CN108470646A - Based on the different ultracapacitor and preparation method thereof of material uniformity coefficient - Google Patents
Based on the different ultracapacitor and preparation method thereof of material uniformity coefficient Download PDFInfo
- Publication number
- CN108470646A CN108470646A CN201810354328.1A CN201810354328A CN108470646A CN 108470646 A CN108470646 A CN 108470646A CN 201810354328 A CN201810354328 A CN 201810354328A CN 108470646 A CN108470646 A CN 108470646A
- Authority
- CN
- China
- Prior art keywords
- electrode
- nickel
- different
- ultracapacitor
- nanocrystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- IYFXESRMJKRSNZ-UHFFFAOYSA-L hydrogen carbonate;nickel(2+) Chemical compound [Ni+2].OC([O-])=O.OC([O-])=O IYFXESRMJKRSNZ-UHFFFAOYSA-L 0.000 claims abstract description 39
- 239000002159 nanocrystal Substances 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006260 foam Substances 0.000 claims abstract description 17
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000001509 sodium citrate Substances 0.000 claims abstract description 6
- 238000012360 testing method Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000012153 distilled water Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000003466 welding Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 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
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- WZWGGYFEOBVNLA-UHFFFAOYSA-N sodium;dihydrate Chemical compound O.O.[Na] WZWGGYFEOBVNLA-UHFFFAOYSA-N 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000002513 implantation Methods 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 6
- 238000003487 electrochemical reaction Methods 0.000 abstract description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 abstract description 4
- 229940038773 trisodium citrate Drugs 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 21
- 238000007599 discharging Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001453 impedance spectrum Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002847 impedance measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000010668 complexation reaction Methods 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
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of ultracapacitor different based on material uniformity coefficient, it is that a kind of have the bicarbonate nickel nanocrystal of one layer of different uniformity coefficient as working electrode using in foam nickel surface, platinized platinum is cooked auxiliary electrode, using Ag/AgCl electrodes as reference electrode, the KOH of 6mol/L is injected as electrolyte, the ultracapacitor of composition；Preparation method is mainly by trisodium citrate as block reagent and stabilizer, the bicarbonate nickel nanocrystal with different uniformity coefficients is prepared by the method for hydro-thermal in a kettle, then it is coated in nickel foam and is used as working electrode, auxiliary electrode is done by platinum plate electrode simultaneously, using Ag/AgCl electrodes as reference electrode, they are respectively inserted on detection cell, the KOH of 6mol/L is injected as electrolyte, forms three-electrode system.Specific surface area of the present invention and space bigger make capacitor react more abundant, electrochemical performance with more exposed electrochemical reaction site.
Description
Technical field
The invention belongs to field of material technology, more particularly to a kind of capacitor and preparation method thereof.
Background technology
Ultracapacitor is also known as electrochemical capacitor, is a kind of novel energy-storing element, the big, charge rate with power density
Soon, the features such as having extended cycle life has good application prospect in electric vehicle, field of hybrid electric vehicles.And electrode material
Research be to improve one of the effective way of performance of the supercapacitor, most common electrode material is broadly divided into three classes, respectively
It is transition metal oxide material, absorbent charcoal material and conducting polymer.In numerous materials, with excellent capacitive property
Transistion metal compound is received significant attention as electrode material.
Ni-based transistion metal compound has very high electro-chemical activity, and in terms of energy storage, nickel based compound is living as electricity
Property substance carry out quick redox reaction in electrode surface and its near surface and can generate fake capacitance, be good faraday
Pseudocapacitors electrode material.The energy-storing efficiency of pseudocapacitors will be far longer than double layer capacitor, this is for filling up battery
Energy blank between traditional capacitor is very important.And active material of the bicarbonate nickel as ultracapacitor, quilt
Researchers done it is detailed probe into, include controlled material pattern, porosity, the electric conductivity etc. for improving material, but inherent pass
Relations problems are not mentioned always between the uniformity coefficient and chemical property of electrode material.Therefore, it is necessary to build a conjunction
Suitable system carrys out the relationship between research structure and performance characteristics, and the system is made to become research structure and property relationship
Good platform.
Traditionally, the electrode material of ultracapacitor is by the way that the mixing of electrode active material and conductive material to be pressed into
Made of in nickel foam, wherein ' dead space ' that many heterogeneous electrode active materials used are formed limit electrolyte to
The transfer rate of electrode surface and its near surface.
