CN104269281A - Method for manufacturing asymmetric super capacitor - Google Patents
Method for manufacturing asymmetric super capacitor Download PDFInfo
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- CN104269281A CN104269281A CN201410503506.4A CN201410503506A CN104269281A CN 104269281 A CN104269281 A CN 104269281A CN 201410503506 A CN201410503506 A CN 201410503506A CN 104269281 A CN104269281 A CN 104269281A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a method for manufacturing an asymmetric super capacitor with a solid phase electrode material and liquid phase electrolyte which provide capacitance at the same time. The super capacitor has superhigh energy density, power density and circulating stability. The positive electrode is made of a cobaltous hydroxide/graphene composite electrode material, and the electrolyte is the mixed electrolyte of potassium hydroxide/potassium ferricyanide. The negative electrode is made of an activated carbon/carbon fiber paper electrode material, and the electrolyte is the mixed electrolyte of potassium hydroxide/p-phenylenediamine. The solid phase electrode material and liquid phase electrolyte synchronously and independently provide the capacitance. The asymmetric super capacitor can have high energy density, power density and circulating density under the high charging and discharging density. The energy density is 124.4 Wh/kg under the 2A/g charging and discharging current density, the corresponding power density is 2,000 W/kg, and specific capacitance of the capacitor hardly attenuates after 20,000 times of circulation.
Description
Technical field:
Prepare and optimize positive electrode material cobalt hydroxide/Graphene, and groped the preparation technology of negative electrode material activated carbon, obtain cobalt hydroxide/Graphene-potassium hydroxide/potassium ferricyanide positive electrode system and the activated carbon/carbon paper-potassium hydroxide/p-phenylenediamine (PPD) negative electrode system of high electrochemical performance.Assemble novel asymmetric ultracapacitor on the basis of the above work.Solid electrode and liquid electrolyte provide fake capacitance simultaneously on the one hand, and capacitor ratio capacitance increases substantially; On the other hand, Proper Match asymmetric ultracapacitor, the operating potential window of capacitor have also been obtained and increases substantially.The novel asymmetric capacitor of our assembling has the energy density of superelevation, power characteristic and cyclical stability.
Background technology:
The energy is day by day short, and environment goes from bad to worse, and reproducible novel Conversion of Energy/storage device that development is cleaned becomes the 21 century mankind and solves the new effective way of energy problem.Current battery and capacitor two kinds of electrochemical appliances receive the concern of researcher, but the battery with high-energy-density has low power density, although ultracapacitor has high power density, energy density is lower.Following energy storage requires to possess high energy density simultaneously, high power density and long cyclical stability.Ultracapacitor charge/discharge rates is fast, and have extended cycle life, environmental friendliness, becomes novel green energy resource.Because energy density is low, the ultracapacitor of identical energy needs larger weight or larger volume, and this is for the electronic equipment of movable type, vehicle, large-scale guided missile military equipment, field work, space flight thing etc. and disadvantageous.Raising energy density has become ultracapacitor and has further developed faced significant challenge.And practical application also concentrates on the material with carbon element symmetrical expression capacitor of stable performance.The capacitor of asymmetric is owing to achieving high mutual capacitance window and ratio capacitance, and its research achieves certain achievement, but energy density (20Whkg
-1) still well below battery levels.There is limited evidence currently of has people to consider the electrolyte of liquid phase also can be stored and discharge electric energy.
Summary of the invention:
The object of the invention is to, from above background, propose the method for the assembling of a kind of Novel asymmetric formula ultracapacitor and preparation.Particularly a kind of with cobalt hydroxide/Graphene for positive electrode material, with potassium hydroxide/potassium ferricyanide mixed aqueous solution for anode electrolyte; With activated carbon/carbon paper for negative electrode material, the preparation method being electrolyte liquid with potassium hydroxide/p-phenylenediamine (PPD) mixed aqueous solution.One side realizes solid electrode and liquid electrolyte provides electric capacity simultaneously, improves the capacitive properties of ultracapacitor; On the other hand, by Proper Match asymmetric ultracapacitor, achieve large operating potential window, the energy density of ultracapacitor is greatly improved.First using chemical vapour deposition (CVD) (PECVD) as means, the few layer graphene of Direct precipitation in collector nickel foam, fundamentally overcomes that Graphene defect prepared by general chemistry method is many, the shortcoming of bad dispersibility and poorly conductive.Then by the method for electrochemical deposition, cobalt hydroxide is deposited on graphenic surface, obtains the positive electrode of ultracapacitor, form novel positive pole system with the potassium ferricyanide/potassium hydroxide mixed electrolytic solution.Adopt the method (carbon fiber paper directly does collector) in carbon fiber paper substrate of spraying to spray AC as negative pole, form novel negative pole system with p-phenylenediamine (PPD)/potassium hydroxide mixed electrolytic solution.Test result shows that this asymmetric ultracapacitor can realize the energy density of superelevation, power density and cyclical stability.
