CN104867681B - Nano-porous copper silver supported manganese dioxide electrode slice and preparation method therefor - Google Patents
Nano-porous copper silver supported manganese dioxide electrode slice and preparation method therefor Download PDFInfo
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- CN104867681B CN104867681B CN201510216607.8A CN201510216607A CN104867681B CN 104867681 B CN104867681 B CN 104867681B CN 201510216607 A CN201510216607 A CN 201510216607A CN 104867681 B CN104867681 B CN 104867681B
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Abstract
The invention relates to a nano-porous copper silver supported manganese dioxide electrode slice and a preparation method therefor. The cross section of the electrode slice comprises three layers. A middle core layer is an amorphous matrix. The other two sides are nano-porous copper silver. A hole wall and a surface of the nano-porous copper silver grow a layer of uniform thin manganese dioxide. The thickness of the electrode slice is about 25-35 mum. The thickness of an inside amorphous matrix layer is about 12-28 mum. The thickness of a single side of nano-porous copper silver or manganese dioxide composite electrode material layer is about 3-11 mum. The amorphous matrix comprises CuxZryAgz alloy components, wherein x is greater than or equal to 40 and less than or equal to 45, y is greater than or equal to 45 and less than or equal to 50, z is greater than or equal to 5 and less than or equal to 15, and x plus y plus z equals 100. The preparation method can realize independent support of the electrode slice. Compared with a conventional complicated process of flaking the electrode slice, the preparation method saves the step of adding substances such as a conductive agent, a binder and so on, thereby overcoming the defects in the prior art that active substances have poor dispersibility, are easy to fall off and have small effective specific surface area.
Description
Technical field：
The invention belongs to supercapacitor technologies field, and in particular to the manganese dioxide electricity that a kind of nano porous copper silver is supported
The preparation method of pole piece.
Background technology：
Ultracapacitor because its have can instantaneous large-current fast charging and discharging, operating temperature range width, memory-less effect, exempt from
Safeguard, safe and pollution-free, power density is high, the features such as have extended cycle life, while manganese dioxide is used as one of metal-oxide,
The theoretical specific capacitance value of Yin Qigao, cheap, rich reserves and it is nontoxic the advantages of can be super capacitor material.But dioxy
Change manganese granule and cluster easily occurs, self-conductive is poor so that capacitive property is limited significantly.Collector is a kind of to collect electric current
Structure or part, major function is to collect in the electric current that active substance is produced, there is provided electron channel, accelerates electric charge transfer,
Discharge and recharge coulombic efficiency is improved, needs to meet the features such as electrical conductivity height, good mechanical property, little internal resistance as collector.Find and close
Suitable current collector material is combined into for emphasis with manganese dioxide.
In recent years, porous material is extensively paid close attention to because of its excellent application performance by people.Nano porous metal is a kind of new
Bore hole size be nano level functional material.It has unique physics such as high specific surface area and low-density and chemical
Can so that have a wide range of applications in terms of catalysis, sensing and fuel cell.Method for preparing nano porous metal material
Mainly there are template and de- alloyage, wherein de- alloyage enjoys people to favor, because material aperture is little obtained in this method,
The size and morphology controllable of nano aperture, and it is simple to operate, with low cost.Nano porous metal is combined with manganese dioxide
Together, the cooperative effect between two kinds of different materials is given full play to, the specific surface area and electrical conductivity of composite is improved, so as to excellent
The chemical property of polarizing electrode material.
First technology, in " the electrode for super capacitor piece and preparation method thereof " of the A of publication number CN 103337374, its
The preparation method of electrode for super capacitor piece is：Nano porous copper is prepared with de- alloyage, then prepares nano porous copper and two
Manganese oxide mixed-powder, finally presses dried nano porous copper and manganese dioxide mixed-powder with polyfluortetraethylene of binding element
Mass ratio 95:5 mixing, used as dispersant, the uniform grinding in agate mortar is tuned into pasty state to dehydrated alcohol, is evenly coated in nickel screen
On, it is pressed into electrode slice under powder compressing machine.The use of binding agent increases the internal resistance of electrode slice, causes the drop of specific capacitance
It is low.Because electrode material needs to be applied to aptitude test on nickel screen for powder, this preparation technology for having resulted in this invention is answered
It is miscellaneous, the shortcomings of the cycle is long.
