CN104900417A - Water system asymmetric type supercapacitor based on Zn(OH)2/Co(OH)2 composite anode and preparing method thereof - Google Patents
Water system asymmetric type supercapacitor based on Zn(OH)2/Co(OH)2 composite anode and preparing method thereof Download PDFInfo
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- CN104900417A CN104900417A CN201510274963.5A CN201510274963A CN104900417A CN 104900417 A CN104900417 A CN 104900417A CN 201510274963 A CN201510274963 A CN 201510274963A CN 104900417 A CN104900417 A CN 104900417A
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 10
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title abstract 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 title abstract 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- 239000002250 absorbent Substances 0.000 claims description 18
- 230000002745 absorbent Effects 0.000 claims description 18
- 239000003610 charcoal Substances 0.000 claims description 18
- 239000011780 sodium chloride Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 239000006230 acetylene black Substances 0.000 claims description 14
- 239000006260 foam Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 230000004888 barrier function Effects 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 238000010291 electrical method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 20
- 230000004087 circulation Effects 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 5
- 239000003365 glass fiber Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 3
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 206010013786 Dry skin Diseases 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
Abstract
The invention discloses a water system asymmetric type supercapacitor based on a Zn(OH)2/Co(OH)2 composite anode and the preparing method thereof, wherein the water system asymmetric type supercapacitor is a buckle type capacitor formed by assembling the Zn(OH)2/Co(OH)2 composite anode, an active-carbon-material cathode, a glass fiber ester diaphragm, potassium hydroxide electrolyte and a housing. The voltage window of the water system asymmetric type supercapacitor reaches to 1.5V. When the power density is 6.2kWkg-1, high circulation stability is still ensured, and the over 99% of starting values can be retained in 5000 times of circulation. The water system asymmetric type supercapacitor has promising business application value, is simple in preparing process, safe in use, low in cost and is environmental friendly.
Description
Technical field
The present invention relates to a kind of based on Zn (OH)
2/ Co (OH)
2water system asymmetrical type ultracapacitor of composite positive pole and preparation method thereof, belongs to supercapacitor technologies field.
Background technology
Ultracapacitor is a kind of novel energy-storing device having traditional capacitor and battery advantage concurrently.Because it possesses high power density, fast discharge and recharge, stable cycle life and advantages of environment protection, obtain worldwide common concern in recent years.At present, business-like ultracapacitor in water system energy density at 3 ~ 4Wh kg
-1, its lower energy density limits the application of further business.Assembling asymmetric super-capacitor is a kind of method of effective raising energy density, its usually by electric double layer material with carbon element as negative material, fake capacitance material assembles as positive electrode.
Fake capacitance material mainly contains metal oxide/hydroxide, conducting polymer with its compound etc.Wherein metal oxide and hydroxide have higher theoretical specific capacity and are widely used.Co (OH)
2theoretical specific capacity be 3460F g
-1, and price is low, environmental friendliness, is one of a kind of very promising electrode material.But the Co that a large amount of results of study shows (OH)
2cyclical stability is lower, therefore improves its cycle performance, the circulation behavior particularly in asymmetric super-capacitor, has important meaning for its further research in ultracapacitor.United States Patent (USP) (US3066178A) has prepared Co (OH)
2with Ni (OH)
2composite material, and show good chemical property.The Co (OH) of the different proportion that Tang etc. (Electrochim.Acta 2015,161,279) prepare
2with Ni (OH)
2composite material shows higher energy density in asymmetric super-capacitor, but its cycle performance (being 84.4% after 1500 circulations) is not ideal enough.
Summary of the invention
The defect that energy density is lower in water system is there is for symmetric form ultracapacitor traditional in prior art, and Co (OH)
2/ Ni (OH)
2although composite material shows higher energy density in asymmetric super-capacitor, there is the defect of cycle performance difference, the object of the invention is to be to provide a kind of energy density higher and have excellent cycling stability containing Zn (OH)
2/ Co (OH)
2the asymmetric sexual type ultracapacitor of water system of anode composite.
Another object of the present invention be to provide a kind of simple, low cost preparation is described based on Zn (OH)
2/ Co (OH)
2the method of the water system asymmetrical type ultracapacitor of anode composite.
