CN104576082B - Two pole rooms add the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor and preparation method thereof respectively - Google Patents
Two pole rooms add the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor and preparation method thereof respectively Download PDFInfo
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- CN104576082B CN104576082B CN201510023879.6A CN201510023879A CN104576082B CN 104576082 B CN104576082 B CN 104576082B CN 201510023879 A CN201510023879 A CN 201510023879A CN 104576082 B CN104576082 B CN 104576082B
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Abstract
The potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor and preparation method thereof are added respectively the present invention relates to two pole rooms.The present invention, which is added in cathode chamber in the potassium ferricyanide, anode chamber, adds potassium ferrocyanide, separates positive and negative pole room using amberplex, is assembled into monomer ultracapacitor or many body ultracapacitor groups.There is provided electric capacity simultaneously by solid electrode and liquid electrolyte realizes the combination of ultracapacitor and flow battery.The positive pole of the capacitor realizes cobalt hydroxide and is superimposed with the fake capacitance of the potassium ferricyanide；Negative pole realizes active charcoal electric double layer capacitance and is superimposed with the fake capacitance of potassium ferrocyanide.Therefore, ultracapacitor of the invention has very high energy density.This patent selects K in anode chamber4Fe(CN)6As reducing agent, self discharge is reduced, the stability of condenser capacitance performance is improved.
Description
Technical field：
In terms of technical field of chemical power, especially Asymmetric Supercapacitor, and in particular to one kind two
The potassium ferricyanide (K is added in the electrolyte of pole respectively3Fe(CN)6) and potassium ferrocyanide (K4Fe(CN)6) Asymmetric Supercapacitor
And preparation method thereof.
Background technology：
Excessive use of traditional energy material causes serious problem of environmental pollution, sustainable development of clean energy and profit
With imperative, energy and environment have become the significant problem of 21 century facing mankind.Ultracapacitor has power density
The advantages of height, environmental protection, service life length, good temp characteristic, use it for startup power supply, it is ensured that high-power military dress
The smooth startup put, can also be as vehicle traction energy, for electric automobile, trolley coach etc..By ultracapacitor
For that in electronic device, can be used as the power supply of long-time stable.With regenerative resources such as wind energy, solar energy energetically
Development, it is huge and novel energy of less pollution effective using seeming more important for these reserves.Ultracapacitor
Storage and conversion equipment as these energy, are electric energy by solar energy, wind energy transformation, produced electric energy are stored,
These energy are discharged when needing, the stability of renewable energy system and transmission system is improved, plays Effective Regulation
Effect.
For battery, there is the low defect of energy density in ultracapacitor, how to improve the energy of ultracapacitor
Metric density turns into the key that ultracapacitor develops.Water system Asymmetric Supercapacitor have environmental protection, power density it is high, into
The advantages of this is low, easy to operate, by the extensive concern of researcher.More than positive pole using metal oxide, metal hydroxides or
Conducting polymer is as electrode active material, and negative pole is using activated carbon etc. as electrode active material, and this unsymmetric structure can
To expand the operating potential window of ultracapacitor, the energy density of ultracapacitor is improved.Research is found, in this super electricity
Redox materials are added in container electrolyte, can be by the regulation and control of volume and concentration so that electrode is with electrolyte to electric capacity
Different contributions are produced, thus the energy density of ultracapacitor can be increased substantially.
The Application No. 2014106901745 that applicant has applied, entitled " the two poles of the earth electrolyte adds the potassium ferricyanide respectively
With the Asymmetric Supercapacitor of p-phenylenediamine and preparation method thereof " patent, in cobalt hydroxide (Co (OH)2)-activated carbon (AC)
In Asymmetric Supercapacitor, cathode chamber adds K3Fe(CN)6, with Co (OH)2Coexist, stability and compatibility are all fine.Due to
K3Fe(CN)6High activity and good redox reversible as catholyte be a selection well.But anode chamber is also
The selection of former agent has a very big difficulty, and cathodic reduction material selection is organic matter p-phenylenediamine to applicant in the above application,
Its advantage is that oxidation-reduction potential is relatively born, with K3Fe(CN)6Oxidation-reduction potential have larger gap, to discharge it is favourable.But
For amberplex, it is difficult to avoid the transmission of neutral organic molecule p-phenylenediamine, its self discharge increase, and organic molecule
Solubility in aqueous is relatively low, is unfavorable for the capacitive property of capacitor.
