurement Technology
A kind of middle highly important research method, it has also become the important means of Electrode process kinetics and superficial phenomenon.In reality
Amplitude-frequency characteristic curve and phase frequency feature can be schemed and be included to impedance spectrum in drawing with the Nyquist drawn by impedance vector value and phase angle
The Bode figures of curve indicate.The fitting of corresponding circuit be used in combination in the electrochemical impedance spectroscopy for analyzing electrode, can obtain capacitance, interior
The a series of information such as the capacitance characteristic of resistance and electrode material.
C cyclical stabilities
High stable circulation performance is the important performance indexes of ultracapacitor, the electrode material with good circulation stability
Material is that also there are one higher capacitances for meeting after the charge and discharge some time.This item purpose cyclical stability is with multiple constant current
The ratio of capacitance and initial capacitance after charge and discharge is weighed.
(2)Feasibility analysis
Electrophoretic deposition technique of the present invention is the nanometer controllable operating technology that assembling synthesizes organic and inorganic material,
Organic polymer, nano material preparation in get the attention.Electrode material specific surface area size directly determines it
Electrochemical capacitor performance.Secondly, quick electrolyte ion diffusion admittance and good electronic conduction ability are also essential
's.But due between most of electrode material its body phase often all in closest packing state so that electrolyte ion be difficult or
It also cannot can not just generate redox current within the faster time close to redox active centre at all.Therefore, if
Design structure is well dispersed or electroactive material with abundant level pore passage structure, can thus greatly shorten electrolyte from
The diffusion length of son and time, to enable electrolyte ion fast free to reach the electroactive of electric activity center's material surface
Point.In addition, in order to improve the electron conduction of electroactive material, it will usually which the active material with fake capacitance characteristic is loaded to
Carbon material.Quick electron-transport not only may be implemented in carbon material, while improving the dispersibility of electroactive material.High electricity as a result,
Solve the contact area of liquid/electroactive material, shorter ion diffusion length, it is good lead electronic capability, these three key points
It solves, so that it may inherently to improve the specific capacity and utilization rate of electroactive material, prepare high-performance and survey electrode material.
Therefore, this patent is prepared for the crosslinked graphite paper/carbon nanometer with three dimensions conducting network structure of activated carbon
Pipe-graphene/polyaniline flexible compound electrode.High-specific surface area, high electronic conductivity, three-dimensional multistage duct graphite paper/carbon
Nanotube-graphene alkene composite material is ideal active material(Polyaniline)Growth substrates, act as electron-transport and ion expands
It is scattered to " highway " of active material;Meanwhile microwave method original position uniform load nano polyaniline, it not only further increases than electricity
Hold, and in-situ consolidation hierarchical pore structure, realizes high electrochemical performance and effectively combined with good mechanical properties.
Using carbon nanotube as carrier, microwave method controllable load nano polyaniline layer, experiment shows:Polyaniline can uniformly be born
It is loaded in carbon nano tube surface, with reference to attached drawing 2.
The specific embodiment of the invention, technical characterstic and advantageous effect:
One, graphite paper/carbon nanotube-Graphene electrodes preparation and chemical property
1. preparation and the characterization of graphite paper/carbon nanometer tube-graphene composite material
Electrophoretic deposition preliminary experimental results show:1. aqueous solution is easy electrolysis, hydrogen and oxygen is precipitated in cathode anode respectively
Gas, generating bubble causes sedimentary to fall off.Therefore, electric field used by us cannot be excessively high.2. due to carbon nanotube and graphite
Alkene surface has formed stable chemisorbed layer, in aqueous medium, substantially near neutral charge, i.e., surface without
Electricity, at this moment they there is no electrophoretic property or very faint, it is necessary to charged adjustment is carried out to its surface.Most efficient method is to be added
Surfactant.Two important function are played in charged adjustment:Same sex particle is mutually exclusive, is not easy to reunite and settle, is formed and stablized
Suspension;Its strong electrophoresis ability is assigned, electrophoretic mobility is high, and deposition velocity is fast.
The specific embodiment of the invention:
Using graphite paper as an electrode, the graphene and carbon nano tube suspension of high dispersive are immersed in together with auxiliary electrode
(It is configured by milk powder)In, spacing is maintained at 5 ~ 15mm.Apply DC electric field between two electrodes, graphene is with carbon nanotube in graphite
Electrophoretic deposition occurs on paper electrode.At this time by electrophoresis, milk powder package is coated on graphene and carbon nanotube, through vacuum high-temperature
Graphite paper/carbon nanotube-graphene with three dimensions conducting network structure that carbonization treatment method prepares activated carbon bonding is soft
Property electrode.Milk powder concentration and graphene and carbon nanotube group in different electric field strengths, sedimentation time, suspension is studied to distribute
Than, carburizing temperature, graphite paper/carbon nanotube-graphene for being prepared under soaking time.Pass through conductivity measurement, specific surface area
Test, field emission scanning electron microscope(FESEM), atomic force microscope(AFM)Deng the material of analysis and observation composite material
Electric conductivity, pore structure, aperture size, surface topography and thickness.By the studies above, obtain activated carbon bonding has three-dimensional
The deposition parameter of graphite paper/carbon nanometer tube-graphene composite material of network structure is connected in space.