First technology, a kind of " system of Graphene and manganese dioxide nano-composite material of the A of publication number CN 102275903
In Preparation Method ", the preparation method of manganese dioxide will be added in saturation potassium permanganate solution in acid, react 1 at 60～80 DEG C～
The manganese dioxide that 5h is obtained.Acid in preparation method is concentrated hydrochloric acid or concentrated sulphuric acid.The strong acid of high concentration is reactant to environment
It is unfriendly, easily human body is produced injure in operation.Reaction also needs to be carried out at a temperature of 60～80 DEG C, causes the energy
Waste, complicated process of preparation.
The content of the invention：
The purpose of the present invention is a kind of nano porous copper silver/manganese dioxide electrode piece that can independently support of invention and its system
Preparation Method.The electrode slice is by control corrosion rate liquid concentration and de- alloy time the noncrystal substrate of band core can be enable to protect
Stay, it is noncrystal substrate to obtain intermediate core layer, and its both sides is the current collector material of nano porous copper silver, and then manganese dioxide is deposited on
This is obtained above the nano porous copper silver/manganese dioxide electrode piece of self-supporting.But the nano porous metal of forefathers' preparation is frangible,
Need when making ultracapacitor as current collector material through loaded down with trivial details tableting processes.The achievable self-supporting of the present invention and
Preparation process is simple.
The technical scheme is that：
A kind of manganese dioxide electrode piece that nano porous copper silver is supported, the transverse section of the electrode slice is divided into three layers, intermediate core
Layer is noncrystal substrate, and both sides are nano porous copper silver, and in the silver-colored hole wall of nano porous copper and superficial growth one layer uniform tiny
Manganese dioxide；The thickness of electrode slice is 25～35 μm, and inner side noncrystal substrate thickness degree is 12～28 μm, unilateral nano porous copper
Silver/manganese dioxide composite electrode material thickness degree is 3～11 μm；
Described noncrystal substrate is CuxZryAgzAlloying component, wherein, 40≤x≤45,45≤y≤50,5≤z≤15, and
X+y+z=100.
Described nano porous copper silver is aperture in 10～90nm.
The preparation method of the manganese dioxide electrode piece that described nano porous copper silver is supported, comprises the following steps：
The first step, prepares amorphous ribbon
Select high-purity C u, Zr, Ag metal as raw material, wherein, Cu, Zr and Ag purity is 99.9wt%；According to
Target component CuxZryAgzPrealloy composition is prepared, wherein, 40≤x≤45,45≤y≤50,5≤z≤15, and x+y+z=
100, it is atomic percent to mark composition, then Cu-Zr-Ag alloy cast ingots is obtained in arc-melting furnace melting, removes skim-coat oxygen
Change skin, be put into after cutting in quartz test tube, 8.0 × 10-4Under Pa vacuums, heating melts alloy cast ingot, then using argon
Gas quickly blows out the alloy of melting, and the liquid alloy of the melting rapid solidification on the copper roller of high speed rotation forms non-crystaline amorphous metal
Band；
It is 1.0MPa to blow casting pressure；Copper wheel rotating speed is 30～40m/s；A length of 60～300cm of prepared AMORPHOUS ALLOY RIBBONS,
A width of 1.5～3mm, thickness is 25～40 μm；
Second step, prepares nano porous copper silver
At room temperature, AMORPHOUS ALLOY RIBBONS is placed in corrosive liquid and soaks after 30～100min, obtains nano porous copper silver material
Material；In corrosive liquid, the concentration of HF is 0.1～0.3M, and the concentration of HCl is 2 for the mol ratio of 0.05～0.15M, HF and HCl:1；
3rd step, the manganese dioxide electrode piece that nano porous copper silver is supported
Nano porous copper silver prepared by previous step is put in container and with dehydrated alcohol by its submergence, then again Deca is high
Potassium manganate solution, stands 2～8h after Deca；After by reacted product washes of absolute alcohol, nano porous copper silver is obtained
The manganese dioxide electrode piece of support；Wherein, about per 10mg nano porous coppers silver Deca 10mL potassium permanganate solution；
Wherein, the concentration of potassium permanganate is 0.05～0.1M.
