CN105655151B - A kind of MnO2The preparation method of/C/CNT combination electrode materials - Google Patents
A kind of MnO2The preparation method of/C/CNT combination electrode materials Download PDFInfo
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- CN105655151B CN105655151B CN201511016064.1A CN201511016064A CN105655151B CN 105655151 B CN105655151 B CN 105655151B CN 201511016064 A CN201511016064 A CN 201511016064A CN 105655151 B CN105655151 B CN 105655151B
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- 239000007772 electrode material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000004070 electrodeposition Methods 0.000 claims abstract description 28
- 239000012528 membrane Substances 0.000 claims abstract description 24
- 238000001471 micro-filtration Methods 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005266 casting Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- 238000007747 plating Methods 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229920002301 cellulose acetate Polymers 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000003115 supporting electrolyte Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000003491 array Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 39
- 229910021393 carbon nanotube Inorganic materials 0.000 description 34
- 239000002041 carbon nanotube Substances 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses a kind of MnO2The preparation method of/C/CNT combination electrode materials.Include the following steps：The casting solution containing CNT is coated on clean sheet metal, so that it is formed 90~150 μm of a thickness on sheet metal, aperture is 0.05~10 μm of organic micro-filtration membrane for including CNT；The method electro-deposition on sheet metal for sheet metal obtained by step 1) being utilized anodic electrodeposition manganese dioxide, is cleaned, dry；So that micro-filtration membrane is carbonized through high-temperature process sheet metal obtained by step 2), MnO is obtained after cooling2/ C/CNT combination electrode materials.MnO of the present invention2With array structure, C/CNT is filled between array manganese dioxide, the MnO of columnar arrays structure2The specific surface area of electrode material can not only effectively be improved and ion can be conducive to and quickly transmitted between equally distributed columnar arrays structure.
Description
Technical field
The invention belongs to technical field of composite materials, it is related to a kind of specific preparation method of electrode material for super capacitor.
Background technology
Ultracapacitor is a kind of a kind of new type of energy storage device between battery and traditional physical capacitor.Super electricity
Container has the characteristics that energy density is high, has extended cycle life, can high current charge-discharge, fast charging and discharging, therefore with extensive
Application prospect, in recent years by extensive research and concern.And electrode is the core component of ultracapacitor, is directly affected
To the performance of ultracapacitor.Its effect of electrode is storage and release charge, is the key that determine condenser charge storage capacity,
Therefore it is required that electrode has the property that：Stability is good, shape or performance change does not occur because of multiple charge and discharge；Electric conductivity
It is good, be conducive to high current charge-discharge, reduce capacitor internal power consumption, improves capacitor high power discharge ability.Electrode
Performance is closely related with electrode surface area, and for electric double layer, electrode surface area is bigger, then the electric double layer area formed is got over
Greatly, condenser capacity is bigger；For faraday fake capacitance, surface area is bigger, can carry more electrodes in electrode surface
Active material, thus condenser capacity is bigger, while electrode surface area is bigger, electrode also bigger with the contact area of electrolyte
Active material utilization is high, and large current discharging capability is stronger.However manganese dioxide as electrode material when, because it is semiconductor,
Therefore conductivity is low, the electron-transport being unfavorable in redox reaction limits the performance of charge and discharge, and it is high theoretical to eventually lead to it
Specific capacity feature is difficult to play.Therefore, it is necessary to be aided with conductive material to make up the feature of its conductivity difference.
In order to improve the electric conductivity of manganese dioxide, existing method is exactly to add into the electrode material containing manganese dioxide
Increase the material of conductivity, common method be exactly added into the active material containing manganese dioxide activated carbon, carbon nanotube with
And the high electrical conductivity materials progress such as conducting polymer is compound.But these materials are carried out in recombination process with conventional method
All must be added to the macromolecules such as polytetrafluoroethylene (PTFE) be stained with knot agent come improve overall electrode substance be stained with knot property and mechanical stability.But
High polymer binder can reduce the electric conductivity of composite material after being added, to influence the chemical property of electrode material entirety.Example
Such as：Yang Shao-Horn et al. [Yang Shao-Horn et.al, ACS NANO. (2010) 4:3889-3896] oxygen is utilized
The method for changing reduction loads manganese dioxide on carbon pipe, and this excessively high easy generation of carbon pipe surface density is reunited to be unfavorable for being electrolysed
Liquid enters inside carbon pipe and the insertion and abjection of ion, causes high-rate charge-discharge capability and cycle performance poor.
