CN106098395A - A kind of manganese dioxide fiber electrode and its preparation method and application - Google Patents
A kind of manganese dioxide fiber electrode and its preparation method and application Download PDFInfo
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- CN106098395A CN106098395A CN201610386971.3A CN201610386971A CN106098395A CN 106098395 A CN106098395 A CN 106098395A CN 201610386971 A CN201610386971 A CN 201610386971A CN 106098395 A CN106098395 A CN 106098395A
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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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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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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- 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 discloses a kind of manganese dioxide fiber electrode, this manganese dioxide fiber electrode includes collector and the manganese dioxide fiber-reactive layer being attached on collector；Described manganese dioxide fiber is big length fiber；Without binding agent in described manganese dioxide fiber electrode.The preparation method of described manganese dioxide fiber electrode includes: the most directly by the manganese dioxide sedimentary of the weak crystalline state of electrochemical deposition, or prepares unformed porous manganese dioxide layer by carrying out anodic oxidation again after negative electrode electrodeposit metals manganese on a current collector；Manganese dioxide layer is carried out hydrothermal treatment consists, makes the manganese dioxide layer of collection liquid surface carry out recrystallization oriented growth, obtain manganese dioxide fiber electrode of the present invention.Manganese dioxide fiber electrode of the present invention can be used for preparing electric chemical super capacitor, and has that integral energy density is big, environmental effect is little, technique is easily controlled, save the advantages such as the energy.
Description
Technical field
The present invention relates to technical field of electrochemistry, be more particularly to a kind of manganese dioxide fiber electrode and preparation method thereof and
Application.
Background technology
Electric chemical super capacitor (electrochemical supercapacitors, ES), also known as electrochemical capacitor
Device (electrochemical capacittors, EC), or abbreviation ultracapacitor (supercapacitorsor,
Ultracapacitors), it is the novel energy-storing device the most widely paid close attention to.Because such capacitor is mainly by electrode and solution
Electrochemical process on interface carries out energy storage, and its capacity is 20～200 times of traditional capacitor, up to farad level even thousand method
Draw level；Its power density is then higher decades of times than battery, it is possible to meet the needs of the high-power outputs such as electric automobile Acceleration of starting.Electricity
Chemistry ultracapacitor has conventional capacitor power density is big and rechargeable battery energy density is high advantage concurrently it is considered to be one
Efficiently, practical novel energy-storing element.
Although ultracapacitor has an advantage that high-power output performance is good and has extended cycle life, but its energy compared with battery
Metric density is low the most on the low side.In order to improve the performance of ultracapacitor, i.e. while improving specific energy, keep its big specific power rate
Etc. advantage, the research around the transition metal oxide electrode with electric double layer capacitance and Faraday pseudo-capacitance behavior enjoys pass
Note.Although RuO2 can not only realize high-power discharge and recharge, specific energy is the highest simultaneously, but because by resource limit, being somebody's turn to do
The key issue that material is faced is that material cost is high, is therefore difficult to obtain business promotion.In order to seek cheap super capacitor
Device electrode material, around preparation and the Electrochemical Properties of the transition metal oxide materials such as NiO, Co3O4, V2O5, MnO2
In succession launch.In many transition metal oxides, MnO2 extremely closes than electric capacity because having aboundresources and higher theory
Note, but the actual material prepared is higher than electric capacity, it is often more important that its as the electrode material of high power device at big times
Capability retention during rate discharge and recharge is the most to be improved.
The method generally preparing ultracapacitor manganese dioxide electrode is first to prepare MnO2 powder body material, then by it with viscous
Knot agent etc. is coated on collector after being configured to slurry and forms final electrode, and this is easy for causing electrode active material and collector
Between loose contact and affect the charge-discharge performance of electrode.Additionally, due to the binding agents added etc. are electrically inactive material, its
Necessarily reduce the energy density of whole electrode.A lot of documents are mentioned directly by anodic oxidation manganese sulfate solution or cathodic reduction
High manganese ion deposits manganese dioxide at collection liquid surface, the manganese dioxide electrode of available binder free, but because of electro-deposition
The manganese dioxide sedimentary gone out is the most dense, and electrode is little with the contact area of electrolyte, and material crystalline is the most bad, self
Ionic conductivity difference and be unfavorable for charged ion at the mass transfer within material crystals, the electrode active material therefore prepared is greatly
Under electric current, ratio electric capacity and the high rate performance of discharge and recharge are the most undesirable.In order to increase in capacitor work process electrode active material with
The contact area of electrolyte, the study hotspot in this field is first to grow various metal, CNT in metal collector at present
Array or Graphene, then at these metals, CNT or graphenic surface electro-deposition manganese dioxide and be used as ultracapacitor
Electrode, but do not change pattern and the crystallinity of deposited manganese dioxide self because these methods only change the pattern of collector,
When the thickness of manganese dioxide sedimentary is thicker, still can not get the electrode of high specific capacitance and capability retention.This external gold
The technical process growing CNT or Graphene on metal surface is more complicated, and cost is high, is difficulty with industrial applications.