Invention content
Both it is an object of the invention to prepare two kinds of different ultracapacitors of electrode material uniformity coefficient, and compare
Chemical property, to obtain equal phase electrode material ultracapacitor be a kind of specific surface area and space bigger, have it is more sudden and violent
The electrochemical reaction site of dew makes the super of its more abundant, electrochemical performance of reaction, capacitive property higher and high frequency multiplication
Capacitor electrode material.
The present invention the ultracapacitors different based on material uniformity coefficient, be it is a kind of will foam nickel surface have one layer
The bicarbonate nickel nanocrystal of different uniformity coefficients does auxiliary electrode, using Ag/AgCl as working electrode by platinum plate electrode
(saturation potassium chloride) electrode injects the KOH of 6mol/L as electrolyte as reference electrode, form three-electrode system based on material
Expect the different ultracapacitor of uniformity coefficient.
The preparation method of the above-mentioned ultracapacitor different based on material uniformity coefficient is as follows：
(1) bicarbonate nickel nanocrystal of the synthesis with different uniformity coefficients：
1. with nickel chloride hexahydrate (NiCl2·6H2O), distilled water and urea are raw material, citrate trisodium dihydrate
(Na3C6H5O7·2H2O) it is additive, wherein nickel chloride hexahydrate：Urea：The mass ratio of citrate trisodium dihydrate is
16-21：15-20：1.6-2.1g nickel chloride hexahydrates and 0.40-0.55g citric acids three is added by per 5mL distilled water in 4-5.5
The ratio of sodium dihydrate, by nickel chloride hexahydrate (NiCl2·6H2O it) is dissolved in distilled water, magnetic agitation 5-10 minutes,
Transparent light green solution is obtained, then citrate trisodium dihydrate is added in solution and is stirred for 6-10 minutes；By every
The ratio of 1.5-2.0g urea is added in 10mL distilled water, by urea (CO (NH2)2) it is dissolved in formation homogeneous transparent solution in distilled water；
2. two kinds of solution for taking step 1. to prepare, are slowly added into container, after stirring 15-20 minutes, it is transferred to hydro-thermal
200 DEG C of reaction 12h in kettle；
3. after waiting for hydro-thermal reaction, making its natural cooling at room temperature, pours out product in kettle and be washed with distilled water 3-4
Secondary, ethyl alcohol washs 2 times, until the clarification that supernatant becomes, taking precipitate, then 60-80 DEG C of dry 12-24h in an oven, is had
There is the bicarbonate nickel nanocrystal of different uniformity coefficients；
(2) preparation of the ultracapacitor working electrode with different uniformity coefficients
1. nickel foam and nickel strap are cut by cutting respectively obtain size be 1.0 × 1.0 × 0.1cm and 8.0 × 0.4 ×
0.1cm；
2. nickel foam and nickel strap are connected and fixed by the method for spot welding and are called empty set backed up for flow；
3. the bicarbonate nickel nanocrystal and acetylene black and polytetrafluoroethyl-ne with different uniformity coefficients prepared by step (1)
Alkene (PTFE) is according to 7：2：1 ratio mixing, the ethyl alcohol for being added a concentration of 99% are made slurry, are spread evenly across empty set stream respectively
On body, then by compacting, the dry working electrode that ultracapacitor is made.
(3) preparation of the ultracapacitor with different uniformity coefficient electrodes
The amount of trying to please is the rectangular test pond of 30-50mL, and the 6mol/L KOH of 25-35mL are added as electrolyte solution, incite somebody to action
The working electrode and auxiliary electrode (platinum plate electrode) that step (2) has prepared are placed in test pond, and ensure to be totally submerged in electricity
It solves in liquid, and two electrode spacings should be maintained at 1-1.5cm, while reference electrode (Ag/AgCl) being put into test pond, connect
Device constitutes three-electrode system, opens electrochemical workstation.Its capacitive property is tested first, carries out cyclic voltammetry, setting
Scanning range and speed is swept, tests the height of its shown capacitive property in the case where difference sweeps speed；Then it waits for that its performance is stablized to carry out
Ac impedance measurement is arranged scan frequency, amplitude and sweeps speed, and observes the variation of impedance spectrum；Finally carry out charge-discharge performance
Test sets specified charging and discharging currents density, and the charge-discharge cycle number of turns is arranged, and opens test, and observation calculates its cyclical stability
The variation of energy.
