CN110415995A - A kind of preparation method of porous NiAl-LDH electrode material - Google Patents
A kind of preparation method of porous NiAl-LDH electrode material Download PDFInfo
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- CN110415995A CN110415995A CN201910680234.8A CN201910680234A CN110415995A CN 110415995 A CN110415995 A CN 110415995A CN 201910680234 A CN201910680234 A CN 201910680234A CN 110415995 A CN110415995 A CN 110415995A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- 229910000943 NiAl Inorganic materials 0.000 claims abstract description 33
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 19
- 239000004202 carbamide Substances 0.000 claims description 19
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 15
- 150000002815 nickel Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 10
- 238000004146 energy storage Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 210000002700 urine Anatomy 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
-
- 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
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation methods of porous NiAl-LDH electrode material, comprising the following steps: 1) preparation NiAl solution is mixed;2) mixed solution carries out hydro-thermal-frozen dried;3) powder of freeze-drying is subjected to alkali process, then stirs, separates, drying obtains porous NiAl-LDH electrode material.Compared with prior art, the present invention obtain porous NiAl-LDH electrode material preparation method simple and environmentally-friendly, morphology controllable, the research that can be used in terms of energy energy storage.
Description
Technical field
The invention belongs to materials chemistry energy storage fields, are related to a kind of combination electrode material of morphology controllable, specifically, relate to
And a kind of preparation method of porous NiAl-LDH electrode material.
Background technique
While scientific and technical innovation, there is an urgent need to a large amount of to make great efforts to be dedicated to production spirit to sustainable and renewable energy
Living, light and environmental-friendly energy storage device.Supercapacitor has power as a kind of efficient energy storage device
The advantages that density is high, charge/discharge speed is fast, good cycling stability and receive significant attention.These excellent performances make super capacitor
Device either in the extensive use of day electronic and portable electronic product or industrial energy management all have it is wide before
Scape, high power density and long cycle life are the essential conditions that can be widely applied for these fields.So far, counterfeit
Capacitor transition metal oxide/hydroxide is widely used in supercapacitor, big, at low cost with capacitor,
Advantages of environment protection.However, the major obstacle of these materials is poorly conductive, the reunion of particle form is serious, results in low
High-speed performance and lower energy output.
In order to solve these problems, a kind of effective method is fixed on electroactive material on specific substrate, preparation
Oldered array electrode, and by the way that highly conductive polymer or carbon material (such as carbon nanotube, active carbon and graphene) Lai Tigao is added
Conductivity.For example, MnO2/ CNT array, Ni (OH)2/ graphene nano plate, V2O5/ carbon nanotube, MnO2/ conducting polymer is coaxial
The mixed electrodes such as nano wire have all explored the method for electrochemical capacitor performance improvement.Although improving capacitor and durability side
Face has been achieved for certain progress, but since these material costs are high, complex manufacturing technology, to be applied to practical power
There are still challenges in manufacturing environment.Therefore, novel mixed electrode is developed by simple approach, it is high performance super to obtain
Capacitor has great importance.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of porous NiAl-
The preparation method of LDH electrode material.This method is easy to operate, environmental-friendly, obtained porous NiAl-LDH electrode material energy
The disadvantages of bimetallic oxide electric conductivity in the prior art is bad, easy to reunite is solved, while the combination electrode material has
Good cyclical stability and mechanical flexibility.
The purpose of the present invention can be achieved through the following technical solutions:
It is lyophilized to obtain NiAl-LDH powder by hydro-thermal, then handles to obtain porous NiAl-LDH electrode material by alkali precipitation
Material, the specific steps are as follows:
(1) NiAl mixed solution is prepared
By soluble nickel salt, as nickel nitrate and deionized water be mixed to obtain certain density nickel nitrate it is water-soluble
Liquid;It is mixed aluminum soluble salt, such as aluminum nitrate and deionized water to obtain certain density aluminum nitrate solution;By nitric acid
Nickel and aluminum nitrate solution carry out the mixing of different proportion;Urea is added according to different proportion and carries out pattern control;
(2) NiAl mixed solution carries out hydro-thermal-frozen dried
The NiAl mixed solution of above-mentioned preparation is subjected to hydro-thermal reaction, room temperature is down to temperature, carries out centrifuge washing;Then
Sample is subjected to frozen dried;
(3) alkali precipitation-drying and processing
The sample of freeze-drying is dissolved in deionized water, is stirred;The NaOH solution that various concentration is added carries out alkali
Precipitate stir process;Then it is centrifuged, vacuum drying, obtains testing required electrode material.
