CN104201004B - Preparation method of flexible hybrid super-capacitor electrode - Google Patents
Preparation method of flexible hybrid super-capacitor electrode Download PDFInfo
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- CN104201004B CN104201004B CN201410359480.0A CN201410359480A CN104201004B CN 104201004 B CN104201004 B CN 104201004B CN 201410359480 A CN201410359480 A CN 201410359480A CN 104201004 B CN104201004 B CN 104201004B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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 provides a preparation method of a flexible hybrid super-capacitor electrode. The preparation method comprises the steps of mixing and stirring a dispersant and deionized water together, next, adding a conductive agent for premixing, pouring the premix into a stirrer for mixing, next, adding a hydroxymethyl cellulose solution and continuing adding activated carbon to the stirrer and stirring, and then adding an binder and stirring to obtain a carbon material electrode active material, injecting the carbon material electrode active material into the ink box of an ink-jet printer and spraying the carbon material electrode active material on the front and back surfaces of a nickel foil in an ink-jet printing manner to form an carbon material electrode active material layer, next, putting the nickel foil in a tubular furnace, introducing oxygen and calcining to obtain the flexible hybrid super-capacitor electrode material. The preparation method of the flexible hybrid super-capacitor electrode has the advantages of highly available raw materials, low cost, good charge/discharge stability and long service life; a metal oxide active material can be prevented from being dissolved by an electrolyte so that the super-capacitor has the characteristics of high capacity, high energy density, wide working temperature range and long service life; as a result, the charge and discharge requirements of the capacitor on different electric appliances can be met.
Description
Technical field
The invention belongs to electrode of super capacitor preparation field, more particularly to a kind of flexible hybrid electrode of super capacitor
Preparation method.
Background technology
Ultracapacitor is a kind of novel energy storage apparatus between traditional capacitor and rechargeable battery.Ultracapacitor
Compared with traditional capacitor, it has, and capacity is big, power density is high, operating temperature range width and the characteristics of long service life, but
The energy density of ultracapacitor is much lower compared with conventional batteries, and the energy density for improving super capacitor system becomes super
The key of level capacitor.
The mixed system of super capacitor material composition, i.e., constituted with activated carbon using the material with redox active
Hybrid super capacitor, such as activated carbon/graphite, activated carbon/metal oxide and activated carbon/polymer, are all by improving
Material electrochemical performance improves electrode voltage, improves the energy density of capacitor.And this hybrid super capacitor is filling
In discharge process, the energy storage mechnism of both positive and negative polarity is different, therefore the double characteristic with ultracapacitor and battery.
The main preparation method of metal oxide base hybrid super capacitor is to mix metal oxide with material with carbon element, is adopted
The mode of coating makes electrode, metal oxide is well dispersed on material with carbon element.The hybrid super that at present prepared by the method
Capacitor composite RuO2/CNT（CNT）, with good chemical property, its specific capacity is up to 953 F/g, work(
Rate density is 5000 kW/kg, and energy density is 16.8 Wh/kg.But metal Ru price is high, largely hinders
RuO2Further applying as electrode material for super capacitor.And other metal oxides are although relatively inexpensive, exist with
Lower problem：One is that, during discharge and recharge, metal oxide is easily dissolved in electrolyte；Two is the process in discharge and recharge
In, the volume of metal oxide is susceptible to change, and before destroying, excellent structure, causes the stable charge/discharge of super capacitor
Property is bad, and the life-span is not long.
The content of the invention
The technical problem to be solved in the present invention be to provide a kind of raw material be easy to get, it is with low cost, stable charge/discharge is good, use
Life-span length, the preparation method of the flexible super capacitor electrode with good chemical property.