The present invention has the following advantages that compared with prior art：
1, the electrode material prepared has higher homogeneous structural, makes the nanocrystal for having high dispersive uniform as electrode
Material can bring the specific surface area of bigger, and can provide the space of bigger in application, avoid the formation of ' dead space ',
To provide more exposed electrochemical reaction site than the bicarbonate nickel nanocrystal of non-homogeneous structural, its reaction is made more to fill
Point.
2, the equal phase electrode material prepared shows more excellent chemical property, including higher capacitive property exists
2Ag-1It is 1596F g down-1, in 30Ag-1It is 1260F g down-1, it is about twice of heterogeneous bicarbonate nickel nanocrystal；
3, the equal phase electrode material prepared has more stable cycle life, in 5A g-1High current density under, it is high uniform
Property bicarbonate nickel nanocrystal capacity retention ratio reach 80%, be higher than heterogeneous bicarbonate nickel nanocrystal.
Description of the drawings
Fig. 1 is the formation mechenism schematic diagram for the bicarbonate nickel nanocrystal that the present invention synthesizes different uniformity coefficients.
Fig. 2 is the XRD spectra of the bicarbonate nickel nanocrystal for the different uniformity coefficients that the embodiment of the present invention 1 synthesizes.
Fig. 3 is the electron microscope of the bicarbonate nickel nanocrystal for the different uniformity coefficients that the embodiment of the present invention 1 synthesizes, in figure：a
For homogeneous bicarbonate nickel nanocrystal, b is heterogeneous bicarbonate nickel nanocrystal.
Fig. 4 is the active electrode for the different uniformity coefficients that the embodiment of the present invention 1 synthesizes in 30mV s-1Sweep speed under
CV curve graphs, in figure：A is the CV curves of homogeneous active electrode, and b is the CV curves of heterogeneous electrode.
Fig. 5 be the embodiment of the present invention 1 synthesize different uniformity coefficients active electrode current density be 2A g-1Under fill
Discharge curve, in figure：A is the charging and discharging curve of homogeneous active electrode, and b is the charging and discharging curve of heterogeneous electrode.
Fig. 6 is multiplying power of the active electrode for the different uniformity coefficients that the embodiment of the present invention 1 synthesizes under different current densities
Curve graph, in figure：A is the curve of double curvature of homogeneous active electrode, and b is the curve of double curvature of heterogeneous electrode.
Fig. 7 be the embodiment of the present invention 1 synthesize different uniformity coefficients active electrode current density be 5A g-1Lower 1000
Secondary charge and discharge cycles stability test curve graph, in figure：A is the stability test curve of homogeneous active electrode, and b is heterogeneous
Electrode stability test curve.
Fig. 8 is the bicarbonate nickel nanocrystal for the different uniformity coefficients that the embodiment of the present invention 1 synthesizes as active electrode material
The schematic diagram of the electrochemical reaction mechanism of material.
Fig. 9 is the bicarbonate nickel nanocrystal for the different uniformity coefficients that the embodiment of the present invention 1 synthesizes as active electrode
N2Absorption-desorption isothermal curve figure, in figure：A is the N of homogeneous active electrode2Absorption-desorption isothermal curve, b are heterogeneous
Electrode N2Absorption-desorption isothermal curve.
Specific implementation mode
Embodiment 1
As shown in Figure 1, the preparation method based on the different ultracapacitor of material uniformity coefficient is as follows：
(1) bicarbonate nickel nanocrystal of the synthesis with different uniformity coefficients：
1. by 1.928g nickel chloride hexahydrates (NiCl2·6H2O it) is dissolved in 5mL distilled water, magnetic agitation 5 minutes,
Obtain transparent light green solution；0.50g citrate trisodium dihydrates are added in above-mentioned solution again and are stirred for 8 minutes；
By 1.813g urea (CO (NH2)2) it is dissolved in formation homogeneous transparent solution in 10mL distilled water；
2. two kinds of solution for taking step 1. to prepare, are slowly added into beaker, after stirring 15 minutes, it is transferred in water heating kettle
200 DEG C of reaction 12h；
3. after waiting for hydro-thermal reaction, making its natural cooling at room temperature, pours out product in kettle and be washed with distilled water 3
Secondary, absolute ethyl alcohol washs 2 times, and then 80 DEG C of dry 12h, synthesis have the bicarbonate nickel nanometer of different uniformity coefficients in an oven
Crystal；
Trisodium citrate and Ni first2+Ionic reaction forms citrate complexation object 1, and the slow decomposition of urea causes
NH3·H2O and CO2Release 2, can slowly be hydrated into OH-Ion and HCO3 -Ion, OH-In ion ratio reaction system
HCO3 -Ion is more difficult to and Ni2+In conjunction with 3, show HCO3 -It immediately can be with Ni2+Reaction forms bicarbonate nickel core.With the growth of core,
Citrate can be adsorbed on by being attached to specific crystal face on plane of crystal as end-capping reagent and stabilizer, this excellent
It first adsorbs the growth of direct limitation nanocrystal, results in high homogeneous nanocrystal 4.Therefore, added by control
The bicarbonate nickel nanocrystal 5 of different uniformity coefficients can be made in the addition of adding citric acid salt.