K4Fe(CN)6As reducing agent, it is difficult to pass through amberplex, makes the electrolyte of the Room of capacitor two be difficult mutually to mix, because
And self discharge is reduced, improve the stability of condenser capacitance performance.And K4Fe(CN)6Solubility is higher in water, favorably
In lifting of the electrolyte to capacitance contribution.Because K3Fe(CN)6And K4Fe(CN)6Precisely a pair of oxidation-reduction pairs, each other instead
Thing and product are answered, simplifies the processing of electrolyte.
The content of the invention：
The technical problems to be solved by the invention add the potassium ferricyanide and ferrous cyanogen respectively to provide a kind of the two poles of the earth electrolyte
Change Asymmetric Supercapacitor of potassium and preparation method thereof, to provide the energy density of capacitor.
In order to solve the above technical problems, the technical scheme that the present invention is provided is as follows：
A kind of the two poles of the earth electrolyte adds the Asymmetric Supercapacitor of the potassium ferricyanide and potassium ferrocyanide respectively, including just
Pole, negative pole, amberplex and electrolyte, the amberplex are located between both positive and negative polarity, by the cathode chamber of capacitor and
Anode chamber is separated；
The electrolyte is alkaline aqueous solution, and added with potassium ferricyanide solution, iron cyaniding in the electrolyte of cathode chamber
Potassium solution concentration is 0.01~0.5mol/L；Potassium ferrocyanide solution is added with the electrolyte of anode chamber, potassium ferrocyanide is molten
Liquid concentration is 0.01~0.5mol/L.
A kind of the two poles of the earth electrolyte adds the preparation side of the Asymmetric Supercapacitor of the potassium ferricyanide and potassium ferrocyanide respectively
Method, is comprised the following steps that：
Step 1：Carbon material is ultrasonically treated by organic solvent, remove organic impurities；By carbon material through persalt or sulphur
Sour acidification, removes inorganic impurity and improves carbon material specific surface area, using constant potential or constant current electrochemical deposition, is passing through
Cobalt hydroxide film is grown on the carbon material of processing, cobalt hydroxide electrode is obtained, used as supercapacitor positive electrode；
Step 2：Using nickel foam or carbon material as substrate, handle, remove by organic solvent, inorganic acid and deionized water
Organic matter and oxide-film, activated carbon is mixed with conductive agent, binding agent, is scratched or is sprayed in treated substrate,
Activated carbon electrodes are obtained, are used as super capacitor anode；
Step 3：Amberplex is passed through into hydrogen peroxide and mineral acid treatment, surface organic matter, inorganic metal ion is removed
Impurity, is put into used alkaline solution after being washed with deionized water only and soaks stand-by；
Step 4：By supercapacitor positive electrode, negative pole, amberplex, seal gasket and end plate, by bolt combination into
Ultracapacitor monomer, or multiple positive poles, negative pole, amberplex, seal gasket and end plate are assembled into the super of multiple electrodes
Level capacitor bank；Using injector for medical purpose or vacuum pump mode, electrolyte is injected separately into cathode chamber, negative pole along reserving hole channel
Room, is sealed after fixing；
Step 5：Connected as needed using the ultracapacitor monomer, ultracapacitor group that assemble in step 4 or
Parallel connection, so as to reach required electric current and voltage；
Step 6：Using three-electrode system or two electrode systems to single electrode, single ultracapacitor or ultracapacitor group
And multigroup ultracapacitor carries out electrochemical measurement, measuring method is cyclic voltammetry, constant current charge-discharge method or exchange resistance
Anti- method.
Further, in step 1, carbon material substrate includes carbon cloth, carbon fiber felt, carbon fiber paper or graphite, right
Above-mentioned carbon material surface is handled, and obtains cleaning carbon material substrate；Specifically, in organic solvent soak 1~5 hour, so
Ultrasonic 5~60 minutes afterwards, the organic solvent is acetone or alcohol；In mineral acid soak 1~5 hour, then ultrasound 5~60
Minute, the inorganic acid is hydrochloric acid or sulfuric acid；Finally, soak in deionized water 1~5 hour, it is then ultrasonic 5~60 minutes,
Remove inorganic acid.