2. graphite paper/carbon nanometer tube-graphene composite material Electrochemical Properties
Using three-electrode system, using graphite paper/carbon nanometer tube-graphene composite material as working electrode, platinum plate electrode is
Auxiliary electrode is saturated calomel or Ag/AgCl reference electrodes, studies in neutrality(Na2SO4Or acidity H2SO4)Cycle volt in the liquid of bottom
Pacify curve, ac impedance characteristic and constant current charge-discharge, research graphite paper/carbon nanometer tube-graphene composite material different structure with
The influence of the pairs of composite material chemical property of group.
Two, graphite paper/carbon nanotube-graphene/polyaniline electrode preparation and chemical property
1. preparation and the characterization of graphite paper/carbon nanotube-graphene/polyaniline combination electrode
The specific embodiment of the invention
Graphite paper/carbon nanometer tube-graphene composite material is handled using vacuum aided pressure inducement method.By aniline
Be sufficiently mixed to obtain homogeneous solution with sulfuric acid, then above-mentioned solution be placed in dropping funel, dropping funel remain turned-off and
Below then filter flask of the connection equipped with graphite paper/carbon nanometer tube-graphene composite material opens filter flask forvacuum
Dropping funel switchs, and under pressure inducement, the solution in dropping funel is injected into graphite paper/carbon nanotube-graphene composite wood
In the three-dimensional multistage duct of material.
It is sunk on above-mentioned processed graphite paper/carbon nanotube-graphene flexible composite with microwave radiation technology polymerization
Product nano polyaniline, prepares graphite paper/carbon nanotube-graphene/polyaniline combination electrode, realizes that nanometer is poly- by microwave radiation
Aniline uniform particle deposits, while further consolidating graphene, carbon nano tube structure, improves the flexibility of entire composite material.
Utilize infrared absorption(FTIR)Spectrum, XRD, HRTEM, FESEM, XPS, AFM, specific surface area test, conductivity are surveyed
It tries instrument etc. and ingredient, structural characterization is carried out to the polyaniline of synthesis.Study the dispersion degree of technological parameter and nano polyaniline, granularity,
The conductivity of composite material, porosity and specific surface area are compared in the relationship of load capacity, analysis.Study what different depositing operations obtained
Interface cohesion feature between polyaniline and graphite paper/carbon nanotube-graphene flexible composite.
2. the Electrochemical Properties of graphite paper/carbon nanotube-graphene/polyaniline combination electrode
Using three-electrode system, using graphite paper/carbon nanotube-graphene/polyaniline combination electrode as working electrode, platinized platinum
Electrode is auxiliary electrode, and it is reference electrode to be saturated calomel or Ag/AgCl, is studied in neutrality(Na2SO4)Or it is acid(H2SO4)Bottom liquid
In CV curves, ac impedance characteristic and constant current charge-discharge, compared with graphite paper/carbon nanometer tube-graphene composite material, research
The influence of different structure, composition, interfacial characteristics to combination electrode chemical property.Announcement graphite paper/carbon nanotube-graphene/
Influence between polyaniline composite electrode structure/interface/chemical property and its mechanism of action.
The art of this patent feature:
(1)Graphite paper/carbon nanotube-of activated carbon bonding is prepared using electrophoretic deposition and through vacuum high-temperature carbonization treatment
Graphene makes its composite material have high-specific surface area, high electronic conductivity, abundant three-dimensional multistage pore passage structure;
(2)Using uniform load nano polyaniline in situ, controllable preparation graphite paper/carbon nanotube-graphene/polyaniline is soft
Property combination electrode, realize in the controllable uniform load polyaniline of nano combined layer surface, study composite layer and nano polyaniline
The load mechanism of layer establishes original position load mechanism and finds optimal processing parameter and rule;
(3)Study the regulation rule of combination electrode micro-structure and the interface rule of composite material, its electrochemistry of system thinking
Performance discloses the influence between structure/interface/chemical property and its mechanism of action.
The technology of the present invention effect:
(1)By controlling electric field strength, sedimentation time and each component proportion of milk power solution concentration, suspension, surface is lived
Property agent addition, prepare uniform, smooth, thickness is controllable carbon nanotube, graphene layer, and through vacuum high-temperature carbonization treatment system
Graphite paper/carbon nanotube-graphene that standby activated carbon bonds;
(2)By uniform load nano polyaniline in situ, controllable preparation graphite paper/carbon nanotube-graphene/polyaniline is soft
Property combination electrode, obtain graphite paper/carbon nanotube-graphene/polyaniline flexible electrode, have high chemical property and machinery
Performance.