A kind of preparation method of flexible hybrid electrode of super capacitor, its step are as follows：
Step one：By dispersant and deionized water according to mass ratio 1:1～1:1.2 are mixed and stirred for 15 min～30min,
Being subsequently adding conductive agent carries out premix 15min～20min, pours into
Mass ratio with dispersant is 1:0.18～1:0.2；The hydroxymethyl cellulose solution that mass fraction is 2%～3% is subsequently adding, is stirred
25min～30 min is mixed, the conductive agent is 1 with the mass ratio of hydroxymethyl cellulose solution:0.2～1:0.3；According to conductive agent
Mass ratio with activated carbon is 1:7.8～1:After 8 continuously add activated carbon stirring 12h～16 h into agitator, according to conduction
Agent is 1 with the mass ratio of binding agent:0. 8～1:1 adds binding agent stirring 12h～16 h, obtains material with carbon element electrode activity thing
Matter；
Step 2：By in the print cartridge of obtained material with carbon element electrode active material injection ink-jet printer in step one, adopt
Material with carbon element electrode active material is sprayed material with carbon element electrode activity thing on positive and negative two faces of nickel foil by inkjet printing mode respectively
Matter layer；
Step 3：The metal forming that Jing processed sprays material with carbon element electrode active material layer is put in tube furnace, oxygen is filled with, plus
Heat is calcined 30min～60min, obtains flexible hybrid electrode material for super capacitor to 750 DEG C～1050 DEG C.
Mixture of the conductive agent for Ketjen black, conductive black and electrically conductive graphite, wherein Ketjen black and conductive black
Mass ratio is 1:0.5～1:0.6, Ketjen black is 1 with the mass ratio of electrically conductive graphite:0.3～1:0.4.
The material with carbon element electrode active material layer thickness is 100 μm～120 μm, and the metal foil thickness is 20 μm～40 μ
M, the metal forming are nickel foil, manganese paper tinsel or cobalt paper tinsel.
Described binding agent is butadiene-styrene rubber solution, polytetrafluoroethylsolution solution or Kynoar solution, wherein, butylbenzene rubber
The mass fraction of sol solution is 40%～50%, and the mass fraction of polytetrafluoroethylsolution solution is 40%～50%, Kynoar solution
Mass fraction be 40%～50%.
The dispersant is alkylnaphthalene sulfonate.
When the metal forming is heating in nickel foil, tube furnace, heating-up temperature is 950 DEG C～1050 DEG C.
When the metal forming is heating in manganese paper tinsel, tube furnace, heating-up temperature is 900 DEG C～1000 DEG C.
When the metal forming is heating in cobalt paper tinsel, tube furnace, heating-up temperature is 750 DEG C～800 DEG C.
When adding activated carbon, activated carbon is divided into into three parts, in adding agitator in three times, so that mixture is stirred more
Uniformly.
The invention has the beneficial effects as follows：
（1）By material with carbon element electrode active material dual coating on metal foil, it is put into tube furnace and is passed through oxygen heating, metal
Paper tinsel is oxidized, and obtains the metal oxide composite electrode of material with carbon element parcel；Material with carbon element has good electric conductivity, by gold
The coating function of category oxide can also increase the electric conductivity of metal oxidation.
（2）Preparation method is simple, and what is obtained by heating is metal oxide/material with carbon element combination electrode material；It is obtained
Electrode can realize that free bend is assembled into capacitor, it is to avoid traditional electrode bending is easily chapped；The composite construction outer layer
Material with carbon element electrode activity thing confrontation metal oxide there is protective effect, it is to avoid metal oxide active material is molten by electrolyte
Solution, also protects the structure of metal oxide active material not to be destroyed, and capacity is big, energy density to have ultracapacitor
The characteristics of high, operating temperature range width and long service life, meet charge-discharge power demand of the capacitor to different electrical appliances.In addition,
Electrode of super capacitor prepares electrode using inkjet technology, the active material particle of electrode material can be made less and be distributed
Uniformly, so as to improving the combination property of capacitor.
Description of the drawings
Fig. 1 is the structure chart of the flexible hybrid electrode material for super capacitor of the present invention.
Specific embodiment
With specific embodiment, the present invention will be further described below.