Summary of the invention
(1) to solve the technical problem that
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art exactly, it is provided that a kind of integral energy density is big,
The simple manganese dioxide electrode of good rate capability, preparation technology, correspondingly provides the preparation method of this manganese dioxide electrode and answers
With
(2) technical scheme
In order to solve above-mentioned technical problem, the invention provides a kind of manganese dioxide fiber electrode, this manganese dioxide fiber
Electrode includes collector and the manganese dioxide fiber-reactive layer being attached on collector；Described manganese dioxide fiber is for greatly enhancing/footpath
Compare fiber；Without binding agent in described manganese dioxide fiber electrode.
Preferably, a diameter of the 5～50nm of described manganese dioxide fiber, a length of 5-50 μm.
Preferably, described manganese dioxide fiber own growth and is intertwined to form firm active substance on collector
Layer.
Preferably, described manganese dioxide fiber-reactive layer is by electrolysis soluble manganese saline solution or cathodic reduction Gao Meng
Acid group and the manganese dioxide sedimentary that formed at collection liquid surface, or first after collection liquid surface sedimentation manganese coating, carry out anode again
The manganese dioxide layer that oxidation obtains.
Preferably, described collector material is electric conductivity and the metal of good thermal stability or nonmetal, including rustless steel
Sheet, stainless (steel) wire, nickel sheet, nickel foam and graphite flake, carbon paper, carbon cloth.
Present invention also offers the preparation method of described manganese dioxide fiber electrode, the method comprises the steps:
(1) the most directly by the manganese dioxide sedimentary of the weak crystalline state of electrochemical deposition, or on a current collector
Unformed porous manganese dioxide layer is prepared by carrying out anodic oxidation after negative electrode electrodeposit metals manganese again.
(2) manganese dioxide layer above-mentioned steps (1) prepared is put into autoclave pressure together with collector and seals laggard
Row hydrothermal treatment consists, makes the manganese dioxide layer of collection liquid surface carry out recrystallization oriented growth, takes out electrode after autoclave pressure cools down
And wash, it is dried, i.e. obtains manganese dioxide fiber electrode.
Preferably, in step (2), before heated sealed, in autoclave pressure, implantation concentration is the alkali metal of 0.01～1mol/L
Sulfate solution.
Preferably, in step (2), the temperature of hydrothermal treatment consists is 100～300 DEG C.
Preferably, in step (2), the time of hydrothermal treatment consists is 8～48 hours.
Present invention also offers described manganese dioxide fiber electrode for preparing answering in electric chemical super capacitor
With
(3) beneficial effect
(1) the manganese dioxide fiber electrode that prepared by the present invention is mainly by the fibre of the big length being grown on collection liquid surface
It is interweaved between dimension and reaches purpose that is fixing and that be fully contacted, it is not necessary to electrically inactive things such as binding agents, therefore can carry
The integral energy density of high electrode；
(2), in the manganese dioxide fibre electrode of the present invention, hole, and fiber diameter itself between manganese dioxide fiber, are formed
Little, increase the contact area of electrode active material and electrolyte, shorten charged balance ion in the diffusion within active substance
Path, improves utilization rate and the high rate performance of electrode active material；
(3) in the manganese dioxide fiber electrode of the present invention, manganese dioxide fibre crystallinity is good, and ionic conductivity is good, internal
Good tunnel structure is also beneficial to the electro-ionic mass transfer of lotus, improves ratio electric capacity and the high rate performance of material further；
(4) in the manganese dioxide fiber electrode preparation process of the present invention, it is not necessary to prepare complicated template or to collector
Carry out the special handlings such as surface nanometer array growth, preparation technology easy clean, with low cost.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to
Other accompanying drawing is obtained according to these accompanying drawings.
Fig. 1 is the SEM figure of manganese dioxide fiber electrode prepared by the present invention；
Fig. 2 is the cyclic voltammetry curve figure of manganese dioxide electrode prepared by the present invention；
Fig. 3 is the cyclic voltammetry curve figure of manganese dioxide electrode prepared by conventional electrodeposition method.
Detailed description of the invention
With embodiment, embodiments of the present invention are described in further detail below in conjunction with the accompanying drawings.Following example are used for
The present invention is described, but can not be used for limiting the scope of the present invention.