Being summarized as follows of basic technical scheme of the present invention:
The positive pole of Novel asymmetric formula ultracapacitor selects cobalt hydroxide/Graphene/foam nickel electrode, and negative pole selects activated carbon/carbon paper electrode.Novel capacitor positive pole selects potassium hydroxide/potassium ferricyanide mixed electrolytic solution, and negative pole selects potassium hydroxide/p-phenylenediamine (PPD) mixed electrolytic solution.Adopt the Nafion film of clean as barrier film.Assemble novel asymmetric ultracapacitor, and electrochemical property test is carried out to it.
Concrete technical parameter of the present invention and optimum Choice are described below:
The preparation of cobalt hydroxide/Graphene-potassium hydroxide/potassium ferricyanide positive pole system in the present invention, with nickel foam, POROUS TITANIUM or other metal materials for substrate, PECVD method is selected to grow few layer graphene, then as substrate, constant potential or constant current electrochemical deposition cobalt hydroxide, obtain positive electrode, then form positive pole system with potassium hydroxide/potassium ferricyanide mixed electrolytic solution, main process is divided into following steps:
1) system vacuumizes, and passes into some gas and makes protection gas heating to predetermined temperature, pass into reacting gas, when temperature reaches reaction temperature, insulation a period of time, make gas and vapor permeation even.
2) carbon-source gas, ionized gas rational proportion, adjustment reactant gas dividing potential drop, setting radio-frequency power and sedimentation time, the abundant ionization of reaction raw materials, decomposition, be transformed into active group, and substrate is prepared few layer graphene.
3) Graphene/nickel foam is put into electrolyte as work electrode, constant temperature water bath is warming up to predetermined temperature, makes electrochemical deposition system maintain constant temperature.
4) regulate the sedimentation potential needed for experiment or electric current, empirically predetermined deposition electricity carries out electrochemical deposition; After deposition, close electrochemical deposition power supply, take out work electrode, with washed with de-ionized water surface repeatedly, naturally dry and can obtain cobalt hydroxide/Graphene positive electrode.
5) configure the potassium hydroxide/potassium ferricyanide mixed solution of finite concentration ratio, introduce anolyte groove as anode electrolyte.
The preparation of activated carbon/carbon paper-potassium hydroxide/p-phenylenediamine (PPD) negative pole system in the present invention, preferred spraying technology, the metal materials such as carbon fiber paper, carbon cloth, nickel foam, POROUS TITANIUM are substrate, spraying/knife coating procedure is adopted to prepare activated carbon/carbon paper negative electrode, then form negative electrode system with potassium hydroxide/p-phenylenediamine (PPD) mixed electrolytic solution, main process is divided into following steps:
1) get appropriate Nafion solution and inject absolute ethyl alcohol, ultrasonic process, makes binding agent fully mix with solvent.
2) add the activated carbon of certain mass ratio, electrically conductive graphite and binding agent again, through ultrasonic process and high-speed stirred a period of time, obtain active material slurry.
3) appropriate slurry is measured, at N
2under the driving of gas by pneumatic airbrush to the tiny drop of collector carbon fiber paper even application.
4) activated carbon/carbon paper electrode sprayed is put into vacuum drying chamber annealing in process.
5) configure the potassium hydroxide/p-phenylenediamine (PPD) mixed solution of finite concentration ratio, introduce electrolyte groove as electrolyte liquid.
When assembling model electrochemical capacitor in the present invention, separate between positive and negative electrode system with selective penetrated property barrier film, potassium ion can freely be passed through, other electrolyte ion can not be through.Electrochemical properties is tested, and adopts Shanghai occasion China electrochemical analyser, the U.S. 2273 electrochemical workstation or other Electrochemical Comprehensive Tester devices to carry out electro-chemical test.
In the present invention, in the preparation process of few layer graphene, protective gas and ionization of gas select inert gas, metallic substrates is put into reaction vessel, carries out vacuumizing process, make the back end pressure of system at below 10Pa.