In order to realize technical purpose of the present invention, the invention provides a kind of based on Zn (OH)
2/ Co (OH)
2the water system asymmetrical type ultracapacitor of anode composite, is made up of positive pole, negative pole, barrier film, electrolyte and shell;
Described positive pole is by Zn (OH)
2/ Co (OH)
2the composite material that composite positive pole and acetylene black and PVDF 70 ~ 80:10 in mass ratio ~ 15:10 ~ 15 form is coated in the Zn (OH) that nickel foam obtains
2/ Co (OH)
2anode composite;
Described Zn (OH)
2/ Co (OH)
2composite positive pole is using two identical cobalt sheets as positive and negative electrode, with NaCl and Zn (CH
3cOO)
2mixed solution as electrolyte, prepared by AC electrical method.
Preferred Zn (OH)
2/ Co (OH)
2zn (OH) in composite positive pole
2with Co (OH)
2mol ratio be 0.1 ~ 1:0.1 ~ 1.
Preferred NaCl and Zn (CH
3cOO)
2mixed solution in the concentration range of NaCl be 0.5 ~ 3.5mol/L, Zn (CH
3cOO)
2concentration range be 0.005 ~ 1mol/L.
The AC electrical method that the present invention adopts preferably uses power frequency for 50Hz, and voltage is the alternating current of 3 ~ 30V.
Present invention also offers one to prepare based on Zn (OH)
2/ Co (OH)
2the method of the water system asymmetrical type ultracapacitor of anode composite, the method comprises the following steps:
Step one: preparation Zn (OH)
2/ Co (OH)
2composite positive pole;
Using two identical cobalt sheets as positive and negative electrode, with NaCl and Zn (CH
3cOO)
2mixed solution as electrolyte, be 50Hz in frequency, voltage is electrolysis 2 ~ 24h under the alternating current of 3 ~ 30V, obtains Zn (OH)
2/ Co (OH)
2composite positive pole; Described NaCl and Zn (CH
3cOO)
2mixed solution in the concentration range of NaCl be 0.5 ~ 3.5mol/L, Zn (CH
3cOO)
2concentration range be 0.005 ~ 1mol/L;
Step 2: preparation Zn (OH)
2/ Co (OH)
2anode composite
By gained Zn (OH)
2/ Co (OH)
2composite positive pole mixes with acetylene black, PVDF 70 ~ 80:10 in mass ratio ~ 15:10 ~ 15, then adds after NMP stirs, and is coated in nickel foam, vacuumize, compressing tablet, obtains Zn (OH)
2/ Co (OH)
2anode composite;
Step 3: prepare absorbent charcoal material negative pole
By mixing of absorbent charcoal material and acetylene black, PVDF 75 ~ 85:10 in mass ratio ~ 15:5 ~ 10, then add after NMP stirs, be coated in nickel foam, vacuumize, compressing tablet, obtain absorbent charcoal material negative pole;
Step 4: assembling water system asymmetrical type ultracapacitor
Using KOH solution as electrolyte, at mounted Zn (OH)
2/ Co (OH)
2anode composite and absorbent charcoal material negative pole arrange one deck barrier film in the middle of assembling, and are assembled into button-shaped water system asymmetrical type ultracapacitor.
Vacuum drying temperature in preferred preparation method in step 2 and three is 80 ~ 120 DEG C, and the pressure of compressing tablet is 2 ~ 25MPa.
The present invention prepares the Zn (OH) of different mol ratio
2/ Co (OH)
2the preparation method of composite positive pole, specifically comprises the following steps:
(1) adopt two identical cobalt sheets as two electrodes, with NaCl and Zn (CH
3cOO)
2mixed solution be electrolyte, alternating current (50Hz) effect under, reaction 2 ~ 24h, reaction after leave standstill a period of time; The concentration range of NaCl is 0.5 ~ 3.5mol/L, Zn (CH
3cOO)
2concentration range be 0.005 ~ 1mol/L;
(2) by the product centrifugation (8000 turns/min) of step (1) gained, spend deionized water, dry (at 80 DEG C dry 24h), obtains Zn (OH)
2/ Co (OH)
2composite positive pole;
(3) Zn (CH is changed
3cOO)
2concentration (from 0.005mol/L to 1mol/L) in mixed liquor, can obtain the Zn (OH) of different mol ratio
2/ Co (OH)
2composite material.
The present invention adopts Zn (OH)
2/ Co (OH)
2composite positive pole makes Zn (OH)
2/ Co (OH)
2the method of anode composite is as follows:
By different proportion Zn (OH)
2/ Co (OH)
2composite positive pole, mix with the ratio of acetylene black, polyvinylidene fluoride (PVDF) 70 ~ 80:10 in mass ratio ~ 15:10 ~ 15, add a small amount of 1-METHYLPYRROLIDONE (NMP), mix, then be coated in nickel foam, vacuum 100 DEG C of dryings, 20MPa lower sheeting, makes a series of Zn (OH)
2/ Co (OH)
2anode composite.