Compared with existing preparing technique process, the technical thought of the present invention and technological principle have outstanding feature and skill
Art advantage:
Prepare electrode of super capacitor at present and mainly first prepare MnO2 powder body material, then it is configured to binding agent etc.
Being coated on after slurry on collector and form final electrode, this is easy for causing loose contact between electrode active material and collector
And affect the charge-discharge performance of electrode.Additionally, due to the binding agent added etc. are electrically inactive material, it necessarily reduces whole
The energy density of electrode.A lot of documents are mentioned directly by anodic oxidation manganese sulfate solution or cathodic reduction high manganese ion
Manganese dioxide, the manganese dioxide electrode of available binder free, but the manganese dioxide gone out because of electro-deposition is deposited at collection liquid surface
Sedimentary is the most dense, and electrode is little with the contact area of electrolyte, and material crystalline is the most bad, and own electronic electrical conductance is poor
And be unfavorable for charged ion in the mass transfer within material crystals, the electrode therefore prepared only with on electrolyte contacts interface
Amount of activated material be obtained by, the active substance of electrode interior because being limited by mass transfer, be difficult to participate in electrochemical reaction, especially
The ratio electric capacity and the high rate performance that are material under high current density are the most undesirable.In order to increase electrode active in capacitor work process
Property material and electrolyte contact area, the study hotspot in this field is first to grow various metal, carbon on metallic matrix at present
Nano-tube array or Graphene, then at these metals, CNT or graphenic surface electro-deposition manganese dioxide and be used as super
Electrode for capacitors, but do not change pattern and the knot of deposited manganese dioxide self because these methods only change the pattern of collector
Crystalline substance, when the thickness of manganese dioxide sedimentary is thicker, the active substance within sedimentary is not used, the big electricity of material
Stream charge/discharge capacity and high rate performance are the most undesirable.Growth CNT or the technical process of Graphene the most on the metal surface
More complicated, cost is high, is difficulty with industrial applications.
The weak crystallinity being deposited on collector through electrochemical method or amorphous manganese dioxide are deposited by the present invention
Layer carries out hydrothermal treatment consists together with collector, makes have weak crystallinity or unformed manganese dioxide is carried out in water-heat process
Recrystallization oriented growth, be converted into and have big length and crystallize more perfect manganese dioxide fiber, and these greatly enhance/footpath
Ratio be interweaved between manganese dioxide fiber in collection liquid surface grow, it is ensured that fiber each other and and collector between not
Need to carry out bonding with binding agent and can be achieved with abundant good contact.On the one hand this make to be formed between manganese dioxide layer internal fiber
Substantial amounts of space, is beneficial to electrolyte and contacts with the manganese dioxide of electrode interior, increases electrode/electrolyte.On the other hand warp
After hydrothermal treatment consists, the manganese dioxide fibre diameter of growth only has 5～50nm, and this shortens electrode active material undoubtedly in discharge and recharge
During the diffusion length of charged balance ion, although the thickness of i.e. electrode surface manganese dioxide layer is bigger, but charged balance
The diffusion length of ion, without increase, is conducive to the multiplying power improving the utilization rate of active substance and high current charge-discharge to keep
Rate.Additionally, compared with the manganese dioxide sedimentary of direct electro-deposition or manganese metal anodic oxidation gained, exist at alkali metal ion
Manganese dioxide fibre crystallinity after lower hydrothermal treatment consists is more preferable, and ionic conductivity is more preferable, and the tunnel structure of fibrous inside has obtained
Kind, this is also beneficial to the diffusion therein of charged balance ion and improves the high current charge-discharge multiplying power conservation rate of material.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art
Identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the present invention
Protection domain.
Except there being special instruction, the various reagent used in the present invention, raw material be can commodity commercially or
The product that person can be prepared by known method.
The detailed description of the invention of the present invention is as follows:
A kind of manganese dioxide fiber electrode, including current collector material and the active substance being attached in current collector material, lives
Property material is mainly manganese dioxide fiber.Manganese dioxide fiber is big length fiber, a diameter of the 5 of fiber～50nm, length
In 5-50 μm.Described big length manganese dioxide fiber own growth and is intertwined to form firm activity on collector
Material layer, it is not necessary to active substance and current collector material are bondd with binding agent, therefore need not in electrode use binding agent.
The preparation method of above-mentioned manganese dioxide fiber electrode, comprises the steps:
(1) manganese dioxide sedimentary is prepared at collection liquid surface.
Prepare manganese dioxide sedimentary at collection liquid surface to complete by conventional known method, as with collector as sun
Pole electrolysis soluble manganese saline solution, with collector for the high violent acid ion of electrochemical cathode reduction, or at collection liquid surface first
Anodic oxidation is being carried out after deposition manganese metal.Raw materials kind, solution concentration electro-deposition parameter etc. do not limit.