As shown in Figure 2, it can be seen that the crystal form of the bicarbonate nickel nanocrystal with different uniformity coefficients of preparation is identical,
It is cubic, and additional diffraction maximum is not present.
As shown in Figure 3, it can be seen that a is when not adding trisodium citrate, and the size of bicarbonate nickel nanocrystal is 5-
120nm；When b is addition trisodium citrate, the size of bicarbonate nickel nanocrystal is about 12nm, it can thus be appreciated that with citric acid three
The addition of sodium, bicarbonate nickel nanocrystal gradually become uniform, and have same shape.
(2) preparation of the ultracapacitor working electrode with different uniformity coefficients
1. nickel foam and nickel strap are cut by cutting respectively obtain size be 1.0 × 1.0 × 0.1cm and 8.0 × 0.4 ×
0.1cm；
2. nickel foam and nickel strap are connected and fixed by the method for spot welding and are called empty set backed up for flow；
3. by the above-mentioned bicarbonate nickel nanocrystal with different uniformity coefficients and acetylene black and polytetrafluoroethylene (PTFE) (PTFE)
According to 7：2：1 ratio mixing, the ethyl alcohol for being added a concentration of 99% are made slurry, are spread evenly across respectively on empty set fluid, so
The working electrode of ultracapacitor is made by suppressing, drying afterwards.
(3) preparation of the supercapacitor device with different uniformity coefficient electrodes
The amount of trying to please is the rectangular test pond of 30mL, and the 6mol/L KOH of 25mL are added as electrolyte solution, by step (2)
The working electrode and auxiliary electrode (platinum plate electrode) prepared is placed in test pond, and ensures to be totally submerged in electrolyte,
And two electrode spacing should be maintained at 1cm, while reference electrode (Ag/AgCl) being put into test pond, connects device and constitute three
Electrode system opens electrochemical workstation.Test its capacitive property first, carry out cyclic voltammetry, setting scanning range with
Speed is swept, the height of its shown capacitive property in the case where difference sweeps speed is tested；Then it waits for that its performance is stablized and carries out AC impedance survey
Examination is arranged scan frequency, amplitude and sweeps speed, and observes the variation of impedance spectrum；Charge-discharge performance test is finally carried out, volume is set
The charge-discharge cycle number of turns is arranged in fixed charging and discharging currents density, opens test, and observation calculates the variation of its stable circulation performance.
As shown in figure 4, electrochemical property test is carried out in -0.1V to 0.5V potential windows, with 30mV s-1Sweep speed
It measures, it can be seen that the integral area of homogeneous active electrode is more than the integral area of heterogeneous active electrode, illustrates homogeneous
Active electrode capacity it is higher than heterogeneous active electrode.
As shown in Figure 5, it can be seen that the specific capacitance of homogeneous active electrode is 1596F g-1, heterogeneous active electrode
Specific capacitance be 990F g-1。
As shown in Figure 6, it can be seen that as current density is from 2Ag-1Increase to 30Ag-1, the ratio of homogeneous active electrode
Capacity is from 1596F g-1It is reduced to 1260F g-1, specific capacitance conservation rate (multiplying power) is 75%, is higher than heterogeneous active electrode
About 45%.
As shown in Figure 7, it can be seen that the capacity retention ratio of homogeneous active electrode is about 80%, heterogeneous activity electricity
The capacity retention ratio of pole is about 61%.
It is more mutually interconnected than heterogeneous active electrode material as shown in figure 8, homogeneous active electrode material is shown
The hole connect, this can provide the space of bigger and specific surface area.