In the present invention, in the preparation process of few layer graphene, step 1) temperature-rise period, its heating time preferred 40min, temperature retention time 5 ~ 30min.
In the present invention, in the preparation process of few layer graphene, step 1) in the preferred argon gas of temperature-rise period do protective gas, flow 10 ~ 40sccm, pressure 100 ~ 500Pa.
In the present invention, in the preparation process of few layer graphene, step 2) radio-frequency power 100 ~ 400W, sputtering time 10 ~ 50min, reaction temperature 600 ~ 900 DEG C, reaction pressure 400 ~ 1200Pa.
In the present invention, in the preparation process of sandwich construction cobalt hydroxide, step 3) temperature retention time 5 ~ 30min.
The object of insulation is to make electrochemical deposition system maintain constant temperature, makes deposition velocity even, effectively controls unitary variant.
In the present invention, in the preparation process of sandwich construction cobalt hydroxide, step 4) sedimentation potential select-0.6V ~-1.2V, deposition electricity constant 0.1 ~ 5.0 × 10
-3ah/cm
2, cobalt nitrate concentration of electrolyte 0.02 ~ 1M.
In the present invention, in the selection of positive pole system electrolyte, step 5) the concentration 0.5 ~ 6M of potassium hydroxide, the potassium ferricyanide 0.01 ~ 0.5M.
In the present invention, in activated carbon/carbon paper electrode preparation process, step 1) sonication treatment time 10 ~ 120min.
In the present invention, in activated carbon/carbon paper electrode preparation process, step 2) mass ratio (50 ~ 90) of activated carbon, electrically conductive graphite and binding agent that adds: (5 ~ 30): (2 ~ 10), through ultrasonic process and each 10 ~ 120min of high-speed stirred, obtain active material slurry
In the present invention, in activated carbon/carbon paper electrode preparation process, step 4) activated carbon/carbon paper electrode sprayed is put into vacuum drying chamber, at 60 ~ 200 DEG C of annealing 2 ~ 20h.
In the present invention, in the selection of negative pole system electrolyte, step 5) the concentration 0.5 ~ 6M of potassium hydroxide, p-phenylenediamine (PPD) is 0.001 ~ 0.5M.
In the present invention, in the assembling of model electrochemical capacitor, positive and negative electrode quality of materials is than being 1:2 ~ 1:6.
In sum, in the present invention, the basic comprising of optimization technique parameter is: with the cobalt hydroxide/Graphene of PECVD combined with electrochemical deposition preparation for positive electrode material, with potassium hydroxide/potassium ferricyanide mixed solution for anode electrolyte; Activated carbon/the carbon paper prepared with spraying/knife coating procedure is for negative electrode material, with potassium hydroxide/p-phenylenediamine (PPD) mixed solution for electrolyte liquid, assembling Novel asymmetric capacitor, this super capacitor energy density and power density all very high, cyclical stability is excellent.
The present invention has following obvious advantage:
1) we utilize PECVD method to prepare Graphene, and the method efficiency is high, graphene conductive good, reunion is few; Utilize electrochemical deposition method to deposit cobalt hydroxide, active material directly can be deposited on substrate surface and need not add other binding agent, thus improves purity and the utilance of active material, is conducive to the raising of fake capacitance performance; And add the bond strength of active material and substrate, improve the stability of electrode.Activated carbon/carbon paper electrode has good capacitance characteristic and stability.
2) in electrolyte, redox materials is added, make Solid electrode materials and liquid electrolyte two-phase provide electric capacity simultaneously, increase substantially the energy density of this electrode system, under same energy density, considerably reduce the volume or weight of electrode system in other words.
3) this kind of novel capacitor achieves the energy density of superelevation, power density and cyclical stability.
Accompanying drawing illustrates:
Fig. 1 (a) is the scanning electron microscope diagram on positive electrode material surface of the present invention.
Fig. 1 (b) is the scanning electron microscope diagram on negative electrode material surface of the present invention.
Fig. 2 (a) is the charging and discharging curve of conventional, asymmetrical capacitor (cobalt hydroxide/Graphene-potassium hydroxide positive electrode system) 2A/g current density.
Fig. 2 (b) is the charging and discharging curve of conventional, asymmetrical capacitor (activated carbon/carbon paper-potassium hydroxide negative electrode system) 2A/g current density.
Fig. 3 Novel asymmetric capacitor is at the cyclic voltammogram of different scanning speed (5mV/s, 10mV/s, 25mV/s).
Fig. 4 Novel asymmetric capacitor at high current density 10A/g through 20000 cyclical stability test results.