Embodiment 1
Step one：2g alkyl naphthalene sulfonic acids dipersant is injected in agitator, plus 2g deionized waters, stir 20 min；Plus
Enter 5g Ketjen blacks, 3g conductive blacks and 2g electrically conductive graphites and premix 15 min, in being subsequently poured into agitator, stir 30 min；Then plus
Enter the hydroxymethyl cellulose solution 2g that mass fraction is 3%, stir 30 min；Then 78g activated carbons stirring 16 is added in three times
H, each addition are 26g；The SBR emulsion that 8g mass fractions are 50% is added into stirring 12h in agitator and obtains final product ink
Watery activated carbon slurry, obtains material with carbon element electrode active material；
Step 2：By in the print cartridge of obtained material with carbon element electrode active material injection ink-jet printer in step one, adopt
It is 100 μm that material with carbon element electrode active material is distinguished thickness on positive and negative two faces that thickness is 20 μm of nickel foils by inkjet printing mode
Spraying material with carbon element electrode active material layer；
Step 3：The nickel foil that Jing processed sprays material with carbon element electrode active material layer is put in tube furnace, oxygen is filled with, is heated
To 950 DEG C, 60min is calcined, flexible hybrid electrode material for super capacitor is obtained；
Step 4：The flexible hybrid electrode material for super capacitor of preparation is put in vacuum drying chamber and is dried 6 h, cutting
Into positive pole and negative pole, positive pole cutting size is long 26.5cm, and wide 1.5cm, negative pole are cut to long 23cm, wide 1.5cm, then middle
Barrier film is put, appropriate aqueous electrolyte 6M KOH electrolyte is filled, being assembled into hybrid super capacitor carries out electro-chemical test.Jing
Electro-chemical test is crossed, the hybrid super capacitor specific capacity for being constituted is 364.53F/g, and energy density can reach 23.4Wh/kg,
Capacitor constant current charge-discharge 3000 times, cycle efficieny is maintained at more than 98%.
Embodiment 2
Step one：2g alkyl naphthalene sulfonic acids dipersant is injected in agitator, plus 2g deionized waters, stir 20 min；Plus
Enter 5g Ketjen blacks, 3g conductive blacks and 2g electrically conductive graphites and premix 15 min, in being subsequently poured into agitator, stir 30 min；Then plus
Enter the hydroxymethyl cellulose solution 2g that mass fraction is 3%, stir 30 min；Then 78g activated carbons stirring 16 is added in three times
H, each addition are 26g；The SBR emulsion that 8g mass fractions are 50% is added into stirring 12h in agitator and obtains final product ink
Watery activated carbon slurry, obtains material with carbon element electrode active material；
Step 2：By in the print cartridge of obtained material with carbon element electrode active material injection ink-jet printer in step one, adopt
It is 120 μm that material with carbon element electrode active material is distinguished thickness on positive and negative two faces that thickness is 40 μm of nickel foils by inkjet printing mode
Spraying material with carbon element electrode active material layer；
Step 3：The nickel foil that Jing processed sprays material with carbon element electrode active material layer is put in tube furnace, oxygen is filled with, is heated
To 1050 DEG C, 30min is calcined, flexible hybrid electrode material for super capacitor is obtained；
Step 4：The flexible hybrid electrode material for super capacitor of preparation is put in vacuum drying chamber and is dried 6 h, cutting
Into positive pole and negative pole, positive pole cutting size is long 26.5cm, and wide 1.5cm, negative pole are cut to long 23cm, wide 1.5cm, then middle
Barrier film is put, appropriate aqueous electrolyte 6M KOH electrolyte is filled, being assembled into hybrid super capacitor carries out electro-chemical test.Jing
Electro-chemical test is crossed, the hybrid super capacitor specific capacity for being constituted is 365.75F/g, and energy density can reach 23.6 Wh/
Kg, capacitor constant current charge-discharge 3000 times, cycle efficieny is maintained at more than 98%.