As shown in Figure 9, it can be seen that the homogeneous aperture with heterogeneous active electrode material be respectively 8.27nm and
18.28nm shows that homogeneous pore-size distribution is more uniformly distributed, and the specific surface area of homogeneous active electrode material is 143.31m2g-1,
It is apparently higher than the specific surface area 56.73m of heterogeneous active electrode material2g-1。
Embodiment 2
(1) bicarbonate nickel nanocrystal of the synthesis with different uniformity coefficients：
1. by 1.618g nickel chloride hexahydrates (NiCl2·6H2O it) is dissolved in 5mL distilled water, magnetic agitation 7 minutes,
Obtain transparent light green solution；0.4g citrate trisodium dihydrates are added in above-mentioned solution again and are stirred for 6 minutes；It will
1.50g urea (CO (NH2)2) it is dissolved in formation homogeneous transparent solution in 10mL distilled water；
2. two kinds of solution for taking step 1. to prepare, are slowly added into beaker, after stirring 16 minutes, it is transferred in water heating kettle
200 DEG C of reaction 12h；
3. after waiting for hydro-thermal reaction, making its natural cooling at room temperature, pours out product in kettle and be washed with distilled water 3
Secondary, absolute ethyl alcohol washs 2 times, and then 75 DEG C of 15h in an oven, it is nanocrystalline to synthesize the bicarbonate nickel with different uniformity coefficients
Body；
(2) preparation of the ultracapacitor working electrode with different uniformity coefficients
1. nickel foam and nickel strap are cut by cutting respectively obtain size be 1.0 × 1.0 × 0.1cm and 8.0 × 0.4 ×
0.1cm；
2. nickel foam and nickel strap are connected and fixed by the method for spot welding and are called empty set backed up for flow；
3. by the above-mentioned bicarbonate nickel nanocrystal with different uniformity coefficients and acetylene black and polytetrafluoroethylene (PTFE) (PTFE)
According to 7：2：1 ratio mixing, the ethyl alcohol for being added a concentration of 99% are made slurry, are spread evenly across respectively on empty set fluid, so
The working electrode of ultracapacitor is made by suppressing, drying afterwards.
(3) preparation of the supercapacitor device with different uniformity coefficient electrodes
The amount of trying to please is the rectangular test pond of 45mL, and the 6mol/L KOH of 30mL are added as electrolyte solution, by step (2)
The working electrode and auxiliary electrode (platinum plate electrode) prepared is placed in test pond, and ensures to be totally submerged in electrolyte,
And two electrode spacing should be maintained at 1.3cm, while reference electrode (Ag/AgCl) being put into test pond, connects device composition
Three-electrode system opens electrochemical workstation.Its capacitive property is tested first, carries out cyclic voltammetry, and scanning range is set
With sweep speed, test its difference sweep speed under shown capacitive property height；Then it waits for that its performance is stablized and carries out AC impedance
Test is arranged scan frequency, amplitude and sweeps speed, and observes the variation of impedance spectrum；Finally carry out charge-discharge performance test, setting
The charge-discharge cycle number of turns is arranged in specified charging and discharging currents density, opens test, and observation calculates the variation of its stable circulation performance.
Embodiment 3
(1) bicarbonate nickel nanocrystal of the synthesis with different uniformity coefficients：
1. by 1.801g nickel chloride hexahydrates (NiCl2·6H2O it) is dissolved in 5mL distilled water, magnetic agitation 8 minutes,
Obtain transparent light green solution；0.45g citrate trisodium dihydrates are added in above-mentioned solution again and are stirred for 8 minutes；
By 1.707g urea (CO (NH2)2) it is dissolved in formation homogeneous transparent solution in 10mL distilled water；
2. two kinds of solution for taking step 1. to prepare, are slowly added into beaker, after stirring 17 minutes, it is transferred in water heating kettle
200 DEG C of reaction 12h；
3. after waiting for hydro-thermal reaction, making its natural cooling at room temperature, pours out product in kettle and be washed with distilled water 4
Secondary, absolute ethyl alcohol washs 2 times, and then 70 DEG C of 18h in an oven, it is nanocrystalline to synthesize the bicarbonate nickel with different uniformity coefficients
Body；
(2) preparation of the ultracapacitor working electrode with different uniformity coefficients
1. nickel foam and nickel strap are cut by cutting respectively obtain size be 1.0 × 1.0 × 0.1cm and 8.0 × 0.4 ×
0.1cm；
2. nickel foam and nickel strap are connected and fixed by the method for spot welding and are called empty set backed up for flow；
3. by the above-mentioned bicarbonate nickel nanocrystal with different uniformity coefficients and acetylene black and polytetrafluoroethylene (PTFE) (PTFE)
According to 7：2：1 ratio mixing, the ethyl alcohol for being added a concentration of 99% are made slurry, are spread evenly across respectively on empty set fluid, so
The working electrode of ultracapacitor is made by suppressing, drying afterwards.