The present invention adopts the method for absorbent charcoal material making negative pole as follows:
The ratio of absorbent charcoal material with acetylene black, PVDF 75 ~ 85:10 in mass ratio ~ 15:5 ~ 10 mixed, add a small amount of NMP, mix, be then coated in nickel foam, vacuum 80 ~ 120 DEG C of dryings, 2 ~ 25MPa lower sheeting, makes absorbent charcoal material negative pole.
Zn (OH) prepared by the present invention
2/ Co (OH)
2anode composite and absorbent charcoal material negative pole, employing KOH solution is electrolyte, and glass fibre ester is barrier film, is assembled into button-shaped water system asymmetrical type ultracapacitor.
Hinge structure, beneficial effect of the present invention: first with Zn (OH) prepared by AC electrical method
2/ Co (OH)
2water system asymmetrical type ultracapacitor prepared by composite positive pole, its voltage window can reach 1.5V, when power density is 6.2kW kg
-1time people there is high cyclical stability, 5000 circulations can keep more than 99% of initial value, thus have potential commercial application value.In addition, the preparation technology of water system asymmetrical type ultracapacitor is simple, use safety, cost are low and environmental friendliness.
Accompanying drawing explanation
[Fig. 1] is Zn (OH) prepared by the embodiment of the present invention 3
2/ Co (OH)
2the X-ray diffractogram of composite material;
[Fig. 2] is Zn (OH) prepared by the embodiment of the present invention 1 and embodiment 2
2/ Co (OH)
2the scanning electron microscope (SEM) photograph of composite material, (a) and (b) is respectively embodiment 1 and embodiment 2 prepares;
[Fig. 3] is the Zn (OH) that in the present invention prepared by embodiment 1
2/ Co (OH)
2the cyclic voltammetry curve of composite material water system asymmetric super-capacitor is for (sweep speed is 10mV s
-1);
[Fig. 4] is the water system asymmetric super-capacitor that in the present invention prepared by embodiment 2 is 6.2kWkg in power density
-1cyclical stability figure.
Embodiment
Below in conjunction with embodiment, content of the present invention is described further, instead of the restriction of protection range to the claims in the present invention.
Embodiment 1
(1) Zn (OH)
2/ Co (OH)
2the preparation of composite material (mol ratio is 0.2:1)
A, adopt two substantially identical cobalt sheets as two electrodes, with NaCl and Zn (CH
3cOO)
2mixed solution be electrolyte, Zn (CH
3cOO)
2concentration be 0.02mol/L, alternating current (50Hz) effect under, reaction 2 ~ 24h, reaction after leave standstill a period of time;
B, by the product centrifugation (8000 turns/min) of above-mentioned steps (1) gained, spend deionized water, dry (at 80 DEG C dry 24h), obtains Zn (OH)
2/ Co (OH)
2composite material, its mol ratio is 0.2:1;
(2) Zn (OH)
2/ Co (OH)
2the preparation of composite material (mol ratio is 0.2:1) electrode
The Zn (OH) that step (1) is obtained
2/ Co (OH)
2composite material, mix with the ratio of acetylene black, PVDF 80:10:10 in mass ratio, add a small amount of NMP, mix, be then coated in nickel foam, vacuum 100 DEG C of dryings, 20MPa lower sheeting, makes the positive pole of asymmetric super-capacitor.
(3) preparation of absorbent charcoal material electrode
The ratio of absorbent charcoal material and acetylene black, PVDF 85:15:10 in mass ratio mixed, add a small amount of NMP, mix, be then coated in nickel foam, vacuum 100 DEG C of dryings, 20MPa lower sheeting, makes the negative pole of asymmetric super-capacitor.
(4) Zn (OH)
2/ Co (OH)
2the assembling of composite material (mol ratio is 0.2:1) water system asymmetric super-capacitor is with Zn (OH)
2/ Co (OH)
2composite material (mol ratio is 0.2:1) electrode is positive pole, and activated carbon electrodes is negative pole, and the KOH of 3mol/L is electrolyte, and glass fibre ester is barrier film, is assembled into button-shaped asymmetric super-capacitor, and power density is 4.8kW kg
-1time 5000 times circulation after conservation rate can reach 98.7%.