(2) manganese dioxide electrode that above-mentioned steps (1) prepares is put in autoclave, and inject pure water or concentration and be not more than
1mol/L lithium sulfate, sodium sulfate or potassium sulfate solution, carry out hydrothermal treatment consists at 100～300 DEG C after sealing, the process time is 8
～48 hours.Band autoclave temperature takes out electrode after being cooled to room temperature, the most i.e. obtains required with deionized water rinsing
Manganese dioxide fiber electrode.
For the ease of understanding the present invention, below in conjunction with accompanying drawing and preferred embodiment, the present invention is made more comprehensively, careful
Ground describes, but protection scope of the present invention is not limited to embodiment in detail below.
Fig. 1 is the SEM figure of the manganese dioxide fiber electrode using the present invention to prepare, the activity on electrode as can be seen from Fig.
Material is that a large amount of intermeshing big L/D ratio manganese dioxide fiber is constituted.
Fig. 2 is the cyclic voltammetry curve of the manganese dioxide electrode using the present invention to prepare, and uses this as can be seen from Fig.
The electrode of bright preparation is in the shape of the sweep speed lower curve of 500mV/s still substantially close to rectangle, and capability retention is good, according to
Curve can calculate the ratio electric capacity of manganese dioxide.
Fig. 3 is the cyclic voltammetry curve of the manganese dioxide electrode using conventional electrodeposition method to prepare, as can be seen from Fig.
The electrode using conventional method to prepare deviates considerably from rectangle, capability retention in the shape of the sweep speed lower curve of 500mV/s
The best, the ratio electric capacity of manganese dioxide can be calculated according to curve.
Embodiment 1:
A kind of manganese dioxide fiber electrode, including current collector material and the active substance dioxy being attached in current collector material
Change manganese fiber, a diameter of the 10 of manganese dioxide fiber～30nm, a length of 5-50 μm.Manganese dioxide fiber growth is on collector
And be interweaved, it is not required to bond with binding agent.
The preparation method of above-mentioned manganese dioxide fiber electrode, comprises the steps:
(1) a certain amount of MnSO is weighed4·H2O、Na2SO4Be dissolved in deionized water, be configured to sulfur acid manganese 0.2mol/L,
The mixed solution of sodium sulfate 0.5mol/L.
(2) 304 stainless steel foils being cut into area is 4 × 1cm2Stainless steel band, as collector, uses 10% sulphuric acid successively
Aqueous solution and acetone carry out ultrasonic washing to this collector, and final rinse water is also dried.With 4 × 4cm2Titanium net is negative electrode,
With above-mentioned sulfur acid manganese mixed solution as electrodeposit liquid, the collector after surface clean as anode (work area is 1 ×
2cm2), use constant-current electrolysis manganese sulfate solution to prepare manganese dioxide sedimentary, constant-current electrolysis in rustless steel current collector material
Time anode electrode current density domination be 4mA/cm2, electrodeposition time is 4 minutes.Electro-deposition uses deionized water rinsing after completing
Manganese dioxide electrode.
(3) manganese dioxide electrode that above-mentioned steps (2) prepares is put in the stainless steel autoclave of inner liner polytetrafluoroethylene,
Implantation concentration is 0.01mol/L lithium sulfate solution, is incubated 20 hours at 150 DEG C, takes after autoclave is cooled to room temperature after sealing
Go out manganese dioxide electrode, within 5 hours, i.e. obtain manganese dioxide fiber electrode with being dried in 60 DEG C after deionized water rinsing.
By the pattern of active substance in Flied emission scanning electron microscope analysis gained manganese dioxide fiber electrode and size, titanium dioxide
A diameter of the 10 of manganese fiber～30nm, a length of 5-50 μm (seeing Fig. 1).It is electrolysis with the lithium sulfate aqueous solution of 0.5mol/L
Liquid, the manganese dioxide fiber electrode of above-mentioned preparation is working electrode, and area is 4 × 4cm2Platinum electrode be that auxiliary electrode is assembled into
Three-electrode system, is circulated volt-ampere test, and test potential scope is-0.4～0.4V (relative to saturated Mercurous sulfate electrode),
When sweep speed is 5mV/s, the ratio electric capacity calculating electrode active material according to cyclic voltammetry curve is 307.6F/g, and sweeping speed is
During 500mV/s, cyclic voltammetry curve is still close to rectangle (seeing Fig. 2), can reach 150.1F/g than electric capacity, and capability retention is respectively
Reach 48.8%.