(3) preparation of the supercapacitor device with different uniformity coefficient electrodes
The amount of trying to please is the rectangular test pond of 40mL, and the 6mol/L KOH of 30mL are added as electrolyte solution, by step (2)
The working electrode and auxiliary electrode (platinum plate electrode) prepared is placed in test pond, and ensures to be totally submerged in electrolyte,
And two electrode spacing should be maintained at 1.5cm, while reference electrode (Ag/AgCl) being put into test pond, connects device composition
Three-electrode system opens electrochemical workstation.Its capacitive property is tested first, carries out cyclic voltammetry, and scanning range is set
With sweep speed, test its difference sweep speed under shown capacitive property height；Then it waits for that its performance is stablized and carries out AC impedance
Test is arranged scan frequency, amplitude and sweeps speed, and observes the variation of impedance spectrum；Finally carry out charge-discharge performance test, setting
The charge-discharge cycle number of turns is arranged in specified charging and discharging currents density, opens test, and observation calculates the variation of its stable circulation performance.
Embodiment 4
(1) bicarbonate nickel nanocrystal of the synthesis with different uniformity coefficients：
1. by 2.066g nickel chloride hexahydrates (NiCl2·6H2O it) is dissolved in 5mL distilled water, magnetic agitation 10 minutes,
Obtain transparent light green solution；0.55g citrate trisodium dihydrates are added in above-mentioned solution again and are stirred for 10 minutes；
By 1.901g urea (CO (NH2)2) it is dissolved in formation homogeneous transparent solution in 10mL distilled water；
2. two kinds of solution for taking step 1. to prepare, are slowly added into beaker, stirring after twenty minutes, is transferred in water heating kettle
200 DEG C of reaction 12h；
3. after waiting for hydro-thermal reaction, making its natural cooling at room temperature, pours out product in kettle and be washed with distilled water 3
Secondary, absolute ethyl alcohol washs 2 times, and then 60 DEG C of dryings for 24 hours, synthesize the bicarbonate nickel nanometer with different uniformity coefficients in an oven
Crystal；
(2) preparation of the ultracapacitor working electrode with different uniformity coefficients
1. nickel foam and nickel strap are cut by cutting respectively obtain size be 1.0 × 1.0 × 0.1cm and 8.0 × 0.4 ×
0.1cm；
2. nickel foam and nickel strap are connected and fixed by the method for spot welding and are called empty set backed up for flow；
3. by the above-mentioned bicarbonate nickel nanocrystal with different uniformity coefficients and acetylene black and polytetrafluoroethylene (PTFE) (PTFE)
According to 7：2：1 ratio mixing, the ethyl alcohol for being added a concentration of 99% are made slurry, are spread evenly across respectively on empty set fluid, so
The working electrode of ultracapacitor is made by suppressing, drying afterwards.
(3) preparation of the supercapacitor device with different uniformity coefficient electrodes
The amount of trying to please is the rectangular test pond of 50mL, and the 6mol/L KOH of 35mL are added as electrolyte solution, by step (2)
The working electrode and auxiliary electrode (platinum plate electrode) prepared is placed in test pond, and ensures to be totally submerged in electrolyte,
And two electrode spacing should be maintained at 1cm, while reference electrode (Ag/AgCl) being put into test pond, connects device and constitute three
Electrode system opens electrochemical workstation, opens electrochemical workstation.Its capacitive property is tested first, carries out cyclic voltammetric survey
Examination is arranged scanning range and sweeps speed, tests the height of its shown capacitive property in the case where difference sweeps speed；Then wait for that its performance is steady
Surely ac impedance measurement is carried out, scan frequency, amplitude are set and sweeps speed, and observes the variation of impedance spectrum；Finally carry out charge and discharge
Electric performance test sets specified charging and discharging currents density, and the charge-discharge cycle number of turns is arranged, and opens test, and observation calculates its cycle
The variation of stability.
Claims (2)
1. a kind of ultracapacitor different based on material uniformity coefficient, it is characterised in that：It is that will have in foam nickel surface
The bicarbonate nickel nanocrystal of one layer of different uniformity coefficient does auxiliary electrode, using Ag/ as working electrode by platinum plate electrode
For AgCl (saturation potassium chloride) electrode as reference electrode, the KOH that implantation concentration is 6mol/L forms three electrode bodies as electrolyte
The ultracapacitors different based on material uniformity coefficient of system.