Embodiment 2
(1) Zn (OH)
2/ Co (OH)
2the preparation of composite material (mol ratio is 0.3:1)
A adopts two substantially identical cobalt sheets as two electrodes, with NaCl and Zn (CH
3cOO)
2mixed solution be electrolyte, Zn (CH
3cOO)
2concentration be 0.035mol/L, alternating current (50Hz) effect under, reaction 2 ~ 24h, reaction after leave standstill a period of time;
B, by the product centrifugation (8000 turns/min) of above-mentioned steps (1) gained, spends deionized water, and dry (at 80 DEG C dry 24h), obtains Zn (OH)
2/ Co (OH)
2composite material, its mol ratio is 0.3:1;
(2) Zn (OH)
2/ Co (OH)
2the preparation of composite material (mol ratio is 0.3:1) electrode
The Zn (OH) that step (1) is obtained
2/ Co (OH)
2composite material, mix with the ratio of acetylene black, PVDF 80:10:10 in mass ratio, add a small amount of NMP, mix, be then coated in nickel foam, vacuum 100 DEG C of dryings, 20MPa lower sheeting, makes the positive pole of asymmetric super-capacitor.
(3) preparation of absorbent charcoal material electrode
The ratio of absorbent charcoal material and acetylene black, PVDF 85:15:10 in mass ratio mixed, add a small amount of NMP, mix, be then coated in nickel foam, vacuum 100 DEG C of dryings, 20MPa lower sheeting, makes the negative pole of asymmetric super-capacitor.
(4) Zn (OH)
2/ Co (OH)
2the assembling of composite material (mol ratio is 0.3:1) water system asymmetric super-capacitor is with Zn (OH)
2/ Co (OH)
2composite material (mol ratio is 0.3:1) electrode is positive pole, and activated carbon electrodes is negative pole, and the KOH of 3mol/L is electrolyte, and glass fibre ester is barrier film, is assembled into button-shaped asymmetric super-capacitor, and power density is 6.2kW kg
-1time 5000 times circulation after conservation rate can reach 99.1%.
Embodiment 3
(1) Zn (OH)
2/ Co (OH)
2the preparation of composite material (mol ratio is 1.2:1)
A adopts two substantially identical cobalt sheets as two electrodes, with NaCl and Zn (CH
3cOO)
2mixed solution be electrolyte, Zn (CH
3cOO)
2concentration be 0.1mol/L, alternating current (50Hz) effect under, reaction 2 ~ 24h, reaction after leave standstill a period of time;
B, by the product centrifugation (8000 turns/min) of above-mentioned steps (1) gained, spends deionized water, and dry (at 80 DEG C dry 24h), obtains Zn (OH)
2/ Co (OH)
2composite material, its mol ratio is 1.2:1;
(2) Zn (OH)
2/ Co (OH)
2the preparation of composite material (mol ratio is 1.2:1) electrode
The Zn (OH) that step (1) is obtained
2/ Co (OH)
2composite material, mix with the ratio of acetylene black, PVDF 80:10:10 in mass ratio, add a small amount of NMP, mix, be then coated in nickel foam, vacuum 100 DEG C of dryings, 20MPa lower sheeting, makes the positive pole of asymmetric super-capacitor.
(3) preparation of absorbent charcoal material electrode
The ratio of absorbent charcoal material and acetylene black, PVDF 85:15:10 in mass ratio mixed, add a small amount of NMP, mix, be then coated in nickel foam, vacuum 100 DEG C of dryings, 20MPa lower sheeting, makes the negative pole of asymmetric super-capacitor.
(4) Zn (OH)
2/ Co (OH)
2the assembling of composite material (mol ratio is 1.2:1) water system asymmetric super-capacitor is with Zn (OH)
2/ Co (OH)
2composite material (mol ratio is 1.2:1) electrode is positive pole, and activated carbon electrodes is negative pole, and the KOH of 3mol/L is electrolyte, and glass fibre ester is barrier film, is assembled into button-shaped asymmetric super-capacitor, and power density is 2.3kW kg
-1time 5000 times circulation after conservation rate can reach 99.3%.
Claims (6)
1. one kind based on Zn (OH)
2/ Co (OH)
2the water system asymmetrical type ultracapacitor of anode composite, is made up of positive pole, negative pole, barrier film, electrolyte and shell, it is characterized in that,
Described positive pole is by Zn (OH)
2/ Co (OH)
2the composite material that composite positive pole and acetylene black and PVDF 70 ~ 80:10 in mass ratio ~ 15:10 ~ 15 form is coated in the Zn (OH) that nickel foam obtains
2/ Co (OH)
2anode composite;
Described Zn (OH)
2/ Co (OH)
2composite positive pole is using two identical cobalt sheets as positive and negative electrode, with NaCl and Zn (CH
3cOO)
2mixed solution as electrolyte, prepared by AC electrical method.