Embodiment:
The invention provides the preparation method of ultracapacitor of a kind of high-energy-density, high power density, long circulation life.First, the compound of electrode material graphene and cobalt hydroxide is realized by plasma enhanced chemical vapor deposition method and electrochemical deposition method, and with cobalt hydroxide/Graphene for positive electrode material, potassium hydroxide/potassium ferricyanide mixed aqueous solution is anode electrolyte composition positive electrode system; Then prepare active carbon electrode with spraying/knife coating procedure, and with activated carbon/carbon paper for negative electrode material, potassium hydroxide/p-phenylenediamine (PPD) mixed aqueous solution is electrolyte liquid composition negative electrode system; Two electrode systems are connected by selectivity permeability film, make two electrodes can independent action, and then carry out electro-chemical test to novel capacitor, concrete steps comprise:
Steps A: base material is placed in vacuum plant, is heated to predetermined temperature, passes into reacting gas under protective gas argon atmosphere, when temperature reaches reaction temperature, insulation a period of time, makes gas and vapor permeation even;
Step B: utilize plasma enhanced chemical vapor deposition method, adjustment reacting gas dividing potential drop, setting radio-frequency power and sputtering time, little deposit layer graphene on the metallic substrate, make the ionization under the effect of radio-frequency power supply of carbon-source gas, argon gas, be decomposed into plasma, by chemical reaction, finally in substrate, deposit few layer graphene;
Step C: after reaction terminates, stops passing into reacting gas, continues logical protective gas, is cooled to room temperature;
Step D: the substrate of little deposit layer graphene immersed and be equipped with in the electrolysis tank of cobalt nitrate electrolyte, and be placed in constant temperature water bath by electrolysis tank, be warming up to predetermined temperature, insulation a period of time, makes electrochemical deposition system maintain constant temperature.
Step e: the current potential of constant voltage constant current power or electric current are adjusted to the required numerical value of experiment, empirically predetermined deposition electricity carries out electro-deposition in cobalt nitrate solution; After electrolysis, with washed with de-ionized water electrode surface repeatedly, naturally dry and can obtain cobalt hydroxide/Graphene electrodes.
Step F: with cobalt hydroxide/graphene combination electrode for positive electrode, with the potassium ferricyanide/potassium hydroxide mixed aqueous solution for anode electrolyte, builds novel positive electrode system.
Step G: get appropriate Nafion solution and inject absolute ethyl alcohol, ultrasonic process, makes binding agent fully mix with solvent.Add the activated carbon of certain mass ratio, electrically conductive graphite and binding agent again, through ultrasonic process and high-speed stirred a period of time, obtain active material slurry.
Step H: measure appropriate slurry, at N
2under the driving of gas by pneumatic airbrush to the tiny drop of collector carbon paper even application.
Step I: the activated carbon/carbon paper electrode sprayed is put into vacuum drying chamber annealing in process.
Step J: using activated carbon/carbon paper electrode as negative electrode, with potassium hydroxide/p-phenylenediamine (PPD) mixed aqueous solution for electrolyte liquid, builds novel negative electrode system.
Step K: using the novel positive and negative electrode system built as positive and negative electrode, assembling Novel asymmetric electrochemical capacitor, separates with selective penetrated property barrier film between positive and negative electrode system, potassium ion can freely be passed through, and other electrolyte ion can not be through.
In described steps A, described base material is selected from nickel foam, POROUS TITANIUM, stainless (steel) wire, nickel sheet, titanium sheet or iron plate etc. and makes collector material; Described protective gas argon gas flow velocity 10 ~ 40sccm, pressure is 100 ~ 500Pa; Described reacting gas is carbon-source gas, is selected from organic molecule hydrocarbons, and preferred gas is methane; Described reaction temperature is at 600 ~ 900 DEG C; Described temperature retention time is 5 ~ 30min.
In described steps A, reaction temperature is preferably 800 DEG C, and heating rate is 20 DEG C/min; The preferred 10min of temperature retention time.
In described step B, described reacting gas pressure is preferably between 400 ~ 1200Pa, and radio-frequency power is 100 ~ 400W, ionization time is 10 ~ 50min, reaction temperature is 600 ~ 900 DEG C, and reacting gas and ionized gas flowrate proportioning are 20:60 ~ 20:120, and unit is sccm.
In described step B, radio-frequency power is preferably 200W, and ionization time is preferably 30min, and reacting gas and ionized gas flowrate proportioning are preferably 20:80, and unit is sccm.