To obtain high-performance super capacitor other than improving electrode material electric conductivity, increase the ion of electrode material
Transmission rate and the specific surface area of material are also a kind of important means.To increase the surface area of electrode material, existing technology master
There are the structures such as porous, hollow ball-shape, lamella to improve electrode reaction contact area.But the fake capacitance master that manganese dioxide provides
If being happened at nearly electrode surface area, other regions cannot apply.Cause the utilization rate of manganese dioxide relatively low in this way.Increase
Add the prior art of ion transportation to have and electrode material is fabricated to array column structure, to improve ion in column structure
Between transmission rate.Such as Pulickel M.Ajayan et al. [Pulickel M.Ajayan et.al, NANO LETTERS.
(2009)9:
1002-1006] using oxide-reduction method the manganese dioxide of oriented tube-shaped structure is generated in alumina formwork, and
It grows carbon nanotube in tubular structure using CVD afterwards and is eventually adding gold to improve its electric conductivity, although in this way may be used
To obtain ideal electrode material, but process is cumbersome, cost is higher.
Invention content
Present invention aims at a kind of preparation method of electrode material for super capacitor is provided, electrode material obtained can have
Effect improves the electric conductivity of electrode material, and the electrode material has higher energy density and power density, and can be straight
It connects and makees electrode without adding any binder, there is preferable stability.
In order to achieve the above objectives, as follows using technical solution：
A kind of MnO2The preparation method of/C/CNT combination electrode materials, includes the following steps：
1) casting solution containing CNT is coated on clean sheet metal, it is made to form a thickness 90~150 on sheet metal
μm, aperture be 0.05~10 μm of organic micro-filtration membrane for including CNT；
2) sheet metal obtained by step 1) is put into the manganese salt solution and 0.1~2mol/L supporting electrolytes of 0.1~3mol/L
In the plating solution formed, the electro-deposition on sheet metal using the method for anodic electrodeposition manganese dioxide is cleaned, dry；
3) so that micro-filtration membrane is carbonized through high-temperature process sheet metal obtained by step 2), MnO is obtained after cooling2/ C/CNT is compound
Electrode material；Wherein MnO2With array structure, C/CNT is filled between array manganese dioxide.
By said program, the step 1) micro-filtration membrane is cellulose acetate film, polytetrafluoroethylene film, polyvinylidene fluoride film
Any one.
By said program, the step 2) manganese salt is manganese sulfate, manganese chloride or manganese nitrate.
By said program, the step 2) conductive salt is sodium sulphate, sodium chloride, potassium chloride, potassium nitrate or sodium nitrate.
By said program, the step 2) electrodeposition condition is：Voltage is 1~10V, sedimentation time is 30~90min, plating
20~80 DEG C of liquid temperature and pH value 4~8.
By said program, step 3) the high-temperature process condition is to handle 20 in 400~1000 DEG C under atmosphere of inert gases
~90 min.
Manganese dioxide is loaded currently with carbon nanotube (CNT) to improve manganese dioxide electric conductivity, so as to improve electrode
Energy density of the material electrochemical performance to obtain is about in 30Wh/kg or so, power density about in 4000W/kg or so.
The present invention utilizes the MnO that column structure is oriented made from the electro-deposition method in micro-filtration membrane aperture2Ion can be improved well to exist
Column MnO2Between transmission rate, CNT can improve the electric conductivity of electrode material.
Advantageous effect of the present invention is：
1) MnO of the present invention2For equally distributed columnar arrays structure, C/CNT is uniformly filled between manganese dioxide；Column
The MnO of array structure2The specific surface area of electrode material can not only effectively be improved and ion can be conducive to and be uniformly distributed
Columnar arrays structure between quickly transmit.
2) C/CNT, which is uniformly filled in the structure between manganese dioxide columnar arrays, can not only improve the electric conductivity of electrode material
It can and improve the energy density and power density of ultracapacitor.
3) electrode material produced by the present invention can directly make electrode without adding any binder, thus electrode is made to have
Preferable stability.
4) preparation process of the present invention is simple, can make variously-shaped electrode.
Specific implementation mode
Following embodiment further illustrates technical scheme of the present invention, but not as limiting the scope of the invention.