Embodiment 2:
A kind of manganese dioxide fiber electrode, including current collector material and the active substance dioxy being attached in current collector material
Change manganese fiber, a diameter of the 30 of manganese dioxide fiber～50nm, a length of 5-50 μm.Manganese dioxide fiber growth is on collector
And be interweaved, it is not required to bond with binding agent.
The preparation method of above-mentioned manganese dioxide fiber electrode, comprises the steps:
(1) a certain amount of KMnO is weighed4And Na2SO4It is dissolved in deionized water, is configured to containing potassium permanganate 0.1mol/L, sulfur
Acid na concn is the mixed solution of 0.5mol/L.
(2) nickel sheet being cut into area is 4 × 1cm2Stainless steel band as collector, successively with 10% aqueous sulfuric acid and
Acetone carries out ultrasonic washing to this collector, and final rinse water is also dried.With 4 × 4cm2Titanium net is anode, uses above-mentioned height
The mixed solution of potassium manganate is as electrodeposit liquid, and as negative electrode, (work area is 1 × 2cm to the collector after surface clean2),
Using constant current cathode reduction method to prepare manganese dioxide layer in current collector material, electrolytic deposition uses deionized water rinsing after completing
Manganese dioxide electrode.
(3) manganese dioxide electrode that above-mentioned steps (1) prepares is put in the stainless steel autoclave of inner liner polytetrafluoroethylene,
Implantation concentration is 0.5mol/L potassium sulfate solution, is incubated 20 hours at 150 DEG C after sealing, takes out after autoclave is cooled to room temperature
Manganese dioxide electrode, i.e. obtains manganese dioxide fiber electrode in 5 hours with being dried in 60 DEG C after deionized water rinsing.
By the pattern of active substance in Flied emission scanning electron microscope analysis gained manganese dioxide fiber electrode and size, titanium dioxide
A diameter of the 30 of manganese fiber～50nm, a length of 5-50 μm.It is electrolyte with the lithium sulfate aqueous solution of 0.5mol/L, above-mentioned preparation
Manganese dioxide fiber electrode be working electrode, area is 4 × 4cm2Platinum electrode be that auxiliary electrode is assembled into three-electrode system,
Being circulated volt-ampere test, test potential scope is-0.4～0.4V (relative to saturated Mercurous sulfate electrode), and sweep speed is
During 5mV/s, the ratio electric capacity calculating electrode active material according to cyclic voltammetry curve is 291.3F/g, sweeps speed when being 500mV/s
Capability retention reach 46.8%.
Embodiment 3:
A kind of manganese dioxide fiber electrode, including current collector material and the active substance dioxy being attached in current collector material
Change manganese fiber, a diameter of the 5 of manganese dioxide fiber～20nm, a length of 7-50 μm.Manganese dioxide fiber growth is on collector
And be interweaved, it is not required to bond with binding agent.
The above-mentioned preparation method containing manganese compound transition metal oxide electrode, comprises the steps:
(1) a certain amount of MnSO is weighed4·H2O, boric acid and (NH4)2SO4It is dissolved in deionized water, is configured to containing manganese ion
0.5mol/L, the concentration of boric acid is 0.5mol/L, and the concentration of ammonium sulfate is the mixed solution of 1.5mol/L, adjusts with ammonia and sulphuric acid
The pH value of economize on electricity plating solution is to 4 and standby after stirring 30 minutes.
(2) carbon fiber paper being cut into area is 4 × 1cm2Carbon paper collector, with acetone, this collector is carried out successively
Ultrasonic washing, final rinse water is also dried.With 4 × 4cm2Titanium net is anode electrode, with above-mentioned containing manganese and ammonium radical ion
Mixed solution is as electroplate liquid, and as negative electrode, (work area is 1 × 2cm to the collector after surface clean2), use constant current
Electrodeposition process prepares manganese coating in current collector material, and cathode-current density during constant current deposition controls as 150mA/cm2, electricity is heavy
The long-pending time is 2 minutes, obtains manganese coating electrode after having deposited.
(3) composite coating anode above-mentioned steps (2) prepared is as anode, stainless steel substrates (area 4 × 4cm2) it is cloudy
Level, saturated calomel electrode is reference electrode, with the aqueous sodium persulfate solution of 0.5mol/L as electrolyte, carries out constant current anodic oxidation
Processing, the anodic current density when carrying out anodized controls as 1mA/cm2, terminate after anode potential reaches 0.8V
Oxidation, the manganese dioxide electrode obtained with deionized water rinsing.