2. according to claim 1 based on Zn (OH)
2/ Co (OH)
2the water system asymmetrical type ultracapacitor of anode composite, is characterized in that, described Zn (OH)
2/ Co (OH)
2zn (OH) in composite positive pole
2with Co (OH)
2mol ratio be 0.1 ~ 1:0.1 ~ 1.
3. according to claim 1 based on Zn (OH)
2/ Co (OH)
2the water system asymmetrical type ultracapacitor of anode composite, is characterized in that, described NaCl and Zn (CH
3cOO)
2mixed solution in the concentration range of NaCl be 0.5 ~ 3.5mol/L, Zn (CH
3cOO)
2concentration range be 0.005 ~ 1mol/L.
4. according to claim 1 based on Zn (OH)
2/ Co (OH)
2the water system asymmetrical type ultracapacitor of anode composite, is characterized in that, the AC current frequency that described AC electrical method uses is 50Hz, and voltage is 3 ~ 30V.
5. preparation is based on Zn (OH)
2/ Co (OH)
2the method of the water system asymmetrical type ultracapacitor of anode composite, is characterized in that, comprise the following steps:
Step one: preparation Zn (OH)
2/ Co (OH)
2composite positive pole;
Using two identical cobalt sheets as positive and negative electrode, with NaCl and Zn (CH
3cOO)
2mixed solution as electrolyte, be 50Hz in frequency, voltage is electrolysis 2 ~ 24h under the alternating current of 3 ~ 30V, obtains Zn (OH)
2/ Co (OH)
2composite positive pole; Described NaCl and Zn (CH
3cOO)
2mixed solution in the concentration range of NaCl be 0.5 ~ 3.5mol/L, Zn (CH
3cOO)
2concentration range be 0.005 ~ 1mol/L;
Step 2: preparation Zn (OH)
2/ Co (OH)
2anode composite
By gained Zn (OH)
2/ Co (OH)
2composite positive pole mixes with acetylene black, PVDF 70 ~ 80:10 in mass ratio ~ 15:10 ~ 15, then adds after NMP stirs, and is coated in nickel foam, vacuumize, compressing tablet, obtains Zn (OH)
2/ Co (OH)
2anode composite;
Step 3: prepare absorbent charcoal material negative pole
By mixing of absorbent charcoal material and acetylene black, PVDF 75 ~ 85:10 in mass ratio ~ 15:5 ~ 10, then add after NMP stirs, be coated in nickel foam, vacuumize, compressing tablet, obtain absorbent charcoal material negative pole;
Step 4: assembling water system asymmetrical type ultracapacitor
Using KOH solution as electrolyte, at mounted Zn (OH)
2/ Co (OH)
2anode composite and absorbent charcoal material negative pole arrange one deck barrier film in the middle of assembling, and are assembled into button-shaped water system asymmetrical type ultracapacitor.
6. preparation method according to claim 5, is characterized in that, the vacuum drying temperature in step 2 and three is 80 ~ 120 DEG C, and the pressure of compressing tablet is 2 ~ 25MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510274963.5A CN104900417B (en) | 2015-05-26 | 2015-05-26 | One kind is based on Zn (OH)2/Co(OH)2Water system asymmetrical type ultracapacitor of anode composite and preparation method thereof |
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|---|---|---|---|
| CN201510274963.5A CN104900417B (en) | 2015-05-26 | 2015-05-26 | One kind is based on Zn (OH)2/Co(OH)2Water system asymmetrical type ultracapacitor of anode composite and preparation method thereof |
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| CN104900417B CN104900417B (en) | 2017-12-12 |
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|---|---|---|---|---|
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103341367A (en) * | 2013-07-15 | 2013-10-09 | 上海交通大学 | Method for synthesizing carbon-supported cobalt polypyrrole oxygen reduction catalyst by alternating current one-step method |
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|---|
| JACQUELINE E. CLOUD等: "A simple and generic approach for synthesizing colloidal metal and metal oxide nanocrystals", 《NANOSCALE》 * |
| JUN TANG等: "Effect of Zn-substitution on cycling performance of α-Co(OH)2 nanosheet electrode for supercapacitors", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| MINGJUN JING等: "Electrochemically alternating voltage tuned Co2MnO4/Co hydroxide chloride for an asymmetric supercapacitor", 《ELECTROCHIMICA ACTA》 * |
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