Raw material and equipment used by the preparation of the manganese dioxide electrode piece that above-mentioned nano porous copper silver is supported is by public affairs
The approach known is obtained, and operating procedure used is that those skilled in the art can grasp.
To detect the capacitance characteristic of the ultracapacitor compound electric pole piece of the present invention, using chi660e electrochemical operations
Station is circulated C-V characteristic (Cyclic Voltammetry) test.Electro-chemical test adopts three-electrode system, wherein working
It is Ag/AgCl, auxiliary electrode is platinum electrode that electrode is the ultracapacitor compound electric pole piece of the present invention, reference electrode, test
Voltage range is -0.2V～0.8V, and sweep speed is 10mV/s, and electro-chemical test is in 0.5M Na2SO4Carry out in solution.CV is bent
The characteristics of line presents obvious rectangle, good symmetry and big enclosed region area, this explanation nano porous copper silver/dioxy
Change manganese electrode and show good reversibility and high specific capacitance value.
Compared with existing technology, beneficial effects of the present invention are as follows：
(1) amorphous by the way that band core just can be made simply by control corrosion rate liquid concentration and de- alloy time of the invention
Matrix is retained.Because internal noncrystal substrate sandwich layer has certain intensity and toughness, realize and electrode material is held
Carry and supporting role.Therefore, the material can be used as the collector of the active substance of ultracapacitor.MnO2The afflux can be deposited on
On body, complex is formed.This complex belongs to a kind of Novel super capacitor composite；
(2) the manganese dioxide electrode piece that the nano porous copper silver that prepared by the present invention is supported, intermediate core layer is noncrystal substrate, its
Both sides are nano porous copper silver, and manganese dioxide in the hole wall of nano porous copper silver and superficial growth.This structure can realize electrode
The independent support of piece, compared with traditional complicated loaded down with trivial details electrode pressing piece process, removes the materials such as addition conductive agent, binding agent from,
And then avoid active substance bad dispersibility, easy to fall off, the effective ratio table that conventional Super electrode for capacitors piece preparation method brings
The drawback such as area is little；
(3) present invention is to deposit manganese dioxide, the nano-porous structure energy of high-specific surface area in nano porous copper silver surface
The manganese dioxide for making itself easily reunite is uniformly dispersed, and improves the utilization rate of active substance manganese dioxide, makes the ratio electricity of electrode slice
Capacitance increases；It is tightly combined between manganese dioxide and nano porous copper silver, the high conductivity of collector, and nanometer can be effectively ensured
Porous Cu silver itself has excellent electric conductivity, therefore has relatively low contact internal resistance between the two, so that the internal resistance (4 of electrode slice
Ω) substantially reduce than the internal resistance (9 Ω) of traditional electrode pressing piece, electric conductivity, specific capacitance value and the circulation that improve electrode slice is steady
It is qualitative；
(4) the electrode slice internal resistance that prepared by the present invention is little, utilization rate of manganese dioxide is high, in simulation ultracapacitor work
The features such as presenting obvious rectangle, good symmetry and big closed area in CV tests, thus illustrates prepared by the present invention
Electrode slice show good reversibility and high specific capacitance value, specific capacitance value is 565F/g, is Publication No. CN
Specific capacitance 150.76F/g of " electrode for super capacitor piece and preparation method thereof " invention electrode slice of 103337374 A
3.75 again.Simultaneously operating procedure is simple, suitable for scale production.