In described step D, temperature retention time is 5 ~ 30min preferably.
In described step e, electrochemical deposition temperature 25 ~ 65 DEG C, sedimentation potential-0.6 ~-1.2V.
Described depositing temperature preferably 45 DEG C, sedimentation potential is-0.9V preferably.
In described step F, in the potassium ferricyanide/potassium hydroxide mixed solution, concentration of potassium hydroxide is 0.5 ~ 6M, potassium ferricyanide concentration 0.01 ~ 0.5M.
In described step G, the mass ratio (50 ~ 90) of the activated carbon added, electrically conductive graphite and binding agent: (5 ~ 30): (2 ~ 10), through ultrasonic process and each 10 ~ 120min of high-speed stirred, obtains active material slurry.
In described step G, the preferred 85:10:5 of mass ratio of activated carbon, electrically conductive graphite and binding agent.Ultrasonic process and high-speed stirred time preferred 30min.
In described step H, N
2flow velocity 2 ~ the 20sccm of gas.
In described step I, the activated carbon/carbon paper electrode sprayed puts into vacuum drying chamber, and annealing temperature is 60 ~ 200 DEG C, annealing time 2 ~ 20h.
In described step J, the concentration 0.5 ~ 6M of potassium hydroxide, PPD are 0.001 ~ 0.5M.
In described step K, using the novel positive and negative electrode system built as positive and negative electrode, assembling Novel asymmetric electrochemical capacitor, separates with selective penetrated property barrier film between positive and negative electrode system, potassium ion can freely be passed through, and other electrolyte ion can not be through.
Particular content of the present invention is further illustrated below in conjunction with instantiation.
Embodiment 1:
1) utilize PECVD device, heat up to metal base material in argon gas, flow velocity 20sccm, pressure is 200Pa, and depositing temperature is 800 DEG C, and heating rate is 20 DEG C/min.
2) after temperature reaches reaction temperature 800 DEG C, pass into methane gas, gas ratio is CH
4/ Ar=20/80, gas pressure intensity is 400Pa.
3) open radio-frequency power supply, radio-frequency power is 200W, and ionization time is 30min.
4), after reaction terminates, continue logical argon gas to room temperature, take out and treat that next step is for subsequent use.
5) constant temperature water bath maintains constant temperature 45 DEG C.Sedimentation potential is adjusted to-0.9V, at three-electrode system empirically predetermined deposition electricity electrochemical deposition; After electrolysis, close constant voltage constant current power, take out work electrode, with washed with de-ionized water surface repeatedly, naturally dry and can obtain cobalt hydroxide/Graphene electrodes.
6) get appropriate Nafion solution and inject absolute ethyl alcohol, ultrasonic process 30min, makes binding agent fully mix with solvent, then adds activated carbon, electrically conductive graphite and binding agent that mass ratio is 85:10:5, through ultrasonic process and each 30min of high-speed stirred, obtain active material slurry.Measure appropriate slurry, at N
2under the driving of gas by pneumatic airbrush to the tiny drop of collector carbon paper even application.Activated carbon/the carbon paper electrode sprayed is put into vacuum drying chamber, at 120 DEG C of annealing 5h.Be cooled to room temperature stand-by.
7) with cobalt hydroxide/graphene composite material for positive electrode, the 1M potassium hydroxide+0.04M potassium ferricyanide is anode electrolyte; Using activated carbon/carbon paper electrode as negative electrode, with 1M potassium hydroxide+0.025M p-phenylenediamine (PPD) for electrolyte liquid.
8) using the novel positive and negative electrode system built as positive and negative electrode, assembling Novel asymmetric electrochemical capacitor, separates with selective penetrated property barrier film between positive and negative electrode system, potassium ion can freely be passed through, and other electrolyte ion can not be through.
9) electrochemical property test is carried out to Novel asymmetric capacitor, comprise cyclic voltammetry and constant current charge-discharge test.Constant current charge-discharge under current density 2A/g condition, ratio capacitance can reach 224.0F/g (by solid electrode cobalt hydroxide Mass Calculation ratio capacitance, lower same) energy density and be up to 124.4Wh/kg, corresponding power density 2000W/kg.
Embodiment 2:
By embodiment 1 step 7) novel mixed electrolytic solution changes traditional potassium hydroxide electrolyte (namely not having adding of the potassium ferricyanide and p-phenylenediamine (PPD)) into.The ratio capacitance 54.0F/g of this capacitor of constant current charge-discharge under 2A/g current density, energy density is up to 16.9Wh/kg, corresponding power density 1500W/kg.