2. the preparation method of the ultracapacitors different based on material uniformity coefficient of claim 1, it is characterised in that：
(1) bicarbonate nickel nanocrystal of the synthesis with different uniformity coefficients：
1. with nickel chloride hexahydrate (NiCl2﹒ 6H2O), distilled water and urea are raw material, citrate trisodium dihydrate
(Na3C6H5O7﹒ 2H2O) it is additive, wherein nickel chloride hexahydrate：Urea：The mass ratio of citrate trisodium dihydrate is
16-21：15-20：1.6-2.1g nickel chloride hexahydrates and 0.40-0.55g citric acids three is added by per 5mL distilled water in 4-5.5
The ratio of sodium dihydrate, by nickel chloride hexahydrate (NiCl2﹒ 6H2O it) is dissolved in distilled water, magnetic agitation 5-10 minutes,
Transparent light green solution is obtained, then citrate trisodium dihydrate is added in solution and is stirred for 6-10 minutes；By every
The ratio of 1.5-2.0g urea is added in 10mL distilled water, by urea (CO (NH2)2) it is dissolved in formation homogeneous transparent solution in distilled water；
2. two kinds of solution for taking step 1. to prepare, are slowly added into container, after stirring 15-20 minutes, it is transferred in water heating kettle
200 DEG C of reaction 12h；
3. after waiting for hydro-thermal reaction, make its natural cooling at room temperature, pour out in kettle product and be washed with distilled water 3-4 times,
Absolute ethyl alcohol washs 2 times, until the clarification that supernatant becomes, taking precipitate, then 60-80 DEG C of dry 12-24h in an oven, obtains
Bicarbonate nickel nanocrystal with different uniformity coefficients；
(2) preparation of the ultracapacitor working electrode with different uniformity coefficients
1. nickel foam and nickel strap are cut by cutting respectively obtain size be 1.0 × 1.0 × 0.1cm and 8.0 × 0.4 ×
0.1cm；
2. nickel foam and nickel strap are connected and fixed by the method for spot welding and are called empty set backed up for flow；
3. the bicarbonate nickel nanocrystal and acetylene black and polytetrafluoroethylene (PTFE) with different uniformity coefficients prepared by step (1)
(PTFE) according to 7：2：1 ratio mixing, the ethyl alcohol for being added a concentration of 99% are made slurry, are spread evenly across empty set fluid respectively
On, then by compacting, the dry working electrode that ultracapacitor is made.
(3) preparation of the ultracapacitor with different uniformity coefficient electrodes
The amount of trying to please is the rectangular test pond of 30-50mL, and the 6mol/L KOH of 25-35mL are added as electrolyte solution, by step
(2) working electrode and auxiliary electrode platinized platinum prepared is placed in test pond, and ensures to be totally submerged in electrolyte, and two
Electrode spacing should be maintained at 1-1.5cm, while reference electrode (Ag/AgCl) being put into test pond, connect device and constitute three
Electrode system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810354328.1A CN108470646A (en) | 2018-04-19 | 2018-04-19 | Based on the different ultracapacitor and preparation method thereof of material uniformity coefficient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810354328.1A CN108470646A (en) | 2018-04-19 | 2018-04-19 | Based on the different ultracapacitor and preparation method thereof of material uniformity coefficient |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108470646A true CN108470646A (en) | 2018-08-31 |
Family
ID=63263585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810354328.1A Pending CN108470646A (en) | 2018-04-19 | 2018-04-19 | Based on the different ultracapacitor and preparation method thereof of material uniformity coefficient |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108470646A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114334481A (en) * | 2021-12-09 | 2022-04-12 | 温州大学新材料与产业技术研究院 | NiCo with three-dimensional cross-linked core-shell structure2S4@ NiCo-HCs composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2444514A1 (en) * | 2010-10-25 | 2012-04-25 | United Technologies Corporation | Low density abradable coating with fine porosity |
| CN106057501A (en) * | 2016-08-11 | 2016-10-26 | 浙江大学 | Ni(OH)2/NiSe nanometer rod material used for super capacitor and preparation method thereof |
| CN106315522A (en) * | 2016-08-11 | 2017-01-11 | 浙江大学 | NiSe three-dimensional porous nanosheet material used for superconductor and preparation method thereof |
| CN106571248A (en) * | 2016-10-26 | 2017-04-19 | 信阳师范学院 | Preparation method for electrode material of Se-doped ZnO-SnO2 supercapacitor taking foamed nickel as substrate |
