CN114300273B - NiGa-LDH@ZnCo2O4Nano-NF composite material and preparation method and application thereof - Google Patents
NiGa-LDH@ZnCo2O4Nano-NF composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 144
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 118
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 83
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000004202 carbamide Substances 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 57
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- 239000006260 foam Substances 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 239000011701 zinc Substances 0.000 claims abstract description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 36
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 33
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 33
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 28
- 229910009111 xH2 O Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
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- 238000004321 preservation Methods 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 48
- 238000001027 hydrothermal synthesis Methods 0.000 description 40
- 238000002484 cyclic voltammetry Methods 0.000 description 38
- 238000012360 testing method Methods 0.000 description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000002243 precursor Substances 0.000 description 25
- 238000001291 vacuum drying Methods 0.000 description 25
- 238000001816 cooling Methods 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 229910001220 stainless steel Inorganic materials 0.000 description 24
- 239000010935 stainless steel Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- 238000010277 constant-current charging Methods 0.000 description 18
- 238000007599 discharging Methods 0.000 description 18
- 239000008151 electrolyte solution Substances 0.000 description 18
- 230000033116 oxidation-reduction process Effects 0.000 description 18
- 241000744472 Cinna Species 0.000 description 17
- 229910021607 Silver chloride Inorganic materials 0.000 description 17
- 125000004122 cyclic group Chemical group 0.000 description 17
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 17
- 238000003756 stirring Methods 0.000 description 13
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 12
- 238000002604 ultrasonography Methods 0.000 description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229910003119 ZnCo2O4 Inorganic materials 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003298 Ni-Ni Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
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- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 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
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof, wherein the composite material is prepared by adopting the following preparation method: (1) Dispersing a zinc source, a cobalt source, ammonium fluoride and urea in water to obtain a solution A; (2) Adding foam nickel into the obtained solution A, and obtaining ZnCo 2O4 @NF material through hydrothermal treatment, washing, drying and calcining; (3) Dispersing a nickel source, a gallium source and urea in water to obtain a solution B; (4) And soaking ZnCo 2O4 @NF material in the solution B, and then carrying out hydrothermal treatment, washing and drying to obtain a target product. According to the composite material, znCo 2O4 is used as an active center to shorten the ion diffusion length, a large amount of active sites are provided by the NiGa-LDH nano sheet with large specific surface area, and the NiGa-LDH nano sheet and ZnCo 2O4 are grown in situ to be compounded, so that the electrochemical performance of the material is improved. Compared with the prior art, the composite material has the advantages of higher energy density, better electrochemical performance, better reversibility and stability, simple preparation method, environment friendliness and convenience for industrial production, and can be used as a working electrode of the supercapacitor.
Description
Technical Field
The invention belongs to the technical field of electrochemical nano materials, and relates to a NiGa-LDH@ZnCo 2O4 @NF composite material, and a preparation method and application thereof.
Background
The rapid consumption of fossil fuels and the ever-deteriorating environment have stimulated intensive research into renewable and pollution-free energy storage/conversion devices, such as Super Capacitors (SCs), lithium ion batteries, fuel cells, and solar cells. Among them, SCs have received a great deal of attention for their advantages of high power output, short charging time, very long cycle life, and safe operation. SCs are classified into Pseudocapacitors (PCs) and Electric Double Layer Capacitors (EDLCs) based on energy storage mechanisms. In contrast to EDLCs, which stores energy through the process of electrostatic adsorption at the electrolyte interface, PCs store charge based on the fast reversible faraday reaction of the active electrode material. It is well known that electrode materials are key factors in determining the properties of SCs, and materials used for EDLCs, PCs are typically conductive polymers or transitional oxides.
Ternary metal oxides MCo 2O4 (M stands for Ni, zn, mg, etc.) are considered to be a very promising energy storage material due to the synergistic effect of the two transition metal components. Among them, znCo 2O4 is receiving a great deal of attention due to its high theoretical specific capacitance, abundant redox active sites and excellent cycling stability. However, single component materials typically have relatively low energy and power densities as electrode materials. Supercapacitors assembled from single component metal oxide materials, including ZnCo 2O4, typically exhibit limited electrochemical kinetics in redox reactions due to a series of drawbacks, such as non-ideal electrochemical performance, poor reversible stability, etc.
Disclosure of Invention
The invention aims to provide a NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof, so as to overcome the defects of low energy density, poor electrochemical performance, poor reversible stability and the like of ZnCo 2O4 in the prior art.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a NiGa-LDH@ZnCo 2O4 @NF composite material, which comprises the following steps:
(1) Dispersing a zinc source, a cobalt source, ammonium fluoride and urea in water to obtain a solution A;
(2) Adding foam nickel into the obtained solution A, and obtaining ZnCo 2O4 @NF material through hydrothermal treatment, washing, drying and calcining;
(3) Dispersing a nickel source, a gallium source and urea in water to obtain a solution B;
(4) Soaking the ZnCo 2O4 @NF material in the solution B, and then carrying out hydrothermal treatment, washing and drying to obtain a target product.
Further, in the step (1), the zinc source is Zn (NO 3)2·6H2 O) and the cobalt source is Co (NO 3)2·6H2 O).