(4) manganese dioxide electrode that above-mentioned steps (3) prepares is put in the stainless steel autoclave of inner liner polytetrafluoroethylene,
Implantation concentration is 1mol/L potassium sulfate solution, is incubated 48 hours at 300 DEG C after sealing, takes out two after autoclave is cooled to room temperature
Manganese oxide electrode, i.e. obtains manganese dioxide fiber electrode in 5 hours with being dried in 60 DEG C after deionized water rinsing.
By the pattern of active substance in Flied emission scanning electron microscope analysis gained manganese dioxide fiber electrode and size, titanium dioxide
A diameter of the 5 of manganese fiber～20nm, a length of 7-50 μm.It is electrolyte with the lithium sulfate aqueous solution of 0.5mol/L, above-mentioned preparation
Manganese dioxide fiber electrode be working electrode, area is 4 × 4cm2Platinum electrode be that auxiliary electrode is assembled into three-electrode system,
Being circulated volt-ampere test, test potential scope is-0.4～0.4V (relative to saturated Mercurous sulfate electrode), and sweep speed is
During 5mV/s, the ratio electric capacity calculating electrode active material according to cyclic voltammetry curve is 301.2F/g, sweeps speed when being 500mV/s,
Capability retention reaches 51.2%.
Embodiment 4:
A kind of manganese dioxide fiber electrode, including current collector material and the active substance dioxy being attached in current collector material
Change manganese fiber, a diameter of the 10 of manganese dioxide fiber～40nm, a length of 5-50 μm.Manganese dioxide fiber growth is on collector
And be interweaved, it is not required to bond with binding agent.
The preparation method of above-mentioned manganese dioxide fiber electrode, comprises the steps:
(1) a certain amount of MnSO is weighed4·H2O、Na2SO4Be dissolved in deionized water, be configured to sulfur acid manganese 0.2mol/L,
The mixed solution of sodium sulfate 0.5mol/L.
(2) 304 stainless steel foils being cut into area is 4 × 1cm2Stainless steel band, as collector, uses 10% sulphuric acid successively
Aqueous solution and acetone carry out ultrasonic washing to this collector, and final rinse water is also dried.With 4 × 4cm2Titanium net is negative electrode,
With above-mentioned sulfur acid manganese mixed solution as electrodeposit liquid, the collector after surface clean as anode (work area is 1 ×
2cm2), use constant-current electrolysis manganese sulfate solution to prepare manganese dioxide sedimentary, constant-current electrolysis in rustless steel current collector material
Time anode electrode current density domination be 4mA/cm2, electrodeposition time is 4 minutes.Electro-deposition uses deionized water rinsing after completing
Manganese dioxide electrode.
(3) manganese dioxide electrode that above-mentioned steps (2) prepares is put in the stainless steel autoclave of inner liner polytetrafluoroethylene,
Implantation concentration is 0.1mol/L metabisulfite solution, is incubated 10 hours at 100 DEG C after sealing, takes out after autoclave is cooled to room temperature
Manganese dioxide electrode, i.e. obtains manganese dioxide fiber electrode in 5 hours with being dried in 60 DEG C after deionized water rinsing.
By the pattern of active substance in Flied emission scanning electron microscope analysis gained manganese dioxide fiber electrode and size, titanium dioxide
A diameter of the 10 of manganese fiber～40nm, a length of 5-50 μm.It is electrolyte with the lithium sulfate aqueous solution of 0.5mol/L, above-mentioned preparation
Manganese dioxide fiber electrode be working electrode, area is 4 × 4cm2Platinum electrode be that auxiliary electrode is assembled into three-electrode system,
Being circulated volt-ampere test, test potential scope is-0.4～0.4V (relative to saturated Mercurous sulfate electrode), and sweep speed is
During 5mV/s, the ratio electric capacity calculating electrode active material according to cyclic voltammetry curve is 304.1F/g, sweeps speed when being 500mV/s,
Capability retention respectively reaches 49.5%.
Embodiment 5:
A kind of manganese dioxide fiber electrode, including current collector material and the active substance dioxy being attached in current collector material
Change manganese fiber, a diameter of the 5 of manganese dioxide fiber～30nm, a length of 5-50 μm.Manganese dioxide fiber growth is on collector
And be interweaved, it is not required to bond with binding agent.
The preparation method of above-mentioned manganese dioxide fiber electrode, comprises the steps:
(1) a certain amount of MnSO is weighed4·H2O、Na2SO4Be dissolved in deionized water, be configured to sulfur acid manganese 0.2mol/L,
The mixed solution of sodium sulfate 0.5mol/L.