Description of the drawings：
Fig. 1：The stereoscan photograph of the nano porous copper silver/manganese dioxide electrode piece prepared in embodiment one.
Fig. 2：The energy spectrum analysis figure of the nano porous copper silver/manganese dioxide electrode piece prepared in embodiment one.
Fig. 3：The cyclic voltammetry curve figure of the nano porous copper silver/manganese dioxide electrode piece prepared in embodiment one.
Fig. 4：The sectional drawing of the nano porous copper silver/manganese dioxide electrode piece prepared in embodiment one.
Fig. 5：Nano porous copper silver/manganese dioxide electrode piece inner silica the manganese prepared in embodiment one and nanoporous
The combination figure of copper silver.
Specific embodiment
Embodiment 1
According to the mass percent of each element in subject alloy：It is 10% for 45%, Ag that Cu is 45%, Zr, and purity is equal
Foundry alloy raw material is mixed to get for the broken copper sheet (7.110g) of 99.9wt%, zirconium grain (10.207g) and silver granuel (2.682g)；Then
Foundry alloy raw material is placed in vacuum arc melting furnace, the pure titanium that 20g purity is 99.9wt% is initially charged molten as oxygen scavenging material
Refining, then under argon protection, repetition 5 foundry alloys of melting (are both needed to overturn foundry alloy every time), 60 seconds or so every time, to guarantee
Alloy structure uniformity.Furnace cooling is obtained Cu45Zr45Ag10Alloy cast ingot.
Obtained alloy cast ingot is removed into superficial oxidation skin, be divided into it is suitably sized be put in quartz test tube, 8.0 ×
10-4Under Pa vacuums, heating melts alloy cast ingot, is then quickly blown out the alloy of melting using inert argon, melts
Liquid alloy high speed rotation copper roller on rapid solidification formed AMORPHOUS ALLOY RIBBONS.It is 1.0MPa to blow casting desirable pressure；Copper
Wheel speed is 35m/s；A width of 1.8mm of prepared AMORPHOUS ALLOY RIBBONS, thickness is 33 μm；
The sample of some 40mm length is intercepted on the amorphous alloy thin band for obtaining, Fluohydric acid. and hydrochloric acid are placed under room temperature
(mol ratio of 0.3M HF+0.15M HCl, wherein HF and HCl is 2 to mixed solution:1) removal alloying is carried out in and processes 30min,
It is non-crystaline amorphous metal so as to intermediate core layer is obtained, both sides are nano porous copper silver structure, and Jing measurements are (using the measuring scale of scanning electron microscope
Can be with the thickness of measuring samples) thickness of unilateral nano porous copper silver is as 5.7 μm.
Intercept 30mm length upper step obtain nano porous copper silver (about 10mg) be put in beaker and with dehydrated alcohol by its
Submergence, the potassium permanganate solution of 10mL0.05M is instilled with glue head dropper in beaker, makes manganese dioxide in nano porous copper silver
Surface forming core growth, course of reaction stands 2h.After by reacted product washes of absolute alcohol, nano porous copper silver is obtained
The manganese dioxide electrode piece of support.
(its chemical equation is：4KMnO4+3CH3CH2OH=3CH3COOK+4MnO2↓+KOH+H2O)
Electrode slice is using chi660e electrochemical workstations in 0.5M Na2SO4CV tests are carried out in solution.Wherein work electricity
It is platinum electrode that ultracapacitor compound electric pole piece extremely of the invention, reference electrode are Ag/AgCl, auxiliary electrode, test electricity
Pressure scope is -0.2V～0.8V, and sweep speed is 10mV/s.
Fig. 1 is the stereoscan photograph of nano porous copper silver/manganese dioxide electrode piece, and the aperture of nano porous copper silver is 25
～30nm, it is possible to it was observed that manganese dioxide is tiny and is evenly distributed.