In the present invention, in step (1), nickel nitrate is 0.5mg:1ml-40mg:1ml with the mixed proportion for having removed ionized water;
The mixing time of nickel nitrate and deionized water is 15-30min.
In the present invention, in step (1), nickel nitrate is 0.5mg:1ml-40mg:1ml with the mixed proportion for having removed ionized water;
The mixing time of nickel nitrate and deionized water is 15-30min;
In the present invention, in step (1), aluminum nitrate is 0.7mg:1ml-30mg:1ml with the mixed proportion for having removed ionized water;
The mixing time of aluminum nitrate and deionized water is 15-30min;
In the present invention, in step (1), the molal weight ratio of nickel nitrate and aluminum nitrate is 9:1-1:1, nickel nitrate and aluminum nitrate
Mixing time be 15-30min.
In the present invention, in step (1), the mass ratio of nickel nitrate and urea is 3:1-1:5;When the stirring of nickel nitrate and urea
Between be 15-30min.
In the present invention, in step (2), the mixed solution hydrothermal temperature of nickel nitrate and aluminum nitrate is 90-120 DEG C;Nickel nitrate
The mixed solution hydro-thermal time with aluminum nitrate is 12-24h;
In the present invention, in step (2), the freeze-drying time of the mixed solution of nickel nitrate and aluminum nitrate is 12-48h.
In the present invention, in step (3), deionized water 25-100ml is added in the sample obtained after freeze-drying;Sample and deionization
The mixing time of water is 15-30min.
In the present invention, in step (3), the concentration for carrying out the NaOH solution that alkali precipitation processing needs is 0.5mol/L-6mol/
L;The volume for the NaOH solution that alkali precipitation processing needs is 100-200ml.
In the present invention, in step (3), when carrying out alkali process, the whipping temp of sample and NaOH solution is 0-30 DEG C;Stirring
Time is 4-12h.
It by conditional filtering, selects the molal weight of nickel nitrate and aluminum nitrate for 4:1, the urea (nitre of controllable appearance is added
The ratio of sour nickel and urea is 1:1), the specific gravity of different urea, which finally will affect, is prepared electrode material pattern, leads to difference
Electrochemical properties.Groped simultaneously by experiment, 20h is reacted in selection under the conditions of 120 DEG C, and frozen dried for 24 hours, and utilizes
4mol/LNaOH alkali process obtains the optimum electrode material needed for finally testing, because different hydrothermal temperatures and time, lead to material
The extent of reaction of material is different, and pattern is different, and the degree of scatter of particle is different, and then influences the electric conductivity of electrode material.
Compared with prior art, the present invention is solved by hydro-thermal and alkali process obtained electrode material is encountered at present
The problem of reunion of poorly conductive, particle form is serious, results in low high-speed performance and the output of lower energy.Institute is much
Hole NiAl-LDH electrode material morphology controllable has excellent charge-discharge performance and ideal cyclical stability, is ideal green
One of color energy storage material.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the electrode material prepared in embodiment 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the electrode material prepared in embodiment 2;
Fig. 3 is the X-ray diffraction figure of the electrode material prepared in embodiment 2;
Fig. 4 is the stable circulation performance figure of the electrode material prepared in embodiment 2;
Fig. 5 is the scanning electron microscope (SEM) photograph of the electrode material prepared in embodiment 3;
Fig. 6 is the transmission scan figure of the electrode material prepared in embodiment 3.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
A kind of preparation method of porous NiAl-LDH electrode material, comprises the following methods:
(1) prepare NiAl mixed solution: compound concentration is the aqueous solution of the soluble nickel salt of 0.5-40mg/L and dense respectively
Degree is the aqueous solution of the aluminum soluble salt of 0.7-30mg/L, is in molar ratio 9:1-1:1 by soluble nickel salt and aluminum soluble salt
The mass ratio of mixing, then addition urea progress pattern control, soluble nickel salt and urea is 3:1-1:5, obtains NiAl mixing
Solution;
(2) NiAl mixed solution carries out hydro-thermal-frozen dried: the temperature by the NiAl mixed solution of preparation at 90-120 DEG C
Lower hydro-thermal reaction 12-24h is down to room temperature to temperature, carries out frozen dried 12-48h after centrifuge washing;
(3) alkali precipitation-drying and processing: the product of freeze-drying is dissolved in deionized water, is stirred;Concentration, which is added, is
The NaOH solution of 0.5mol/L-6mol/L carries out alkali precipitation stir process 4-12h, controlled at 0-30 during being somebody's turn to do;Then
It is centrifuged, vacuum drying, obtains porous NiAl-LDH electrode material.