MnO of the present invention2The preparation process of/C/CNT combination electrode materials is as follows：
1) casting solution containing CNT is coated on clean sheet metal, it is made to form a thickness 90~150 on sheet metal
μm, aperture be 0.05~10 μm of micro-filtration membrane for including CNT.Casting solution is that membrane material-high-molecular compound is dissolved in good solvent
In, micro-filtration membrane Polymer Solution can be formed under certain condition by adding pore-foaming agent.Micro-filtration membrane is cellulose acetate film, gathers
Organic microfiltration membranes such as vinylidene fluoride film.
2) the sheet metal of above-mentioned processing be put into 0.1~3mol/L manganese salt solution and 0.1~2mol/L supporting electrolytes,
In the plating solution that 20~80 DEG C of temperature and pH value are 4~8, using the method for anodic electrodeposition manganese dioxide in electricity on sheet metal
30~90min of electro-deposition under the constant pressure that pressure is 1~10V.It waits for taking out after electro-deposition, is cleaned with deionized water, is dry.
3) being placed on during inert gas atmosphere encloses 20~90min of processing under 400 DEG C~1000 DEG C high temperature keeps organic micro-filtration thin
Film is carbonized.It is allowed to naturally cool to room temperature under atmosphere of inert gases after pending, you can to obtain MnO2/ C/CNT is compound
Electrode material, wherein MnO2With array structure, C/CNT is filled between array manganese dioxide.
Embodiment 1
Step 1：The cellulose acetate casting solution containing CNT is coated in clean titanium sheet, it is made to form one in titanium sheet
90 μm of thickness, aperture are 0.05 μm of cellulose acetate micro-filtration membrane for including CNT.
Step 2：The titanium sheet of above-mentioned processing be put into the manganese sulfate solution of 0.15mol/L, 0.1mol/L metabisulfite solutions,
20 DEG C of bath temperature and pH value be in 4 plating solutions, using the method for anodic electrodeposition manganese dioxide in titanium sheet in voltage be 1V's
Electro-deposition 30min under constant pressure.It waits for taking out after electro-deposition, is cleaned with deionized water, is dry.
Step 3：There is the titanium sheet of manganese dioxide to be placed in nitrogen atmosphere electro-deposition after drying to handle under 400 DEG C of high temperature
90min makes cellulose acetate micro-filtration membrane be carbonized.It is allowed to naturally cool to room temperature after pending, you can to obtain MnO2/C/
CNT combination electrode materials, wherein MnO2With array structure, C/CNT is filled between array manganese dioxide.
1M Na are put into the electrode material obtained by above-mentioned steps2SO4Electrochemical property test is carried out in solution, it is measured
The energy density of electrode material is 55Wh/kg, power density 3500W/kg, and capacity retention ratio is 95% after recycling 5000 times.
Embodiment 2
Step 1：The polysulfones casting solution containing CNT is coated in clean nickel sheet, it is made to form a thickness 90 in nickel sheet
μm, aperture be 5 μm of polysulfones micro-filtration membranes for including CNT.
Step 2：The nickel sheet of above-mentioned processing is put into the manganese sulfate solution and 1mol/L sodium chloride solutions, plating solution of 2mol/L
Temperature 50 C and pH value are in 5 plating solutions, using the method for anodic electrodeposition manganese dioxide in voltage in the nickel sheet for have microfiltration membranes
For electro-deposition 30min under the constant pressure of 2V.It waits for taking out after electro-deposition, is cleaned with deionized water, is dry.
Step 3：There is the nickel sheet of manganese dioxide to be placed in argon atmosphere electro-deposition after drying to handle under 600 DEG C of high temperature
60min makes polysulfones micro-filtration membrane be carbonized.It is allowed to naturally cool to room temperature after pending, you can to obtain MnO2/ C/CNT is multiple
Composite electrode material, wherein MnO2With array structure, C/CNT is filled between array manganese dioxide.
1M Na are put into the electrode material obtained by above-mentioned steps2SO4Electrochemical property test is carried out in solution, it is measured
The energy density of electrode material is 52Wh/kg, power density 4000W/kg, and capacity retention ratio is 95% after recycling 5000 times.
Embodiment 3
Step 1：The polytetrafluoroethylene (PTFE) casting solution containing CNT is coated in clean titanium sheet, it is made to form one in titanium sheet
60 μm of thickness, aperture are 5 μm of polytetrafluoroethylene (PTFE) micro-filtration membranes for including CNT.
Step 2：The titanium sheet of above-mentioned processing is put into the manganese sulfate solution and 1mol/L metabisulfite solutions, plating solution of 2mol/L
80 DEG C of temperature and pH value are in 8 plating solutions, using the method for anodic electrodeposition manganese dioxide in electricity on the sheet metal for have microfiltration membranes
Electro-deposition 30min under the constant pressure that pressure is 3V.It waits for taking out after electro-deposition, is cleaned with deionized water, is dry.