Further, in step 1, using electrochemical deposition technique, carbon material/cobalt hydroxide electrode is obtained, as super
Level capacitor anode is used；In electrochemical deposition process, sedimentation time is 10min~2h, and electrolyte nitric acid cobalt concentration is 0.1
~2mol/L, depositing temperature is 30~60 DEG C, sedimentation potential selection -0.6V~-1.3V, and deposited per area unit size of current is
0.01A~2A/cm2, unit area active material cobalt hydroxide quality is 0.5~15mg/cm2。
Further, in step 2, nickel foam or carbon material surface are handled, the nickel foam or carbon cleaned
Material substrate；Nickel foam or carbon material soak 1~5 hour in organic solvent respectively, then ultrasonic 5~60 minutes, You Jirong
Agent includes acetone or alcohol；In mineral acid soak 1~5 hour, then ultrasound 5~60 minutes, inorganic acid be mainly hydrochloric acid or
Sulfuric acid；Finally, soak in deionized water 1~5 hour, then ultrasound 5~60 minutes, remove inorganic acid.
Further, in step 2, using blade coating or spraying method, nickel foam or carbon material/activated carbon electrodes are obtained,
Used as super capacitor anode, activated carbon is with conductive agent, binding agent according to 80~90:5~15:3~7 ratio mixing,
The quality that the mixture on nickel foam or carbon material is scratched or be sprayed in unit area is 1~50mg/cm2。
Further, in step 3, diaphragm of supercapacitor amberplex is handled, specifically, dioxygen water body
Fraction is 2~10%, and treatment temperature is 60~80 DEG C, and processing time is 0.5~3 hour, removes organic impurities；It is inorganic
Acid includes watery hydrochloric acid or dilute sulfuric acid, and treatment temperature is 60~80 DEG C, and processing time is 0.5~3 hour, removes inorganic matter miscellaneous
Matter.
Further, in step 4, capacitor is assembled and sealed using end plate, bolt and rubber cushion；Super capacitor
Device shell is square, rectangle or circle, and electrolyte volume changes according to the change of shell sizes and number of electrodes, and monomer surpasses
Level capacitor electrolyte volume is 5ml~2000ml.
Further, in step 4, electrolyte is alkaline aqueous solution, containing potassium hydroxide, sodium hydroxide or lithium hydroxide
Alkali solute, concentration is 0.5~6mol/L；In cathode chamber add the oxidizing substance potassium ferricyanide, its concentration be 0.01~
0.5mol/L；Reducing substances potassium ferrocyanide is added in anode chamber, its concentration is 0.01~0.5mol/L.
Further, in steps of 5, ultracapacitor includes different size electrode area ultracapacitor and multiple or many
Group ultracapacitor assembling；Electrode area is 1cm2~2500cm2；Ultracapacitor group is composed in parallel by multiple ultracapacitors,
Its quantity is 2~100 or more, and the built-up circuit by way of serial or parallel connection obtains required electric current and voltage.
Further, in step 6, cyclic voltammetry is carried out to electrode, ultracapacitor using different scanning speed,
Sweep speed scope is 0.1~100mV/s.Charge-discharge test, electricity are carried out to electrode, ultracapacitor using different current densities
Current density scope is 0.5A/g~100A/g or 0.1mA/cm2~100mA/cm2。
Beneficial effects of the present invention are：
1st, this patent selects K in anode chamber4Fe(CN)6As reducing agent, its solubility in water is higher, is conducive to bearing
Lifting of the pole electrolyte to capacitance contribution.And be difficult to pass through amberplex, make the electrolyte of the Room of capacitor two be difficult mutually to mix, because
And self discharge is reduced, improve the stability of condenser capacitance performance.Fe(CN)6 3-With Fe (CN)6 4-It is a pair of redox
Electricity is right, each other the reactant and product of two pole rooms, and electrolyte processing is simpler.
2nd, the pure cerium hydroxide cobalt thin film electrode prepared in the present invention using electro-deposition method, with high specific capacitance and excellent
Cyclical stability, key element is provided for high-energy ultracapacitor.
3rd, matched in the present invention using pure cerium hydroxide cobalt electrode with activated carbon electrodes, two electrode capacitances are functional, circulation
Stability is high.This capacitor can not only work long-term and stably, and have wider electrochemical operation window, with higher
Energy density.
4th, the present invention in high reversible redox electrolyte is introduced into electrolytic solution for super capacitor, make electrolyte with
Electrode material simultaneously, non-interfering offer electric capacity, increase substantially super capacitor energy density.Such an approach achieves
The combination of electrode and electrolyte solution in ultracapacitor, improves notable to the capacitive property of ultracapacitor.