According to the citing of foregoing invention, can prepare high performance with cobalt hydroxide/Graphene-potassium hydroxide/potassium ferricyanide for positive electrode system and the Novel asymmetric capacitor that is negative electrode system with activated carbon/carbon paper-potassium hydroxide/p-phenylenediamine (PPD), this Novel asymmetric capacitor has following feature:
1) Graphene provides high-ratio surface sum high conductivity, and good stability, is conducive to electric transmission, and internal resistance is low, and power characteristic is good.
2) scanning electron microscopic observation is carried out to the cobalt hydroxide/Graphene prepared by said method, cobalt hydroxide/the graphene composite material of preparation is in the network configuration of intersecting, cobalt hydroxide nanometer sheet is very thin, form a large amount of holes, this structure is not only conducive to the conduction of electrolyte diffusion and ion, and be conducive to the specific area improving electrode material, improve the activity of electrode material, and redox reaction good reversibility.Activated carbon is dispersed on carbon fiber paper simultaneously, is conducive to the raising of activated carbon utilance.
3) the Novel asymmetric capacitor introducing redox materials (potassium ferricyanide and p-phenylenediamine (PPD)) in the electrolytic solution has the ratio capacitance more a lot of than traditional potassium hydroxide electrolyte height and potential window, thus realizes high energy density.
5) the Novel asymmetric capacitor under example 1 condition has high energy density, power density and cyclical stability.Under the charging and discharging currents density of 2A/g, energy density is 124.4Wh/kg, and power density is 2000W/kg, and novel capacitor is not almost decayed through 20000 recycle ratio electric capacity.
Claims (17)
1. the manufacture method of asymmetric ultracapacitor, comprises preparation and the assembling of capacitor positive and negative electrode system and electrode material and electrode solution, it is characterized in that:
Positive pole electrode used therein material is cobalt hydroxide/graphene combination electrode material, and electrolyte is the mixed electrolytic solution of potassium hydroxide/potassium ferricyanide; Negative pole electrode material used is activated carbon/carbon fiber paper, and electrolyte is the mixed electrolytic solution of potassium hydroxide/p-phenylenediamine (PPD), realizes solid electrode and liquid electrolyte provides ratio capacitance simultaneously, and concrete steps comprise:
Steps A: base material is placed in vacuum plant, is heated to predetermined temperature at protective gas argon atmosphere, passes into reacting gas, when temperature reaches reaction temperature, insulation a period of time, makes gas and vapor permeation even;
Step B: utilize plasma enhanced chemical vapor deposition method, adjustment reacting gas dividing potential drop, setting radio-frequency power and sputtering time, little deposit layer graphene in substrate, make the ionization under the effect of radio-frequency power supply of carbon-source gas, argon gas, be decomposed into plasma, by chemical reaction, finally in substrate, deposit few layer graphene;
Step C: after reaction terminates, stops passing into reacting gas, continues logical protective gas, is cooled to room temperature;
Step D: the foam nickel electrode of little deposit layer graphene is immersed and is equipped with in the electrolysis tank of cobalt nitrate electrolyte, cobalt nitrate concentration of electrolyte 0.02 ~ 1M, and electrolysis tank is placed in constant temperature water bath, be warming up to predetermined temperature 35 ~ 65 DEG C, insulation a period of time, electrochemical deposition system is made to maintain constant temperature;
Step e: the current potential of constant voltage constant current power or electric current are adjusted to the required numerical value of experiment, empirically predetermined deposition electricity carries out electrochemical deposition in cobalt nitrate solution; After electrolysis, with deionized water repeatedly cleaning electrode, naturally dry and can obtain cobalt hydroxide/Graphene electrodes;
Step F: with cobalt hydroxide/graphene combination electrode for positive electrode, with potassium hydroxide/potassium ferricyanide mixed aqueous solution for anode electrolyte, builds positive electrode system;
Step G: get appropriate Nafion solution and inject absolute ethyl alcohol, ultrasonic process, makes binding agent fully mix with solvent, then adds the activated carbon of certain mass ratio, electrically conductive graphite and binding agent, through ultrasonic process and high-speed stirred a period of time, obtain active material slurry;
Step H: measure appropriate slurry, at N
2under the driving of gas by pneumatic airbrush to the tiny drop of collector carbon fiber paper even application;
Step I: the activated carbon/carbon paper electrode sprayed is put into vacuum drying chamber annealing in process;
Step J: using activated carbon/carbon paper electrode as negative electrode, with potassium hydroxide/p-phenylenediamine (PPD) mixed aqueous solution for electrolyte liquid, builds negative electrode system;
Step K: using the positive and negative electrode system built as positive and negative electrode, assembling asymmetric electrochemical capacitor, positive and negative electrode system separates with selective penetrated property barrier film, and potassium ion is freely passed through, and other electrolyte ion can not be through.