Fig. 2 is the energy spectrum diagram of nano porous copper silver/manganese dioxide electrode piece.From energy spectrum diagram as can be seen that electrode slice by Mn,
O, Cu and Ag, i.e. nano porous copper silver and manganese dioxide are constituted, and are generated without novel substance.
Fig. 3 is the cyclic voltammetry curve figure of obtained nano porous copper silver/manganese dioxide electrode piece in the present embodiment.Jing is counted
Calculate, the specific capacitance value of electrode slice manufactured in the present embodiment is 399.7F/g, " the super electricity much larger than publication number CN103337374A
The specific capacitance value of the electrode for super capacitor piece prepared in container electrode slice and preparation method thereof ".Illustrate the electricity of the present invention
Not only process is simple, the specific capacitance performance of easy to operate but also preparation electrode slice are good for the preparation method of pole piece.
Fig. 4 is the sectional drawing of nano porous copper silver/manganese dioxide electrode piece manufactured in the present embodiment.Can from sectional drawing
Go out, because the de- alloy time is shorter, unilateral nano porous copper silver/manganese dioxide composite electrode material thickness degree is about 5.7 μm, interior
Side is noncrystal substrate.
Fig. 5 is nano porous copper silver manufactured in the present embodiment/manganese dioxide electrode piece inner silica manganese and nanoporous
The combination figure of copper silver.As seen from the figure, one layer of uniform tiny manganese dioxide in the superficial growth of nano porous copper silver ligament.
The manganese dioxide that the nano-porous structure of high-specific surface area can make itself easily reunite is uniformly dispersed, and improves active substance titanium dioxide
The utilization rate of manganese；It is tightly combined between manganese dioxide and nano porous copper silver, the high conductivity of collector, Er Qiena can be effectively ensured
Rice Porous Cu silver itself has excellent electric conductivity, therefore has relatively low contact internal resistance between the two, makes the specific capacitance value of electrode slice
Increase.
Embodiment 2
According to the mass percent of each element in subject alloy：It is 10% for 45%, Ag that Cu is 45%, Zr, and purity is equal
Foundry alloy raw material is mixed to get for the copper sheet (7.110g) of 99.9wt%, zirconium grain (10.207g) and silver granuel (2.682g)；Then will
Foundry alloy raw material is placed in vacuum arc melting furnace, by the use of the pure titanium that 20g purity is 99.9wt% as oxygen scavenging material, in argon
Under protection, repetition melting 5 times (being both needed to overturn foundry alloy every time), 60 seconds or so every time, to guarantee alloy structure uniformity.With stove
Cooling is obtained Cu45Zr45Ag10Alloy cast ingot.
Obtained alloy cast ingot is removed into superficial oxidation skin, be divided into it is suitably sized be put in quartz test tube, 8.0 ×
10-4Under Pa vacuums, heating melts alloy cast ingot, is then quickly blown out the alloy of melting using inert argon, melts
Liquid alloy high speed rotation copper roller on rapid solidification formed AMORPHOUS ALLOY RIBBONS.It is 1.0MPa to blow casting desirable pressure；Copper
Wheel speed is 35m/s；A width of 1.8mm of prepared AMORPHOUS ALLOY RIBBONS, thickness is 33 μm；
The sample of some 40mm length is intercepted on the amorphous alloy thin band for obtaining, Fluohydric acid. and hydrochloric acid are placed under room temperature
(mol ratio of 0.3M HF+0.15M HCl, wherein HF and HCl is 2 to mixed solution:1) removal alloying is carried out in and processes 60min,
It is non-crystaline amorphous metal so as to intermediate core layer is obtained, both sides are the structure of nano porous copper silver, the unilateral nano porous copper silver of Jing measurements
Thickness is 8.3 μm.