Embodiment 3
Step one：1.8g alkyl naphthalene sulfonic acids dipersant is injected in agitator, plus 2g deionized waters, stir 15min；Plus
Enter 5.4g Ketjen blacks, 2.7g conductive blacks and 1.9g electrically conductive graphites and premix 20 min, in being subsequently poured into agitator, stir 25 min；
The hydroxymethyl cellulose solution 2.5g that mass fraction is 3% is subsequently adding, 25 min are stirred；Then add 78.9g active in three times
Charcoal stirs 12h, and each addition is 26.3g；The SBR emulsion that 9g mass fractions are 45% is added in agitator and is stirred
Mix 16h and obtain final product ink shaped activated carbon slurry, obtain material with carbon element electrode active material；
Step 2：By in the print cartridge of obtained material with carbon element electrode active material injection ink-jet printer in step one, adopt
Material with carbon element electrode active material is that coating thickness is respectively on positive and negative two faces of 110 μm of manganese paper tinsels in thickness by inkjet printing mode
30 μm of material with carbon element electrode active material layers；
Step 3：The manganese paper tinsel that Jing processed sprays material with carbon element electrode active material layer is put in tube furnace, oxygen is filled with, is heated
900 DEG C, 45min is calcined, flexible hybrid electrode material for super capacitor is obtained；
Step 4：The flexible hybrid electrode material for super capacitor of preparation is put in vacuum drying chamber and is dried 6 h, cutting
Into positive pole and negative pole, positive pole cutting size is long 26.5cm, and wide 1.5cm, negative pole are cut to long 23cm, wide 1.5cm, then middle
Barrier film is put, appropriate aqueous electrolyte 6M KOH electrolyte is filled, being assembled into hybrid super capacitor carries out electro-chemical test.Jing
Electro-chemical test is crossed, the hybrid super capacitor specific capacity for being constituted is 371.33F/g, and energy density can reach 21.56 Wh/
Kg, capacitor constant current charge-discharge 3000 times, cycle efficieny is maintained at more than 98%.
Embodiment 4
Step one：1.8g alkyl naphthalene sulfonic acids dipersant is injected in agitator, plus 2g deionized waters, stir 15min；Plus
Enter 5.4g Ketjen blacks, 2.7g conductive blacks and 1.9g electrically conductive graphites and premix 20 min, in being subsequently poured into agitator, stir 25 min；
The hydroxymethyl cellulose solution 2.5g that mass fraction is 3% is subsequently adding, 25 min are stirred；Then add 78.9g active in three times
Charcoal stirs 12h, and each addition is 26.3g；The polytetrafluoroethylsolution solution that 9g mass fractions are 45% is added in agitator
Stirring 16h obtains final product ink shaped activated carbon slurry, obtains material with carbon element electrode active material；
Step 2：By in the print cartridge of obtained material with carbon element electrode active material injection ink-jet printer in step one, adopt
Material with carbon element electrode active material is that coating thickness is respectively on positive and negative two faces of 30 μm of manganese paper tinsels in thickness by inkjet printing mode
100 μm of material with carbon element electrode active material layers；
Step 3：The manganese paper tinsel that Jing processed sprays material with carbon element electrode active material layer is put in tube furnace, oxygen is filled with, is heated
1000 DEG C, 45min is calcined, flexible hybrid electrode material for super capacitor is obtained；
Step 4：The flexible hybrid electrode material for super capacitor of preparation is put in vacuum drying chamber and is dried 6 h, cutting
Into positive pole and negative pole, positive pole cutting size is long 26.5cm, and wide 1.5cm, negative pole are cut to long 23cm, wide 1.5cm, then middle
Barrier film is put, appropriate aqueous electrolyte 6M KOH electrolyte is filled, being assembled into hybrid super capacitor carries out electro-chemical test.Jing
Electro-chemical test is crossed, the hybrid super capacitor specific capacity for being constituted is 371.95F/g, and energy density can reach 21.44 Wh/
Kg, capacitor constant current charge-discharge 3000 times, cycle efficieny is maintained at more than 98%.