(2) carbon fiber paper being cut into area is 4 × 1cm2Carbon paper collector, with acetone, this collector is carried out successively
Ultrasonic washing, final rinse water is also dried.With 4 × 4cm2Titanium net is anode electrode, with 4 × 4cm2Titanium net is negative electrode, uses
State sulfur acid manganese mixed solution as electrodeposit liquid, the collector after surface clean as anode (work area is 1 ×
2cm2), use constant-current electrolysis manganese sulfate solution to prepare manganese dioxide sedimentary, constant-current electrolysis in rustless steel current collector material
Time anode electrode current density domination be 4mA/cm2, electrodeposition time is 4 minutes.Electro-deposition uses deionized water rinsing after completing
Manganese dioxide electrode.
(3) manganese dioxide electrode that above-mentioned steps (2) prepares is put in the stainless steel autoclave of inner liner polytetrafluoroethylene,
Implantation concentration is 0.5mol/L lithium sulfate solution, is incubated 30 hours at 300 DEG C after sealing, and band autoclave takes out after being cooled to room temperature
Manganese dioxide electrode, i.e. obtains manganese dioxide fiber electrode in 5 hours with being dried in 60 DEG C after deionized water rinsing.
By the pattern of active substance in Flied emission scanning electron microscope analysis gained manganese dioxide fiber electrode and size, titanium dioxide
A diameter of the 5 of manganese fiber～30nm, a length of 5-50 μm.It is electrolyte with the lithium sulfate aqueous solution of 0.5mol/L, above-mentioned preparation
Manganese dioxide fiber electrode be working electrode, area is 4 × 4cm2Platinum electrode be that auxiliary electrode is assembled into three-electrode system,
Being circulated volt-ampere test, test potential scope is-0.4～0.4V (relative to saturated Mercurous sulfate electrode), and sweep speed is
During 5mV/s, the ratio electric capacity calculating electrode active material according to cyclic voltammetry curve is 297.7F/g, sweeps speed when being 500mV/s,
Capability retention reaches 51.2%.
Comparative example 1:
(1) a certain amount of MnSO is weighed4·H2O、Na2SO4Be dissolved in deionized water, be configured to sulfur acid manganese 0.2mol/L,
The mixed solution of sodium sulfate 0.5mol/L.
(2) 304 stainless steel foils being cut into area is 4 × 1cm2Stainless steel band, as collector, uses 10% sulphuric acid successively
Aqueous solution and acetone carry out ultrasonic washing to this collector, and final rinse water is also dried.With 4 × 4cm2Titanium net is negative electrode,
With above-mentioned sulfur acid manganese mixed solution as electrodeposit liquid, the collector after surface clean as anode (work area is 1 ×
2cm2), use constant-current electrolysis manganese sulfate solution to prepare manganese dioxide sedimentary, constant-current electrolysis in rustless steel current collector material
Time anode electrode current density domination be 4mA/cm2, electrodeposition time is 4 minutes.Electro-deposition uses deionized water rinsing after completing
Manganese dioxide electrode is also dried, in 60 DEG C, the manganese dioxide electrode i.e. obtaining contrasting 5 hours.
With the pattern of active substance, gained comparison electrode in Flied emission scanning electron microscope analysis gained contrast manganese dioxide electrode
Middle manganese dioxide is fine and close sedimentary.It is electrolyte with the lithium sulfate aqueous solution of 0.5mol/L, the contrast dioxy of above-mentioned preparation
Changing manganese electrode is working electrode, and area is 4 × 4cm2Platinum electrode be that auxiliary electrode is assembled into three-electrode system, be circulated volt
Peace test, test potential scope is-0.4～0.4V (relative to saturated Mercurous sulfate electrode), when sweep speed is 5mV/s, root
The ratio electric capacity calculating electrode active material according to cyclic voltammetry curve is 270.0F/g；Sweeping speed when being 500mV/s, cyclic voltammetric is bent
Line deviates considerably from rectangle (such as accompanying drawing 3), and ratio electric capacity 72.2F/g, capability retention is only 26.7%.
Conclusion: compared with manganese dioxide membrane electrode prepared by conventional electrodeposition method, manganese dioxide prepared by the present invention
Fiber electrode has higher than electric capacity and capability retention.
Embodiment of above is merely to illustrate the present invention, rather than limitation of the present invention.Although with reference to embodiment to this
Bright be described in detail, it will be understood by those within the art that, technical scheme is carried out various combination,
Amendment or equivalent, without departure from the spirit and scope of technical solution of the present invention, all should contain the right in the present invention and want
Ask in the middle of scope.
Claims (10)
1. a manganese dioxide fiber electrode, it is characterised in that this manganese dioxide fiber electrode includes collector and is attached to collection
Manganese dioxide fiber-reactive layer on fluid；Described manganese dioxide fiber is big length fiber；Described manganese dioxide fiber electricity
Without binding agent in extremely.