5th, in the present invention in this new ultracapacitor, using amberplex as barrier film, the effect of barrier film
It is not to separate both positive and negative polarity merely so that both positive and negative polarity is electrically insulated, and the electrolyte of positive and negative pole room is different, the oxygen that cathode chamber contains
The reducing substances that the property changed material and anode chamber contain will not be mixed, it is ensured that the electric charge of two materials storage will not be damaged because of self discharge
Consumption.
6th, catholyte adds oxidizing substance in the present invention, and anolyte adds reducing substances so that filling
In discharge process, the common electric capacity to capacitor of electrode and electrolyte is contributed, and realizes ultracapacitor and flow battery
With reference to.Because ultracapacitor has higher power density, and flow battery has larger energy density, therefore this dress
Put with ultracapacitor and the respective advantage of flow battery, the ultracapacitor with higher energy density can more meet mesh
Preceding needs of production.
Brief description of the drawings：
The structural representation of Fig. 1 capacitors of the present invention；
Fig. 2 electrode areas are 1cm20.2mol/L K are added in the electrolyte of the two poles of the earth respectively3Fe(CN)6With 0.2mol/L K4Fe
(CN)6Asymmetric Supercapacitor sweep speed be 25mV/s when cyclic voltammetry curve；
Fig. 3 electrode areas are 1cm20.2mol/L K are added in the electrolyte of the two poles of the earth respectively3Fe(CN)6With 0.2mol/L K4Fe
(CN)6Asymmetric Supercapacitor current density be 5mA/cm2When charging and discharging curve；
Fig. 4 electrode areas are 100cm20.1mol/L K are added in the electrolyte of the two poles of the earth respectively3Fe(CN)6And 0.1mol/L
K4Fe(CN)6Asymmetric Supercapacitor difference sweep speed cyclic voltammetry curve；
Fig. 5 electrode areas are 100cm20.1mol/L K are added in the electrolyte of the two poles of the earth respectively3Fe(CN)6And 0.1mol/L
K4Fe(CN)6The different current density of Asymmetric Supercapacitor under charging and discharging curve.
Fig. 6 electrode areas are 100cm2The K of various concentrations is added in the electrolyte of the two poles of the earth respectively3Fe(CN)6And K4Fe(CN)6's
The comparison diagram of Asymmetric Supercapacitor charging and discharging curve.
Embodiment：
With reference to Figure of description, the embodiment to the present invention is further described in detail：
As shown in figure 1, a kind of the two poles of the earth electrolyte adds the asymmetric super capacitor of the potassium ferricyanide and potassium ferrocyanide respectively
Device, including positive pole, negative pole, amberplex and electrolyte, the amberplex are located between both positive and negative polarity, by capacitor
Cathode chamber and anode chamber are separated；
The electrolyte is alkaline aqueous solution, and added with potassium ferricyanide solution, iron cyaniding in the electrolyte of cathode chamber
Potassium solution concentration is 0.01~0.5mol/L；Potassium ferrocyanide solution is added with the electrolyte of anode chamber, potassium ferrocyanide is molten
Liquid concentration is 0.01~0.5mol/L.
A kind of the two poles of the earth electrolyte adds the preparation side of the Asymmetric Supercapacitor of the potassium ferricyanide and potassium ferrocyanide respectively
Method, specific embodiment is as follows：
Embodiment 1：
(1) using area 1cm2Carbon paper is substrate, ultrasound 30 after being soaked 2 hours in acetone, ethanol, deionized water respectively
Minute.Using constant potential electrodeposition process, carbon paper/cobalt hydroxide electrode is prepared.In electrochemical deposition process, nitric acid cobalt concentration is
1.2mol/L, sedimentation time is 1h, and sedimentation potential is -0.9V, and temperature is 45 DEG C.
(2) using area 1cm2Nickel foam is substrate, ultrasound after being soaked 2 hours in acetone, ethanol, deionized water respectively
30 minutes.Nickel foam/activated carbon electrodes are prepared using knife coating.By activated carbon, electrically conductive graphite and Nafion solution according to quality
Than for 85:10:5 ratio is well mixed, and is scratched in nickel foam.
(3) diaphragm of supercapacitor amberplex is handled, specifically, dioxygen water volume fraction is 5%, processing
Temperature is 80 DEG C, and processing time is 1 hour, removes organic impurities；Handled using dilute sulfuric acid, treatment temperature is 80 DEG C, processing
Time is 1 hour, removes inorganic contaminants.It regard carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes conduct
Negative pole, using amberplex as barrier film, assembles electrode Asymmetric Supercapacitor.