Embodiment 5
Step one：1.9g alkyl naphthalene sulfonic acids dipersant is injected in agitator, plus 2.28g deionized waters, stirring
30min；5.2g Ketjen blacks, 2.72g conductive blacks and 2.08g electrically conductive graphites premix 18min is added, is stirred in being subsequently poured into agitator
Mix 28min；The hydroxymethyl cellulose solution 3g that mass fraction is 2% is subsequently adding, 28min is stirred；Then add in three times
79.98g activated carbons stir 14h, and each addition is 26.66g；The SBR emulsion that 10g mass fractions are 40% is added
14h is stirred in agitator and obtains final product ink shaped activated carbon slurry, obtain material with carbon element electrode active material；
Step 2：By in the print cartridge of obtained material with carbon element electrode active material injection ink-jet printer in step one, adopt
Material with carbon element electrode active material is that coating thickness is respectively on positive and negative two faces of 20 μm of cobalt paper tinsels in thickness by inkjet printing mode
100 μm of material with carbon element electrode active material layers；
Step 3：The cobalt paper tinsel that Jing processed sprays material with carbon element electrode active material layer is put in tube furnace, oxygen is filled with, is heated
To 750 DEG C, 60min is calcined, flexible hybrid electrode material for super capacitor is obtained；
Step 4：The flexible hybrid electrode material for super capacitor of preparation is put in vacuum drying chamber and is dried 6 h, cutting
Into positive pole and negative pole, positive pole cutting size is long 26.5cm, and wide 1.5cm, negative pole are cut to long 23cm, wide 1.5cm, then middle
Barrier film is put, aqueous electrolyte 6M KOH electrolyte is filled, being assembled into hybrid super capacitor carries out electro-chemical test.Through electricity
Test chemical, the hybrid super capacitor specific capacity for being constituted are 265.23F/g, and energy density can reach 17.79 Wh/kg, electric
Container constant current charge-discharge 3000 times, cycle efficieny is maintained at more than 98%.
Embodiment 6
Step one：1.9g alkyl naphthalene sulfonic acids dipersant is injected in agitator, plus 2.28g deionized waters, stirring
30min；5.2g Ketjen blacks, 2.72g conductive blacks and 2.08g electrically conductive graphites premix 18min is added, is stirred in being subsequently poured into agitator
Mix 28min；The hydroxymethyl cellulose solution 3g that mass fraction is 2% is subsequently adding, 28min is stirred；Then add in three times
79.98g activated carbons stir 14h, and each addition is 26.66g；The Kynoar solution that 10g mass fractions are 40% is added again
14h is stirred in entering agitator and obtains final product ink shaped activated carbon slurry, obtain material with carbon element electrode active material；
Step 2：By in the print cartridge of obtained material with carbon element electrode active material injection ink-jet printer in step one, adopt
It is 120 μm of carbon that material with carbon element electrode active material is distinguished coating thickness on positive and negative two faces of 40 μm of cobalt paper tinsels by inkjet printing mode
Material electrodes active material layer；
Step 3：The cobalt paper tinsel that Jing processed sprays material with carbon element electrode active material layer is put in tube furnace, oxygen is filled with, is heated
To 800 DEG C, 50min is calcined, flexible hybrid electrode material for super capacitor is obtained；
Step 4：The flexible hybrid electrode material for super capacitor of preparation is put in vacuum drying chamber and is dried 6 h, cutting
Into positive pole and negative pole, positive pole cutting size is long 26.5cm, and wide 1.5cm, negative pole are cut to long 23cm, wide 1.5cm, then middle
Barrier film is put, aqueous electrolyte 6M KOH electrolyte is filled, being assembled into hybrid super capacitor carries out electro-chemical test.Through electricity
Test chemical, the hybrid super capacitor specific capacity for being constituted are 265.88F/g, and energy density can reach 18.07Wh/kg, electric
Container constant current charge-discharge 3000 times, cycle efficieny is maintained at more than 98%.
Claims (8)
1. a kind of preparation method of flexible hybrid electrode of super capacitor, is characterized in that：Step is as follows：
Step one：By dispersant and deionized water according to mass ratio 1:1～1:1.2 are mixed and stirred for 15 min～30min, then
Add conductive agent carry out premix 15min～20min, pour into, the conductive agent with point
The mass ratio of powder is 1:0.18～1:0.2；The hydroxymethyl cellulose solution that mass fraction is 2%～3% is subsequently adding, is stirred
25min～30 min, the conductive agent are 1 with the mass ratio of hydroxymethyl cellulose solution:0.2～1:0.3；According to conductive agent with
The mass ratio of activated carbon is 1:7.8～1:After 8 continuously add activated carbon stirring 12h～16 h into agitator, according to conductive agent
Mass ratio with binding agent is 1:0. 8～1:1 adds binding agent stirring 12h～16 h, obtains material with carbon element electrode active material；
Step 2：Obtained material with carbon element electrode active material in step one is injected in the print cartridge of ink-jet printer, using ink-jet
Material with carbon element electrode active material is sprayed material with carbon element electrode active material layer on positive and negative two faces of nickel foil by printing type respectively；
Step 3：The nickel foil that Jing processed sprays material with carbon element electrode active material layer is put in tube furnace, oxygen is filled with, is heated to
750 DEG C～1050 DEG C, 30min～60min is calcined, obtain composite and flexible hybrid super capacitor electrode material, composite and flexible is mixed
Close electrode material for super capacitor to be from top to bottom made up of carbon material layer, nickel oxide layer, carbon material layer successively.