More detailed case study on implementation below, by following case study on implementation further illustrate technical solution of the present invention with
And the technical effect that can be obtained.
Embodiment 1
A kind of preparation method of porous NiAl-LDH electrode material, includes the following steps:
(1) NiAl mixed solution is prepared
Nickel nitrate proportionally carries out 10mg:10ml with deionized water and mixes, and stirs 15min;Aluminum nitrate and deionization
Water proportionally carries out 10mg:10ml mixing, stirs 15min;The above-mentioned solution prepared is by nickel nitrate and nitric acid al mole ratio 2:1
It is mixed, and stirs 15min;And in the NiAl mixed solution prepared be added urea carry out pattern control, nickel nitrate with
The ratio of urea is 3:1, is then being stirred solution 15min.
(2) NiAl mixed solution carries out hydro-thermal-frozen dried
The NiAl mixed solution of above-mentioned preparation is placed in 100 DEG C of water heating kettle and is reacted, reaction time 16h;
Etc. temperature be down to room temperature, carry out centrifuge washing, 14h be then lyophilized, obtain the sample powder needed in next step.
(3) alkali precipitation-drying and processing
The sample of freeze-drying is dissolved in 50ml deionized water and is dispersed, and stirs 15min;Then concentration, which is added, is
The NaOH solution 100ml of 2mol/L, and 8h is stirred under conditions of 10 DEG C.Processing is centrifuged, is placed in 60 DEG C of vacuum
Baking oven drying, obtains porous NiAl-LDH electrode material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to above-mentioned resulting porous
NiAl-LDH electrode material powder is scanned, and resulting scanning electron microscope (SEM) photograph is as shown in Figure 1, as can be seen from Figure 1 electrode material
Expect into the sheet distribution of hexagon.
Electrochemical property test:
Under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt electrode, and reference electrode is Ag/AgCl electrode, work
The Pt net of carrying active substance as electrode, with three-electrode system electrochemical workstation and blue electric system test material electrification
Learn performance.The results show that the combination electrode material of preparation is in 2Ag-1Charging and discharging curve under galvanostatic conditions at symmetrical triangular shape,
Show good fake capacitance behavior.It is 2Ag in electric current-1It sweeps in the stable circulation linearity curve under speed, the specific capacity variation of material
Less, after 4000 circulations, specific capacity is still positively retained at 80% or so, protrudes it with good cyclical stability.
Embodiment 2
A kind of preparation method of porous NiAl-LDH electrode material, includes the following steps:
(1) NiAl mixed solution is prepared
Nickel nitrate proportionally carries out 20mg:10ml with deionized water and mixes, and stirs 20min;Aluminum nitrate and deionization
Water proportionally carries out 20mg:10ml mixing, stirs 20min;The above-mentioned solution prepared is by nickel nitrate and nitric acid al mole ratio 4:1
It is mixed, and stirs 20min;And in the NiAl mixed solution prepared be added urea carry out pattern control, nickel nitrate with
The ratio of urea is 1:1, is then being stirred solution 20min.
(2) NiAl mixed solution carries out hydro-thermal-frozen dried
The NiAl mixed solution of above-mentioned preparation is placed in 120 DEG C of water heating kettle and is reacted, the reaction time is for 24 hours;
Etc. temperature be down to room temperature, carry out centrifuge washing, the sample powder for obtaining needing in next step for 24 hours be then lyophilized.
(3) alkali precipitation-drying and processing
The sample of freeze-drying is dissolved in 40ml deionized water and is dispersed, and stirs 20min;Then concentration, which is added, is
The NaOH solution 150ml of 4mol/L, and 10h is stirred under conditions of 20 DEG C.Processing is centrifuged, is placed in 60 DEG C of vacuum
Baking oven drying, obtains porous NiAl-LDH electrode material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to above-mentioned resulting porous
NiAl-LDH electrode material powder is scanned, and resulting scanning electron microscope (SEM) photograph is as shown in Figure 2.As can be seen from Figure 2 porous
NiAl-LDH electrode material is collected as flower-like structure, and is tested using X-ray diffraction instrument (XRD) at 2-80 °, such as Fig. 3 institute
Show, NiAl peak value is corresponding with the peak value of standard card.
Electrochemical property test method is with embodiment 1, and under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt
Electrode, reference electrode are Ag/AgCl electrodes, and working electrode is the Pt net of carrying active substance, with three-electrode system in electrochemistry
The chemical property of work station and blue electric system test material.The results show that the combination electrode material of preparation is in 2Ag-1Constant current
Under the conditions of charging and discharging curve at symmetrical triangular shape, after 4000 circulations, as shown in figure 4, specific capacity is still positively retained at
90% or so, it is protruded with good cyclical stability.