(4) 50ml 1mol/L KOH and 0.2mol/L K are prepared3Fe(CN)6Mixed solution be used as catholyte, note
Enter cathode chamber；Prepare 50ml 1mol/L KOH and 0.2mol/LK4Fe(CN)6Mixed solution as anolyte, be assembled into
Electrode area is 1cm2Electrode is asymmetric, the asymmetrical Novel asymmetric ultracapacitor of electrolyte.
(5) cyclic voltammetric (as shown in Figure 2) and charge-discharge test are carried out to above-mentioned Novel asymmetric ultracapacitor (as schemed
Shown in 3), when current density is 5mA/cm2When, the specific capacitance and energy density of the Novel super capacitor are respectively 256.1F/g
And 80Wh/kg.
Embodiment 2：
(1) using area 100cm2Carbon paper is substrate, ultrasound after being soaked 2 hours in acetone, ethanol, deionized water respectively
30 minutes.Using constant potential electrodeposition process, carbon paper/cobalt hydroxide electrode is prepared.In electrochemical deposition process, nitric acid cobalt concentration
For 1.2mol/L, sedimentation time is 1h, and sedimentation potential is -0.9V, and temperature is 45 DEG C.
(2) using area 100cm2Nickel foam is substrate, is surpassed after being soaked 2 hours in acetone, ethanol, deionized water respectively
Sound 30 minutes.Nickel foam/activated carbon electrodes are prepared using knife coating.By activated carbon, electrically conductive graphite and Nafion solution according to matter
Amount is than being 85:10:5 ratio is well mixed, and is scratched in nickel foam.
(3) diaphragm of supercapacitor amberplex is handled, specifically, dioxygen water volume fraction is 5%, processing
Temperature is 80 DEG C, and processing time is 1 hour, removes organic impurities；Handled using dilute sulfuric acid, treatment temperature is 80 DEG C, processing
Time is 1 hour, removes inorganic contaminants.
(4) above-mentioned electrode is tested with charging/discharging thereof using cyclic voltammetric.When charging and discharging currents density is 1mA/
cm2When, the specific capacitance of carbon paper/cobalt hydroxide electrode is 513F/g, and the specific capacitance of nickel foam/activated carbon electrodes is 211F/g.
(5) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes are as negative pole, with modified polypropene
Film is barrier film, is assembled into Asymmetric Supercapacitor, adds 1mol/L KOH solutions and is used as electrolyte.When current density is 1mA/
cm2When, the specific capacitance and energy density of the Asymmetric Supercapacitor are respectively 77.2F/g and 27.4Wh/kg.(such as Fig. 6 (a)
It is shown) embodiment 3：
(1) it is identical with embodiment 2 (1).
(2) it is identical with embodiment 2 (2).
(3) it is identical with embodiment 2 (3).
(4) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes are as negative pole, with amberplex
For barrier film, positive pole injection 50ml 1mol/L KOH and 0.05mol/L K3Fe(CN)6Mixed solution, negative pole injection 50ml
1mol/L KOH and 0.05mol/L K4Fe(CN)6Mixed solution, be assembled into two pole rooms be separately added into Oxidizing and Reducing Agents,
Electrode area is 100cm2New cobalt hydroxide-activated carbon asymmetric capacitor.Above-mentioned Novel asymmetric capacitor is carried out
Charge-discharge test, maximum potential window 1.6V, current density is 1mA/cm2, the specific capacitance and energy density of the novel capacitor
Respectively 90.2F/g and 32.1Wh/kg.(shown in such as Fig. 6 (b))
Embodiment 4：
(1) it is identical with embodiment 2 (1).
(2) it is identical with embodiment 2 (2).
(3) it is identical with embodiment 2 (3).
(4) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes are as negative pole, with amberplex
For barrier film, positive pole injection 50ml 1mol/L KOH and 0.08mol/L K3Fe(CN)6Mixed solution, negative pole injection 50ml
1mol/L KOH and 0.08mol/L K4Fe(CN)6Mixed solution, be assembled into two pole rooms be separately added into Oxidizing and Reducing Agents,
Electrode area is 100cm2New cobalt hydroxide-activated carbon asymmetric capacitor.Above-mentioned Novel asymmetric capacitor is carried out
Charge-discharge test, maximum potential window 1.6V, current density is 1mA/cm2, the specific capacitance and energy density of the novel capacitor
Respectively 99.4F/g and 35.3Wh/kg.(shown in Fig. 6 (c))
Embodiment 5：
(1) it is identical with embodiment 2 (1).