Step 3：There is the titanium sheet of manganese dioxide to be placed in nitrogen atmosphere electro-deposition after drying to handle under 700 DEG C of high temperature
80min makes cellulose acetate micro-filtration membrane be carbonized.It is allowed to naturally cool to room temperature after pending, you can to obtain MnO2/C/
CNT combination electrode materials, wherein MnO2With array structure, C/CNT is filled between array manganese dioxide.
1M Na are put into the electrode material obtained by above-mentioned steps2SO4Electrochemical property test is carried out in solution, it is measured
The energy density of electrode material is 50Wh/kg, power density 4100W/kg, and capacity retention ratio is 90% after recycling 5000 times.
Embodiment 4
Step 1：The Kynoar casting solution containing CNT is coated in clean nickel sheet, it is made to be formed on sheet metal
One 90 μm of thickness, aperture are 10 μm of polyvinylidene fluoride microporous filtering films for including CNT.
Step 2：The nickel sheet of above-mentioned processing is put into the manganese sulfate solution and 1mol/L sodium chloride solutions, plating solution of 2mol/L
In the plating solution that temperature 60 C and pH value are 7, using the method for anodic electrodeposition manganese dioxide in electricity in the nickel sheet for have microfiltration membranes
Electro-deposition 40min under the constant pressure that pressure is 2.5V.It waits for taking out after electro-deposition, is cleaned with deionized water, is dry.
Step 3：There is the nickel sheet of manganese dioxide to be placed in nitrogen atmosphere electro-deposition after drying to handle under 1000 DEG C of high temperature
50min makes cellulose acetate micro-filtration membrane be carbonized.It is allowed to naturally cool to room temperature after pending, you can to obtain MnO2/C/
CNT combination electrode materials, wherein MnO2With array structure, C/CNT is filled between array manganese dioxide.
1M Na are put into the electrode material obtained by above-mentioned steps2SO4Electrochemical property test is carried out in solution, it is measured
The energy density of electrode material is 53Wh/kg, power density 4600W/kg, and capacity retention ratio is 89% after recycling 5000 times.
Claims (4)
1. a kind of MnO2The preparation method of/C/CNT combination electrode materials, it is characterised in that include the following steps：
1) casting solution containing CNT is coated on clean sheet metal, make its formed on sheet metal 90~150 μm of a thickness,
Aperture is 0.05~10 μm of organic micro-filtration membrane for including CNT；The micro-filtration membrane is cellulose acetate film, polytetrafluoroethylene (PTFE)
Any one of film, polyvinylidene fluoride film；
2) sheet metal obtained by step 1) is put into the manganese salt solution and 0.1~2mol/L supporting electrolytes institute group of 0.1~3mol/L
At plating solution in, the electro-deposition on sheet metal using the method for anodic electrodeposition manganese dioxide is cleaned, dry；The electro-deposition
Condition is：Voltage is 1~10V, sedimentation time is 30~90min, 20~80 DEG C of bath temperature and pH value 4~8；
3) so that micro-filtration membrane is carbonized through high-temperature process sheet metal obtained by step 2), MnO is obtained after cooling2/ C/CNT combination electrodes
Material；Wherein MnO2With array structure, C/CNT is filled between array manganese dioxide.
2. MnO as described in claim 12The preparation method of/C/CNT combination electrode materials, it is characterised in that the step 2) manganese salt
For manganese sulfate, manganese chloride or manganese nitrate.
3. MnO as described in claim 12The preparation method of/C/CNT combination electrode materials, it is characterised in that the step 2) conduction
Salt is sodium sulphate, sodium chloride, potassium chloride, potassium nitrate or sodium nitrate.
4. MnO as described in claim 12The preparation method of/C/CNT combination electrode materials, it is characterised in that the step 3) high temperature
Treatment conditions are to handle 20~90min in 400~1000 DEG C under atmosphere of inert gases.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102468056A (en) * | 2010-11-11 | 2012-05-23 | 中国科学院青岛生物能源与过程研究所 | Electrode material of supercapacitor, and manufacturing method and application of electrode material |
| CN103337639A (en) * | 2013-06-24 | 2013-10-02 | 太原理工大学 | Preparation method of carbon nano tube array/carbon fiber fabric integrated three-dimensional porous air electrode |
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