Embodiment 3
A kind of preparation method of porous NiAl-LDH electrode material, includes the following steps:
(1) NiAl mixed solution is prepared
Nickel nitrate proportionally carries out 30mg:20ml with deionized water and mixes, and stirs 30min;Aluminum nitrate and deionization
Water proportionally carries out 30mg:20ml mixing, stirs 30min;The above-mentioned solution prepared is by nickel nitrate and nitric acid al mole ratio 1:1
It is mixed, and stirs 30min;And in the NiAl mixed solution prepared be added urea carry out pattern control, nickel nitrate with
The ratio of urea is 1:2, is then being stirred solution 30min.
(2) NiAl mixed solution carries out hydro-thermal-frozen dried
The NiAl mixed solution of above-mentioned preparation is placed in 120 DEG C of water heating kettle and is reacted, reaction time 20h;
Etc. temperature be down to room temperature, carry out centrifuge washing, 32h be then lyophilized, obtain the sample powder needed in next step.
(3) alkali precipitation-drying and processing
The sample of freeze-drying is dissolved in 60ml deionized water and is dispersed, and stirs 30min;Then concentration, which is added, is
The NaOH solution 120ml of 6mol/L, and 12h is stirred under conditions of 30 DEG C.Processing is centrifuged, is placed in 60 DEG C of vacuum
Baking oven drying, obtains porous NiAl-LDH electrode material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to above-mentioned resulting porous
NiAl-LDH electrode material powder is scanned, and resulting scanning electron microscope (SEM) photograph is as shown in Figure 5.As can be seen from Figure 5 porous
The flower-like structure under coherent condition is presented in NiAl-LDH electrode material, due to the control of concentration.And use transmission scan electronic display
Micro mirror instrument carries out transmission scan to the sample of preparation, and obtained scanning transmission is as shown in fig. 6, can be clearly seen that battery
Porous structure is presented in material.
Electrochemical property test:
Under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt electrode, and reference electrode is Ag/AgCl electrode, work
The Pt net of carrying active substance as electrode, with three-electrode system electrochemical workstation and blue electric system test material electrification
Learn performance.The combination electrode material of preparation is in 2Ag-1Charging and discharging curve under galvanostatic conditions is shown very at symmetrical triangular shape
Good fake capacitance behavior, after 4000 circulations, specific capacity is still positively retained at 70% or so, due to the original of concentration ratio
Cause influences the test of chemical property.
Embodiment 4
A kind of preparation method of porous NiAl-LDH electrode material, includes the following steps:
(1) NiAl mixed solution is prepared
Nickel sulfate is mixed with deionized water, and stirs 30min, obtains the solution that concentration is 0.5mg/L;Aluminum sulfate and go from
Sub- water mixing, stirs 30min, obtains the solution that concentration is 0.7mg/L;The above-mentioned solution prepared is by nickel sulfate and aluminum sulfate mole
It is mixed than 9:1, and stirs 30min;And urea is added in the NiAl mixed solution prepared and carries out pattern control, sulfuric acid
The ratio of nickel and urea is 3:1, is then being stirred solution 30min.
(2) NiAl mixed solution carries out hydro-thermal-frozen dried
The NiAl mixed solution of above-mentioned preparation is placed in 90 DEG C of water heating kettle and is reacted, the reaction time is for 24 hours;Deng
Temperature is down to room temperature, carries out centrifuge washing, 48h is then lyophilized, and obtains the sample powder needed in next step.
(3) alkali precipitation-drying and processing
The sample of freeze-drying is dissolved in deionized water and is dispersed, and stirs 30min;Then it is 0.5mol/L that concentration, which is added,
NaOH solution, and stir 4h under conditions of 0 DEG C.Processing is centrifuged, is placed in 30 DEG C of vacuum drying oven drying, obtains
Porous NiAl-LDH electrode material.
Embodiment 5
A kind of preparation method of porous NiAl-LDH electrode material, includes the following steps:
(1) NiAl mixed solution is prepared
Nickel chloride is mixed with deionized water, stirs to get the solution that concentration is 40mg/L;Alchlor and deionized water are mixed
It closes, stirs to get the solution that concentration is 30mg/L;;The above-mentioned solution prepared according to nickel chloride and alchlor molar ratio 1:1 into
Row mixing, and stir 30min;And urea is added in the NiAl mixed solution prepared and carries out pattern control, nickel chloride and urine
The ratio of element is 1:5, is then being stirred solution 60min.