(2) it is identical with embodiment 2 (2).
(3) it is identical with embodiment 2 (3).
(4) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes are as negative pole, with amberplex
For barrier film, positive pole injection 50ml 1mol/L KOH and 0.1mol/L K3Fe(CN)6Mixed solution, negative pole injection 50ml
1mol/L KOH and 0.1mol/L K4Fe(CN)6Mixed solution, be assembled into two pole rooms be separately added into Oxidizing and Reducing Agents,
Electrode area is 100cm2New cobalt hydroxide-activated carbon asymmetric capacitor.
Above-mentioned Asymmetric Supercapacitor difference sweeps the cyclic voltammetry curve of speed, as shown in Figure 4；
Charging and discharging curve under the different current densities of above-mentioned Asymmetric Supercapacitor, as shown in Figure 5；From charging and discharging curve
In as can be seen that the Asymmetric Supercapacitor is when containing redox materials, its multiplying power property needs further improve.
To above-mentioned Novel asymmetric capacitor progress charge-discharge test, maximum potential window 1.6V, current density is 1mA/
cm2, the specific capacitance and energy density of the novel capacitor are respectively 107F/g and 38Wh/kg.(shown in Fig. 6 (d))
Embodiment 6：
(1) it is identical with embodiment 2 (1).
(2) it is identical with embodiment 2 (2).
(3) it is identical with embodiment 2 (3).
(4) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes are as negative pole, with amberplex
For barrier film, positive pole injection 50ml 1mol/L KOH and 0.4mol/L K3Fe(CN)6Mixed solution, negative pole injection 50ml
1mol/L KOH and 0.4mol/L K4Fe(CN)6Mixed solution, be assembled into two pole rooms be separately added into Oxidizing and Reducing Agents,
Electrode area is 100cm2New cobalt hydroxide-activated carbon asymmetric capacitor.Above-mentioned Novel asymmetric capacitor is carried out
Charge-discharge test, maximum potential window 1.6V, current density is 1mA/cm2, the specific capacitance and energy density of the novel capacitor
Respectively 320F/g and 113.8Wh/kg.(and shown in Fig. 6 (e)).
To sum up, influence of the redox materials concentration of ultracapacitor to capacitive property is summarized as follows in embodiment 1-6：
Table 1
Embodiment 1 and 2 from table, it can be seen that add K respectively in capacitor both positive and negative polarity3Fe(CN)6And K4Fe
(CN)6Difference with not dosing any redox materials, capacitor specific capacitance and energy density, added with K3Fe(CN)6And K4Fe
(CN)6Ultracapacitor specific capacitance and energy density it is significantly raised.
The embodiment 3 to 6 from table, it can be seen that the specific capacitance and energy density and K of ultracapacitor3Fe(CN)6With
K4Fe(CN)6The variation relation of concentration, with K3Fe(CN)6And K4Fe(CN)6The increase of concentration, the discharge and recharge time increases, and surpasses
Level capacitor specific capacitance and energy density are significantly raised (as shown in Figure 6).
Claims (10)
1. a kind of two pole room adds the preparation method of the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, its feature
It is：
Step 1：Carbon material is ultrasonically treated by organic solvent, remove organic impurities；By carbon material through persalt or sulfuric acid acid
Change is handled, and removes inorganic impurity, carbon material specific surface area is improved, using constant potential or constant current electrochemical deposition, at process
Cobalt hydroxide film is grown on the carbon material of reason, cobalt hydroxide electrode is obtained, used as supercapacitor positive electrode；
Step 2：Using nickel foam or carbon material as substrate, handle, remove organic by organic solvent, inorganic acid and deionized water
Thing and oxide-film, activated carbon is mixed with conductive agent, binding agent, is scratched or is sprayed in treated substrate, obtains
Activated carbon electrodes, are used as super capacitor anode；
Step 3：Amberplex is passed through into hydrogen peroxide and mineral acid treatment, surface organic matter, inorganic metal ion impurity is removed,
Soak stand-by in alkaline solution used in being put into after being washed with deionized water only；
Step 4：By supercapacitor positive electrode, negative pole, amberplex, seal gasket and end plate, by bolt combination into super
Capacitor monomer, or multiple positive poles, negative pole, amberplex, seal gasket and end plate are assembled into the super electricity of multiple electrodes
Container group；Using injector for medical purpose or vacuum pump mode, electrolyte is injected separately into cathode chamber, anode chamber along reserving hole channel,
Sealed after fixation；
Step 5：Serial or parallel connection is carried out using the ultracapacitor monomer, ultracapacitor group that are assembled in step 4 as needed,
So as to reach required electric current and voltage；
Step 6：Using three-electrode system or two electrode systems to single electrode, single ultracapacitor or ultracapacitor group and
Multigroup ultracapacitor carries out electrochemical measurement, and measuring method is cyclic voltammetry, constant current charge-discharge method or AC impedence method.