2. the manufacture method of asymmetric ultracapacitor as claimed in claim 1, is characterized in that:
The preparation of described capacitor positive electrode material is as steps A, and described base material is selected from nickel foam, nickel sheet or titanium sheet common substrate materials; Background pressure in described vacuum plant is at below 10Pa; Described protective gas argon gas flow velocity is 10 ~ 40sccm, and pressure is 100 ~ 500Pa; Described reacting gas is carbon-source gas; Described reaction temperature is at 600 ~ 900 DEG C; Described temperature retention time is between 5 ~ 30min.
3. the manufacture method of asymmetric ultracapacitor as claimed in claim 2, is characterized in that:
The preparation of described capacitor positive electrode material is as steps A, and described carbon-source gas is selected from the hydro carbons comprising methane, and reaction temperature elects 800 DEG C as, and heating rate is 20 DEG C/min; Temperature retention time 10min.
4. the manufacture method of asymmetric ultracapacitor as claimed in claim 1, is characterized in that:
The preparation of described capacitor positive electrode material is as step B, described reacting gas pressure selects between 400 ~ 1200Pa, radio-frequency power is 100 ~ 400W, sputtering time is 10 ~ 50min, reaction temperature is 600 ~ 900 DEG C, reacting gas and sputter gas flowrate proportioning are 20:60 ~ 20:120, and unit is sccm, standard state ml/min.
5. the manufacture method of asymmetric ultracapacitor as claimed in claim 4, is characterized in that:
The preparation of described capacitor positive electrode material is as step B, and described radio-frequency power elects 200W as, and sputtering time is 30min, and reaction temperature is 800 DEG C, and reacting gas and sputter gas flowrate proportioning are 20:80.
6. the manufacture method of asymmetric ultracapacitor as claimed in claim 1, is characterized in that:
The preparation of described capacitor positive electrode material is as step D, and temperature retention time selects more than 10min.
7. the manufacture method of asymmetric ultracapacitor as claimed in claim 1, is characterized in that:
The preparation of described capacitor positive electrode material, as step e, deposits electricity constant 0.1 ~ 5 × 10
-3ah/cm
2, cobalt nitrate concentration of electrolyte 0.02 ~ 1M, electrochemical deposition temperature preferably 35 ~ 65 DEG C, sedimentation potential-0.6 ~-1.2V.
8. the manufacture method of asymmetric ultracapacitor as claimed in claim 1, is characterized in that:
The preparation of described capacitor positive electrode material as step e, deposition electricity preferably 0.37 × 10
-3ah/cm
2, the preferred 0.1M of cobalt nitrate concentration of electrolyte, electrochemical deposition temperature preferably 45 DEG C, sedimentation potential is-0.9V preferably.
9. the manufacture method of asymmetric ultracapacitor as claimed in claim 1, is characterized in that:
The preparation of described capacitor positive electrode material is as step F, and electrolyte is selected in potassium hydroxide/potassium ferricyanide mixed solution, and concentration of potassium hydroxide is 0.5 ~ 6M, potassium ferricyanide concentration 0.01 ~ 0.5M.
10. the manufacture method of asymmetric ultracapacitor as claimed in claim 1, is characterized in that:
The preparation of described capacitor negative electrode material is as step G, the mass ratio (50 ~ 90) of the activated carbon added, electrically conductive graphite and binding agent: (5 ~ 30): (2 ~ 10), through ultrasonic process and each 10 ~ 120min of high-speed stirred, obtain active material slurry.
The manufacture method of 11. asymmetric ultracapacitors as claimed in claim 1, is characterized in that:
The preparation of described capacitor negative electrode material is as step G, and the mass ratio of activated carbon, electrically conductive graphite and binding agent selects 85:10:5, and ultrasonic process and high-speed stirred time select 30min.
The manufacture method of 12. asymmetric ultracapacitors as claimed in claim 1, is characterized in that:
The preparation of described capacitor negative electrode material is as step H, and described base material is selected from carbon fiber paper, carbon cloth, nickel foam, nickel sheet or titanium sheet common substrate materials.