(2) NiAl mixed solution carries out hydro-thermal-frozen dried
The NiAl mixed solution of above-mentioned preparation is placed in 100 DEG C of water heating kettle and is reacted, reaction time 18h;
Etc. temperature be down to room temperature, carry out centrifuge washing, 12h be then lyophilized, obtain the sample powder needed in next step.
(3) alkali precipitation-drying and processing
The sample of freeze-drying is dissolved in deionized water and is dispersed, and stirs 30min;Then it is 1mol/L's that concentration, which is added,
NaOH solution, and 8h is stirred under conditions of 10 DEG C.Processing is centrifuged, is placed in 60 DEG C of vacuum drying oven drying, obtains
Porous NiAl-LDH electrode material.
In conclusion a kind of preparation method of porous NiAl-LDH electrode material of the invention, is comprehensively compared each embodiment
Charge-discharge performance, XRD and scanning electron microscope performance map, chemical property prepared by embodiment 2 is best, porous NiAl-LDH electricity
Material specific capacity with 2243F/g in 2A/g constant current charge-discharge in pole there remains nearly 90% after circulation 4000 times
Specific capacity, it is prominent its with good cyclical stability, prepare that chemical property is good to can be applied to supercapacitor
Electrode material.
Composite material of the present invention makes full use of the synergistic effect of double-level-metal, overcomes the capacitive property of original electrode material not
The problem of foot.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one of the utility model
In embodiment or example.In the present specification, schematic expression of the above terms be not necessarily referring to identical embodiment or
Example.Moreover, particular features, structures, materials, or characteristics described can be in any one or more embodiment or examples
In can be combined in any suitable manner.
The above-mentioned description to embodiment is for ease of ordinary skill in the art to understand and use the invention.It is ripe
The personnel for knowing art technology obviously easily can make various modifications to these embodiments, and general original described herein
It ought to use in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, this field
Technical staff's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in guarantors of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of porous NiAl-LDH electrode material characterized by comprising
It prepares NiAl mixed solution: preparing the aqueous solution of soluble nickel salt and the aqueous solution of aluminum soluble salt respectively, add after mixing
Enter urea, obtains NiAl mixed solution;
NiAl mixed solution carries out hydro-thermal-frozen dried: the NiAl mixed solution of preparation being carried out hydro-thermal reaction, is down to temperature
Room temperature carries out frozen dried after centrifuge washing;
Alkali precipitation-drying and processing: the product of freeze-drying is dissolved in deionized water, is stirred;Various concentration is added
NaOH solution carries out alkali precipitation stir process;Then it is centrifuged, vacuum drying, obtains porous NiAl-LDH electrode material
Material.
2. a kind of preparation method of porous NiAl-LDH electrode material according to claim 1, which is characterized in that it is described can
Insoluble nickel salt is nickel nitrate, nickel sulfate or nickel chloride, and the aluminum soluble salt is aluminum nitrate, alchlor or aluminum sulfate.
3. a kind of preparation method of porous NiAl-LDH electrode material according to claim 1 or 2, which is characterized in that institute
The concentration of aqueous solution for stating soluble nickel salt is 0.5-40mg/L, and the concentration of aqueous solution of the aluminum soluble salt is 0.7-30mg/L.
4. a kind of preparation method of porous NiAl-LDH electrode material according to claim 1 or 2, which is characterized in that institute
The molar ratio for stating soluble nickel salt and the aluminum soluble salt is 9:1-1:1.
5. a kind of preparation method of porous NiAl-LDH electrode material according to claim 1, which is characterized in that it is described can
The mass ratio of insoluble nickel salt and urea is 3:1-1:5.
6. a kind of preparation method of porous NiAl-LDH electrode material according to claim 1, which is characterized in that hydro-thermal is anti-
The temperature answered is 90-120 DEG C, time 12-24h.
7. a kind of preparation method of porous NiAl-LDH electrode material according to claim 1, which is characterized in that at freeze-drying
The time of reason is 12-48h.
8. a kind of preparation method of porous NiAl-LDH electrode material according to claim 1, which is characterized in that addition
The concentration of NaOH solution is 0.5mol/L-6mol/L.
9. a kind of preparation method of porous NiAl-LDH electrode material according to claim 1, which is characterized in that alkali precipitation
The temperature of stir process is 0-30 DEG C;Mixing time is 4-12h.
10. the porous NiAl-LDH electrode material being prepared such as any one of claim 1-9 the method.
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