-
2018
- 2018-04-19 CN CN201810354328.1A patent/CN108470646A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2444514A1 (en) * | 2010-10-25 | 2012-04-25 | United Technologies Corporation | Low density abradable coating with fine porosity |
| CN106057501A (en) * | 2016-08-11 | 2016-10-26 | 浙江大学 | Ni(OH)2/NiSe nanometer rod material used for super capacitor and preparation method thereof |
| CN106315522A (en) * | 2016-08-11 | 2017-01-11 | 浙江大学 | NiSe three-dimensional porous nanosheet material used for superconductor and preparation method thereof |
| CN106571248A (en) * | 2016-10-26 | 2017-04-19 | 信阳师范学院 | Preparation method for electrode material of Se-doped ZnO-SnO2 supercapacitor taking foamed nickel as substrate |
Non-Patent Citations (1)
| Title |
|---|
| JIANMIN GU: "Controllable synthesis of nickel bicarbonate nanocrystals with high homogeneity for a high-performance supercapacitor", 《NANOTECHNOLOGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114334481A (en) * | 2021-12-09 | 2022-04-12 | 温州大学新材料与产业技术研究院 | NiCo with three-dimensional cross-linked core-shell structure2S4@ NiCo-HCs composite material and preparation method and application thereof |
| CN114334481B (en) * | 2021-12-09 | 2024-05-14 | 温州大学新材料与产业技术研究院 | NiCo with three-dimensional cross-linked core-shell structure2S4@NiCo-HCs composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | A general fabrication approach on spinel MCo2O4 (M= Co, Mn, Fe, Mg and Zn) submicron prisms as advanced positive materials for supercapacitor | |
| Li et al. | Electrochemically-deposited nanostructured Co (OH) 2 flakes on three-dimensional ordered nickel/silicon microchannel plates for miniature supercapacitors | |
| CN105023768B (en) | Ni-based nickel oxide electrode material of foam and preparation method thereof | |
| CN104876282B (en) | CoS as electrode of super capacitorxnano material and preparation method thereof | |
| CN105845904B (en) | A kind of sodium-ion battery metal oxide/polypyrrole hollow nanotube anode material and preparation method thereof | |
| CN109585177A (en) | A kind of preparation method of the nickel cobalt phosphorus integral electrodes material of core-shell structure | |
| CN103762090B (en) | A kind of from afflux electrode material for super capacitor and preparation method thereof | |
| CN110223851A (en) | A kind of method of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material | |
| CN108133831A (en) | A kind of preparation method of Ni3S2@rGO@LDHs | |
| CN105470000A (en) | Integrated composite electrode for supercapacitor and preparation method of integrated composite electrode | |
| CN105845448A (en) | Homogeneous core-shell structure cobaltosic sulfide nanometer material, preparation method and application of being as super capacitor electrode material thereof | |
| CN109767924A (en) | A kind of LDH based super capacitor combination electrode material and preparation method and purposes | |
| CN102760583A (en) | Hollow honeycomb MnO2/C micro nanosphere and microrod preparation method | |
| CN109786135A (en) | A kind of copper oxide@nickel molybdate/foam copper combination electrode material and preparation method thereof | |
| CN110079846A (en) | Nickelous selenide with different-shape/nickel base electrode material electro-deposition preparation method | |
| CN105702475A (en) | Super capacitor negative electrode material nickel ferrite and preparation method therefor | |
| CN106571248A (en) | Preparation method for electrode material of Se-doped ZnO-SnO2 supercapacitor taking foamed nickel as substrate | |
| CN108172407A (en) | A kind of combination electrode, preparation method and application | |
| CN106006576A (en) | Nanomaterial used as supercapacitor electrode material, and preparation method thereof | |
| CN104658771A (en) | Method for preparing urchin-like vanadium base nanometer electrode material and application of the material | |
| CN106783202A (en) | A kind of preparation method of bimetallic selenides electrode material for super capacitor CuxMoySez | |
| CN109411238A (en) | A kind of layered double-hydroxide combination electrode material and its preparation method and application | |
| CN111268745A (en) | NiMoO4@Co3O4Core-shell nano composite material, preparation method and application | |
| CN103456521B (en) | The preparation method of cobalt hydroxide/bismuth sulfide composite nano-line super capacitance electrode material | |
| Gopi et al. | Designing nanosheet manganese cobaltate@ manganese cobaltate nanosheet arrays as a battery-type electrode material towards high-performance supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180831 |