2. a kind of two pole room as claimed in claim 1 adds the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively
Preparation method, it is characterised in that：In step 1, carbon material substrate includes carbon cloth, carbon fiber felt, carbon fiber paper or stone
Ink, is handled above-mentioned carbon material surface, obtains cleaning carbon material substrate；Specifically, immersion 1~5 is small in organic solvent
When, then ultrasonic 5~60 minutes, the organic solvent is acetone or alcohol；Soak in mineral acid 1~5 hour, it is then ultrasonic
5~60 minutes, the inorganic acid was hydrochloric acid or sulfuric acid；Finally, in deionized water soak 1~5 hour, then ultrasound 5~60
Minute, remove inorganic acid.
3. a kind of two pole room as claimed in claim 1 adds the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively
Preparation method, it is characterised in that：In step 1, using electrochemical deposition technique, carbon material/cobalt hydroxide electrode is obtained, is made
Used for supercapacitor positive electrode；In electrochemical deposition process, sedimentation time is 10min~2h, electrolyte nitric acid cobalt concentration
For 0.1~2mol/L, depositing temperature is 30~60 DEG C, and sedimentation potential selection -0.6V~-1.3V, deposited per area unit electric current is big
Small is 0.01A~2A/cm2, unit area active material cobalt hydroxide quality is 0.5~15mg/cm2。
4. a kind of two pole room as claimed in claim 1 adds the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively
Preparation method, it is characterised in that：In step 2, nickel foam or carbon material surface are handled, obtains cleaning foam nickel or carbon materials
Expect substrate；Nickel foam or carbon material soak 1~5 hour in organic solvent respectively, then ultrasonic 5~60 minutes, organic solvent
Including acetone or alcohol；Soak in mineral acid 1~5 hour, then ultrasonic 5~60 minutes, inorganic acid is mainly hydrochloric acid or sulphur
Acid；Finally, soak in deionized water 1~5 hour, then ultrasound 5~60 minutes, remove inorganic acid.
5. a kind of two pole room as claimed in claim 1 adds the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively
Preparation method, it is characterised in that：In step 2, using blade coating or spraying method, nickel foam or carbon material/activated carbon are obtained
Electrode, is used as super capacitor anode, and activated carbon is with conductive agent, binding agent according to 80~90:5~15:3~7 ratio
The quality for scratching or being sprayed at the mixture on nickel foam or carbon material in mixing, unit area is 1~50mg/cm2。
6. a kind of two pole room as claimed in claim 1 adds the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively
Preparation method, it is characterised in that：In step 3, diaphragm of supercapacitor amberplex is handled, specifically, double
Oxygen water volume fraction is 2~10%, and treatment temperature is 60~80 DEG C, and processing time is 0.5~3 hour, removes organic matter miscellaneous
Matter；Inorganic acid includes watery hydrochloric acid or dilute sulfuric acid, and treatment temperature is 60~80 DEG C, and processing time is 0.5~3 hour, removes nothing
Machine thing impurity.
7. a kind of two pole room as claimed in claim 1 adds the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively
Preparation method, it is characterised in that：In step 4, capacitor is assembled and sealed using end plate, bolt and rubber cushion；It is super
Level capacitor case is square, rectangle or circle, and electrolyte volume changes according to the change of shell sizes and number of electrodes,
Monomer electrolytic solution for super capacitor volume is 5ml~2000ml.
8. a kind of two pole room as claimed in claim 1 adds the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively
Preparation method, its preparation method is characterised by that in step 4, electrolyte is alkaline aqueous solution, containing potassium hydroxide, hydroxide
The alkali solute of sodium or lithium hydroxide, concentration is 0.5~6mol/L；The oxidizing substance potassium ferricyanide is added in cathode chamber, its is dense
Spend for 0.01~0.5mol/L；Reducing substances potassium ferrocyanide is added in anode chamber, its concentration is 0.01~0.5mol/L.