The manufacture method of 13. asymmetric ultracapacitors as claimed in claim 1, is characterized in that:
The preparation of described capacitor negative electrode material is as step H, N
2flow velocity 2 ~ the 20sccm of gas.
The manufacture method of 14. asymmetric ultracapacitors as claimed in claim 1, is characterized in that:
The preparation of described capacitor negative electrode material is as step I, and the activated carbon/carbon paper electrode sprayed puts into vacuum drying chamber, and annealing temperature is 60 ~ 200 DEG C, annealing time 2 ~ 20h.
The preparation method of 15. asymmetric ultracapacitors as claimed in claim 1, is characterized in that:
The preparation of described capacitor negative electrode material is as step J, and the concentration 0.5 ~ 6M of potassium hydroxide, p-phenylenediamine (PPD) is 0.001 ~ 0.5M.
The manufacture method of 16. asymmetric ultracapacitors as claimed in claim 1, is characterized in that:
The assembling of described capacitor is as step K, and positive and negative electrode quality of materials is than being 1:2 ~ 1:6.
The manufacture method of 17. asymmetric ultracapacitors as claimed in claim 16, is characterized in that:
In the number of assembling steps K of described capacitor, using the positive and negative electrode system built as positive and negative electrode, assembling asymmetric electrochemical capacitor, separates with selectivity permeability film between positive and negative electrode system, potassium ion is freely passed through, and other electrolyte ion can not be through.
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| CN105023764A (en) * | 2015-08-14 | 2015-11-04 | 安徽大学 | Composite electrolyte for super capacitor |
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| CN106033695A (en) * | 2015-03-13 | 2016-10-19 | 同济大学 | Asymmetric super-capacitor and preparation method for the same |
| CN106128787A (en) * | 2016-08-25 | 2016-11-16 | 王进 | A kind of super capacitor |
| CN107481865A (en) * | 2017-08-09 | 2017-12-15 | 华南师范大学 | A kind of all-solid-state flexible micro super capacitor based on GQD/ cobalt hydroxide composites |
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| CN109801795A (en) * | 2018-12-27 | 2019-05-24 | 河南师范大学 | A kind of construction method of catalysis electrode-redox electrolyte electric capacity system |
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| CN104576082B (en) * | 2015-01-16 | 2017-08-29 | 吉林大学 | Two pole rooms add the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor and preparation method thereof respectively |
| CN104576082A (en) * | 2015-01-16 | 2015-04-29 | 吉林大学 | Asymmetric supercapacitor with potassium ferricyanide and potassium ferrocyanide added to two electrode chambers respectively and preparation method thereof |
| CN106033695B (en) * | 2015-03-13 | 2018-12-18 | 同济大学 | A kind of Asymmetric Supercapacitor and preparation method thereof |
| CN106033695A (en) * | 2015-03-13 | 2016-10-19 | 同济大学 | Asymmetric super-capacitor and preparation method for the same |
| RU2592863C1 (en) * | 2015-04-16 | 2016-07-27 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела и механохимии Сибирского отделения РАН (ИХТТМ СО РАН) | Supercapacitor with inorganic solid electrolyte and carbon electrodes |
| CN105023764A (en) * | 2015-08-14 | 2015-11-04 | 安徽大学 | Composite electrolyte for super capacitor |
| CN106128787A (en) * | 2016-08-25 | 2016-11-16 | 王进 | A kind of super capacitor |
| CN107481865A (en) * | 2017-08-09 | 2017-12-15 | 华南师范大学 | A kind of all-solid-state flexible micro super capacitor based on GQD/ cobalt hydroxide composites |
| CN107481865B (en) * | 2017-08-09 | 2019-08-16 | 华南师范大学 | A kind of all-solid-state flexible micro super capacitor based on GQD/ cobalt hydroxide composite material |
| CN109473290A (en) * | 2017-09-08 | 2019-03-15 | 中国科学院物理研究所 | A kind of aqueous solution kalium ion battery capacitor and application |
| CN107845506A (en) * | 2017-10-26 | 2018-03-27 | 中国科学院福建物质结构研究所 | A kind of reinforced stone mertenyl ultracapacitor and preparation method thereof |
| CN108807011A (en) * | 2018-06-29 | 2018-11-13 | 北京理工大学 | A kind of ultracapacitor oxidation-reduction type composite electrolyte |
| CN109637821A (en) * | 2018-12-05 | 2019-04-16 | 南通科技职业学院 | A kind of flexible asymmetric super-capacitor and preparation method thereof |
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