Intercept 30mm length upper step obtain nano porous copper silver (about 10mg) be put in beaker and with dehydrated alcohol by its
Submergence, the potassium permanganate solution of 10mL 0.08M is instilled with glue head dropper in beaker, makes manganese dioxide in nano porous copper silver
Forming core growth in the environment of presence, course of reaction stands 6h.After by reacted product washes of absolute alcohol, nanometer is obtained many
The manganese dioxide electrode piece that hole copper silver is supported.
Electrode slice is using chi660e electrochemical workstations in 0.5M Na2SO4CV tests are carried out in solution.Wherein work electricity
It is platinum electrode that ultracapacitor compound electric pole piece extremely of the invention, reference electrode are Ag/AgCl, auxiliary electrode, test electricity
Pressure scope is -0.2V～0.8V, and sweep speed is 10mV/s.
Specific capacitance 426F/g of super capacitor electrode slice manufactured in the present embodiment.
Embodiment 3
According to the mass percent of each element in subject alloy：It is 10% for 45%, Ag that Cu is 45%, Zr, and purity is equal
Foundry alloy raw material is mixed to get for the copper sheet (7.110g) of 99.9wt%, zirconium grain (10.207g) and silver granuel (2.682g)；Then will
Foundry alloy raw material is placed in vacuum arc melting furnace, by the use of the pure titanium that 20g purity is 99.9wt% as oxygen scavenging material, in argon
Under protection, repetition melting 5 times (being both needed to overturn foundry alloy every time), 60 seconds or so every time, to guarantee alloy structure uniformity.With stove
Cooling is obtained Cu45Zr45Ag10Alloy cast ingot.
Obtained alloy cast ingot is removed into superficial oxidation skin, be divided into it is suitably sized be put in quartz test tube, 8.0 ×
10-4Under Pa vacuums, heating melts alloy cast ingot, is then quickly blown out the alloy of melting using inert argon, melts
Liquid alloy high speed rotation copper roller on rapid solidification formed AMORPHOUS ALLOY RIBBONS.It is 1.0MPa to blow casting desirable pressure；Copper
Wheel speed is 35m/s；A width of 1.8mm of prepared AMORPHOUS ALLOY RIBBONS, thickness is 33 μm；
The sample of some 40mm length is intercepted on the amorphous alloy thin band for obtaining, Fluohydric acid. and hydrochloric acid are placed under room temperature
(mol ratio of 0.3M HF+0.15M HCl, wherein HF and HCl is 2 to mixed solution:1) removal alloying is carried out in and processes 90min,
It is non-crystaline amorphous metal so as to intermediate core layer is obtained, both sides are the structure of nano porous copper silver, the unilateral nano porous copper silver of Jing measurements
Thickness is 10.5 μm.
Intercept 30mm length upper step obtain nano porous copper silver (about 10mg) be put in beaker and with dehydrated alcohol by its
Submergence, the potassium permanganate solution of 10mL 0.1M is instilled with glue head dropper in beaker, manganese dioxide is deposited in nano porous copper silver
Environment in forming core growth, course of reaction stand 8h.After by reacted product washes of absolute alcohol, nanoporous are obtained
The manganese dioxide electrode piece that copper silver is supported.
Electrode slice is using chi660e electrochemical workstations in 0.5M Na2SO4CV tests are carried out in solution.Wherein work electricity
It is platinum electrode that ultracapacitor compound electric pole piece extremely of the invention, reference electrode are Ag/AgCl, auxiliary electrode, test electricity
Pressure scope is -0.2V～0.8V, and sweep speed is 10mV/s.
The specific capacitance of super capacitor electrode slice manufactured in the present embodiment is 565F/g.
Unaccomplished matter of the present invention is known technology.