Manganese dioxide fiber electrode the most according to claim 1, it is characterised in that described manganese dioxide fiber a diameter of
5～50nm, a length of 5-50 μm.
Manganese dioxide fiber electrode the most according to claim 1 and 2, it is characterised in that described manganese dioxide fiber self
It is grown on collector and is intertwined to form firm active material layer.
Manganese dioxide fiber electrode the most according to claim 1 and 2, it is characterised in that described manganese dioxide fiber-reactive
Layer is that the manganese dioxide formed at collection liquid surface by electrolysis soluble manganese saline solution or cathodic reduction MnO4 is sunk
Lamination, or first after collection liquid surface sedimentation manganese coating, carry out the manganese dioxide layer that anodic oxidation obtains again.
Manganese dioxide fiber electrode the most according to claim 1 and 2, it is characterised in that described collector material is conduction
Property and the metal of good thermal stability or nonmetal, including stainless steel substrates, stainless (steel) wire, nickel sheet, nickel foam and graphite flake, carbon
Paper, carbon cloth.
6. the preparation method of the manganese dioxide fiber electrode described in any one of claim 1-5, it is characterised in that the method includes
Following step:
(1) the most directly by the manganese dioxide sedimentary of the weak crystalline state of electrochemical deposition, or pass through on a current collector
Carry out anodic oxidation after negative electrode electrodeposit metals manganese again and prepare unformed porous manganese dioxide layer；
(2) manganese dioxide layer above-mentioned steps (1) prepared carries out water after putting into autoclave pressure together with collector and seal
Heat treatment, makes the manganese dioxide layer of collection liquid surface carry out recrystallization oriented growth, takes out electrode and go forward side by side after autoclave pressure cools down
Row washing, is dried, i.e. obtains manganese dioxide fiber electrode.
The preparation method of manganese dioxide fiber electrode the most according to claim 6, it is characterised in that in step (2),
Before heated sealed, in autoclave pressure, implantation concentration is the alkali metal sulphuric acid saline solution of 0.01～1mol/L, described alkali metal sulphuric acid
Salt is lithium sulfate, sodium sulfate or potassium sulfate.
The preparation method of manganese dioxide fiber electrode the most according to claim 6, it is characterised in that in step (2), water
The temperature of heat treatment is 100～300 DEG C.
The preparation method of manganese dioxide fiber electrode the most according to claim 6, it is characterised in that in step (2), water
The time of heat treatment is 8～48 hours.
10. the manganese dioxide fiber electrode described in any one of claim 1-5 is for preparing in electric chemical super capacitor
Application.
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| CN106952747A (en) * | 2017-03-27 | 2017-07-14 | 中南大学 | A kind of preparation method of high power capacity self-supporting manganese dioxide/carbon combination electrode |
| CN112701295A (en) * | 2020-12-29 | 2021-04-23 | 蜂巢能源科技有限公司 | Graphite fibrofelt flexible current collector, preparation method thereof and flexible battery |
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| CN102030371A (en) * | 2010-12-21 | 2011-04-27 | 北京化工大学 | Preparation method of manganese dioxide nanowire with high aspect ratio |
| CN102664107A (en) * | 2012-05-31 | 2012-09-12 | 北京科技大学 | Preparation method of nano-manganese dioxide electrode |
| CN103193273A (en) * | 2013-05-03 | 2013-07-10 | 广东工业大学 | Preparation method of extra-long manganese dioxide nanowires |
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| CN102030371A (en) * | 2010-12-21 | 2011-04-27 | 北京化工大学 | Preparation method of manganese dioxide nanowire with high aspect ratio |
| CN102664107A (en) * | 2012-05-31 | 2012-09-12 | 北京科技大学 | Preparation method of nano-manganese dioxide electrode |
| CN103193273A (en) * | 2013-05-03 | 2013-07-10 | 广东工业大学 | Preparation method of extra-long manganese dioxide nanowires |
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| CN106952747A (en) * | 2017-03-27 | 2017-07-14 | 中南大学 | A kind of preparation method of high power capacity self-supporting manganese dioxide/carbon combination electrode |
| CN106952747B (en) * | 2017-03-27 | 2018-09-11 | 中南大学 | A kind of preparation method of high power capacity self-supporting manganese dioxide/carbon combination electrode |
| CN112701295A (en) * | 2020-12-29 | 2021-04-23 | 蜂巢能源科技有限公司 | Graphite fibrofelt flexible current collector, preparation method thereof and flexible battery |
| CN112701295B (en) * | 2020-12-29 | 2022-02-22 | 蜂巢能源科技有限公司 | Graphite fibrofelt flexible current collector, preparation method thereof and flexible battery |
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