2. the preparation method of flexible hybrid electrode of super capacitor according to claim 1, is characterized in that：The conductive agent
For the mixture of Ketjen black, conductive black and electrically conductive graphite, wherein Ketjen black is 1 with the mass ratio of conductive black:0.5～1:
0.6, Ketjen black is 1 with the mass ratio of electrically conductive graphite:0.3～1:0.4.
3. the preparation method of flexible hybrid electrode of super capacitor according to claim 1, is characterized in that：The material with carbon element
Electrode active material layer thickness is 100 μm～120 μm.
4. the preparation method of flexible hybrid electrode of super capacitor according to claim 1, is characterized in that：The nickel foil is thick
Spend for 20 μm～40 μm.
5. the preparation method of flexible hybrid electrode of super capacitor according to claim 1, is characterized in that：Described bonding
Agent is butadiene-styrene rubber solution, polytetrafluoroethylsolution solution or Kynoar solution, and wherein, the mass fraction of butadiene-styrene rubber solution is
40%～50%, the mass fraction of polytetrafluoroethylsolution solution is 40%～50%, the mass fraction of Kynoar solution is 40%～
50%。
6. the preparation method of flexible hybrid electrode of super capacitor according to claim 1, is characterized in that：The dispersant
For alkylnaphthalene sulfonate.
7. the preparation method of flexible hybrid electrode of super capacitor according to claim 1, is characterized in that：Add in tube furnace
When hot, heating-up temperature is 950 DEG C～1050 DEG C.
8. the preparation method of flexible hybrid electrode of super capacitor according to claim 1, is characterized in that：Add activated carbon
When, activated carbon is divided into into three parts, in adding agitator in three times.
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| CN107680822A (en) * | 2017-06-21 | 2018-02-09 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of preparation method of double electric layers supercapacitor electrode slurry |
| CN107731564A (en) * | 2017-06-21 | 2018-02-23 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of preparation method of double electric layers supercapacitor organic system electrode slurry |
| CN107369811A (en) * | 2017-08-21 | 2017-11-21 | 柔电（武汉）科技有限公司 | A kind of preparation method of flexible pole piece |
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| CN1437278A (en) * | 2003-03-13 | 2003-08-20 | 复旦大学 | Ultrathin electrode, diaphragm, ultrathin primary battery, ultrathin secondary recyclable charge-discharge battery and preparation methods of electrode, diaphragm and battery |
| CN103515109A (en) * | 2013-09-16 | 2014-01-15 | 哈尔滨工程大学 | Preparation method of electrode material of supercapacitor made of carbon-coating titanium dioxide loading nickel and nickel oxide composite materials |
| CN103762095A (en) * | 2013-12-29 | 2014-04-30 | 渤海大学 | Method for manufacturing mixed-type supercapacitor in ink-jet printing mode |
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| US20030160215A1 (en) * | 2002-01-31 | 2003-08-28 | Zhenhua Mao | Coated carbonaceous particles particularly useful as electrode materials in electrical storage cells, and methods of making the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1437278A (en) * | 2003-03-13 | 2003-08-20 | 复旦大学 | Ultrathin electrode, diaphragm, ultrathin primary battery, ultrathin secondary recyclable charge-discharge battery and preparation methods of electrode, diaphragm and battery |
| CN103515109A (en) * | 2013-09-16 | 2014-01-15 | 哈尔滨工程大学 | Preparation method of electrode material of supercapacitor made of carbon-coating titanium dioxide loading nickel and nickel oxide composite materials |
| CN103762095A (en) * | 2013-12-29 | 2014-04-30 | 渤海大学 | Method for manufacturing mixed-type supercapacitor in ink-jet printing mode |
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