Claims (3)
1. the manganese dioxide electrode piece that a kind of nano porous copper silver is supported, it is characterized by the transverse section of the electrode slice is divided into three layers,
Intermediate core layer is noncrystal substrate, and both sides are nano porous copper silver, and one layer in the silver-colored hole wall of nano porous copper and superficial growth
Even and fine little manganese dioxide；The thickness of electrode slice is 25～35 m, and inner side noncrystal substrate thickness degree is 12～28 m, and one side is received
Rice Porous Cu silver/manganese dioxide composite electrode material thickness degree is 3～11 m；
Described noncrystal substrate is CuxZryAgzAlloying component, wherein, 40≤x≤45,45≤y≤50,5≤z≤15, and x+y+
z=100；
Described nano porous copper silver is aperture in 10 ~ 90 nm.
2. the preparation method of the manganese dioxide electrode piece that nano porous copper as claimed in claim 1 silver is supported, it is characterized by bag
Include following steps：
The first step, prepares amorphous ribbon
Select high-purity C u, Zr, Ag metal as raw material, wherein, Cu, Zr and Ag purity is 99.9 wt%；According to target
Composition CuxZryAgzPrealloy composition is prepared, wherein, 40≤x≤45,45≤y≤50,5≤z≤15, and x+y+z=100, marked
Composition is atomic percent, then Cu-Zr-Ag alloy cast ingots is obtained in arc-melting furnace melting, removes superficial oxidation skin, cutting
After be put in quartz test tube, 8.0 × 10-4Under Pa vacuums, heating melts alloy cast ingot, then will be melted using argon
Alloy quickly blow out, the liquid alloy of the melting rapid solidification on the copper roller of high speed rotation forms AMORPHOUS ALLOY RIBBONS；
It is 1.0 MPa to blow casting pressure；Copper roller rotating speed is 30 ~ 40 m/s；A length of 60 ~ 300 cm of prepared AMORPHOUS ALLOY RIBBONS, it is wide
For 1.5 ~ 3 mm, thickness is 25 ~ 40 m；
Second step, prepares nano porous copper silver
At room temperature, AMORPHOUS ALLOY RIBBONS is placed in the mixed solution of Fluohydric acid. and hydrochloric acid and soaks after 30 ~ 100 min, is received
Rice Porous Cu ag material；In mixed solution, the concentration of HF is 0.1 ~ 0.3 M, and the concentration of HCl is 0.05 ~ 0.15 M, HF and HCl
Mol ratio be 2:1；
3rd step, the manganese dioxide electrode piece that nano porous copper silver is supported
Nano porous copper silver prepared by previous step is put in container and with dehydrated alcohol by its submergence, then Deca permanganic acid again
Potassium solution, stands 2 ~ 8 h after Deca；After by reacted product washes of absolute alcohol, obtain what nano porous copper silver was supported
Manganese dioxide electrode piece；Wherein, every 10 mg nano porous coppers silver mL potassium permanganate solutions of Deca 10.
3. the preparation method of the manganese dioxide electrode piece that nano porous copper as claimed in claim 2 silver is supported, it is characterized by high
The concentration of potassium manganate is 0.05 ~ 0.1 M.
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| CN102275903A (en) * | 2011-05-24 | 2011-12-14 | 东华大学 | Preparation method of graphene and manganese dioxide nanocomposite |
| CN103337374A (en) * | 2013-07-03 | 2013-10-02 | 河北工业大学 | Electrode plate for super capacitor and preparation method of electrode plate |
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| FR2759087B1 (en) * | 1997-02-06 | 1999-07-30 | Electricite De France | POROUS COMPOSITE PRODUCT WITH HIGH SPECIFIC SURFACE, PREPARATION METHOD AND ELECTRODE FOR ELECTROCHEMICAL ASSEMBLY FORMED FROM POROUS COMPOSITE FILM |
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| CN102275903A (en) * | 2011-05-24 | 2011-12-14 | 东华大学 | Preparation method of graphene and manganese dioxide nanocomposite |
| CN103337374A (en) * | 2013-07-03 | 2013-10-02 | 河北工业大学 | Electrode plate for super capacitor and preparation method of electrode plate |
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