9. a kind of two pole room as claimed in claim 1 adds the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively
Preparation method, it is characterised in that：In steps of 5, ultracapacitor includes different size electrode area ultracapacitor and many
Individual or multigroup ultracapacitor assembling；Electrode area is 1cm2~2500cm2；Ultracapacitor group by multiple ultracapacitors simultaneously
Joint group into, its quantity be 2~100 or more, the built-up circuit by way of serial or parallel connection, obtain required electric current and
Voltage.
10. a kind of two pole room as claimed in claim 1 adds the potassium ferricyanide and the asymmetric super capacitor of potassium ferrocyanide respectively
Ultracapacitor prepared by the preparation method of device, including positive pole, negative pole, amberplex and electrolyte, it is characterised in that：
The amberplex is located between both positive and negative polarity, and the cathode chamber and anode chamber of capacitor are separated；
The electrolyte is alkaline aqueous solution, and added with potassium ferricyanide solution in the electrolyte of cathode chamber, the potassium ferricyanide is molten
Liquid concentration is 0.01~0.5mol/L；Potassium ferrocyanide solution is added with the electrolyte of anode chamber, potassium ferrocyanide solution is dense
Spend for 0.01~0.5mol/L.
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| CN106601497A (en) * | 2016-09-05 | 2017-04-26 | 吉林大学 | Preparation method of two-pole chamber cobalt hydroxide symmetric type super capacitor comprising potassium ferricyanide and p-phenylenediamine |
| CN106449137A (en) * | 2016-09-06 | 2017-02-22 | 吉林大学 | Preparation method for asymmetric super capacitor with cobalt hydroxide and active carbon as anode and cathode respectively |
| CN106206059B (en) * | 2016-09-22 | 2018-07-20 | 福州大学 | NiCo2S4The preparation method and application of/graphite felt combination electrode material |
| CN106356203B (en) * | 2016-10-31 | 2019-02-22 | 福州大学 | A kind of cobalt acid nickel nano film/graphite felt composite material and its preparation and application |
| CN106486296B (en) * | 2016-11-22 | 2018-12-25 | 福州大学 | A kind of preparation method of nitrogen/nickel cobalt codope graphite felt electrode material |
| CN106898499B (en) * | 2017-02-23 | 2019-08-13 | 武汉科技大学 | A kind of dual chamber pseudocapacitors and preparation method thereof adding fuel |
| CN108807011A (en) * | 2018-06-29 | 2018-11-13 | 北京理工大学 | A kind of ultracapacitor oxidation-reduction type composite electrolyte |
| CN113113676B (en) * | 2021-03-29 | 2022-11-29 | 南京理工大学 | Method for expanding voltage of water system energy storage device by introducing competitive type oxidation-reduction reaction |
| CN113415811B (en) * | 2021-05-20 | 2022-03-25 | 哈尔滨工业大学 | Preparation method of ferrocyanide and application of ferrocyanide in flow battery |
| CN113675002A (en) * | 2021-08-19 | 2021-11-19 | 成都理工大学 | Supercapacitor based on cobalt-based material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102176380A (en) * | 2011-01-26 | 2011-09-07 | 中国海洋大学 | Oxidation-reduction reaction electrochemical capacitor |
| CN104269281A (en) * | 2014-09-24 | 2015-01-07 | 吉林大学 | Method for manufacturing asymmetric super capacitor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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-
2015
- 2015-01-16 CN CN201510023879.6A patent/CN104576082B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102176380A (en) * | 2011-01-26 | 2011-09-07 | 中国海洋大学 | Oxidation-reduction reaction electrochemical capacitor |
| CN104269281A (en) * | 2014-09-24 | 2015-01-07 | 吉林大学 | Method for manufacturing asymmetric super capacitor |
Non-Patent Citations (2)
| Title |
|---|
| Capacitive Properties of Activated Carbon in K4Fe(CN)6;Ying Tian等;《Journal of the Electrochemical Society》;20110511;第158卷(第7期);第A818-A821页 * |
| Improvement of the capacitive performances for Co–Al layered double hydroxide by adding hexacyanoferrate into the electrolyte;Ling-Hao Su等;《Physical Chemistry Chemical Physics》;20090210;第11卷(第13期);第2195-2202页 * |
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