Further, the ratio of the addition amount of Zn (NO 3)2·6H2O、Co(NO3)2·6H2 O, ammonium fluoride, urea, water) is (0.5-2) mmol (1-2) mmol:2mmol:5mmol (35-45) mL.
In the step (1), stirring and ultrasonic are used for dispersing a zinc source, a cobalt source, ammonium fluoride and urea in water at room temperature, wherein the ultrasonic time is 5-10min.
Further, in the step (2), the size of the foam nickel is 1cm×1cm×8mm, and the volume of the solution A to be added is 35-45mL.
Further, in the step (2), the hydrothermal temperature is 100-140 ℃ and the hydrothermal time is 5.5-6.5h.
Further, in the step (2), calcination is carried out under an air atmosphere, the calcination temperature is 350-450 ℃, the heat preservation time is 1.5-2.5h, and the heating rate is 1.5-2.5 ℃/min.
Further, in the step (2), the foam nickel is also subjected to the following pretreatment before use:
The nickel foam was washed sequentially with acetone, ethanol, and water.
Further, in the step (3), the nickel source is Ni (NO 3)2·6H2 O) and the gallium source is Ga (NO 3)3·xH2 O).
Further, the ratio of Ni (NO 3)2·6H2O、Ga(NO3)3·xH2 O, urea, water was (1-2) mmol to 12mmol (25-35) mL.
Further, in the step (4), the hydrothermal temperature is 110-130 ℃ and the hydrothermal time is 8-12h.
Further, in the step (2) and the step (4), vacuum drying is adopted, the drying temperature is 60-80 ℃, and the drying time is 12-24 hours.
The second technical scheme of the invention provides a NiGa-LDH@ZnCo 2O4 @NF composite material, which is prepared by adopting the preparation method.
The third technical scheme of the invention provides application of the NiGa-LDH@ZnCo 2O4 @NF composite material, and the composite material can be used as a working electrode for a supercapacitor, and the specific application process is as follows:
After grinding the NiGa-LDH@ZnCo 2O4 @NF composite material, uniformly mixing the ground NiGa-LDH@ZnCo 2O4 @NF composite material with carbon black and polytetrafluoroethylene, and then pressing the mixture on a foam nickel sheet to obtain the working electrode.
Further, the mass ratio of the NiGa-LDH@ZnCo 2O4 @NF composite material, carbon black and polytetrafluoroethylene is 8: (0.8-1.2): (0.8-1.2).
The core-shell heterostructure is beneficial to realizing breakthrough in electrochemical performance. Bimetallic layered hydroxides (LDHs) have attracted considerable attention in the field of supercapacitor applications due to their layered structure, rich interlayer channels, rapid redox reactions and flexible ions during charge and discharge. Nickel-based hydroxide, as a kind of double metal layered hydroxide, has been proved as one of the energy materials due to its rapid redox reaction, superior electrical activity and high electrochemical stability. Ga 3+ inserted in the synthesis process of LDHs can remarkably improve the electrochemical performance of LDHs. Research shows that the length of Ga-Ga bond is smaller than that of Ni bond, and the shorter the bond, the higher the binding energy and the more stable the structure. Since the ionic radius of Ga 3+ is smaller than that of nickel and cobalt ions, the lengths of Ga-Co bonds and Ga-Ni bonds are smaller than those of Ni-Co bonds, co-Co bonds and Ni-Ni bonds. This finding suggests that equivalent substitution of gallium may improve conductivity. Therefore, in-situ growth of NiGa-LDH@ZnCo 2O4 @NF composite material on high-conductivity framework foam nickel is a viable strategy for improving electrochemical performance exhibited by ZnCo 2O4 and NiGa-LDH respectively as single-component materials.
According to the invention, the ternary metal oxide ZnCo 2O4 and nano flaky bimetal layered hydroxide NiGa-LDH are compounded on a highly porous foam nickel matrix, so that the purpose of enhancing electrochemical performance is achieved, and the problems of application limitation on super capacitor electrode materials and the like existing in ZnCo 2O4 and NiGa-LDH are further solved.
Compared with the prior art, the NiGa-LDH@ZnCo 2O4 @NF composite material prepared by the invention uses a 3D porous foam nickel skeleton as a matrix, ternary metal oxide as an active center and a bimetal layered hydroxide nano sheet as an active site, so that not only can the conductivity be enhanced, but also a large number of effective active sites are provided, and therefore, the composite material has excellent electrochemical performance; in addition, the preparation method is two-step hydrothermal, is simple and easy to operate, is environment-friendly, and is convenient for large-scale industrial production.
In the reaction process, urea is subjected to hydrothermal decomposition in a high-temperature and high-pressure reaction kettle to form hydroxide ions, the hydroxide ions are combined with zinc ions decomposed in a zinc source and cobalt ions decomposed in a cobalt source to form ZnCo layered double hydroxide, and the hydroxide is subjected to high-temperature annealing in a tube furnace (air atmosphere) to perform dehydrogenation and oxidation, so that the ZnCo 2O4 material is finally formed. In the reaction process, the ammonium fluoride plays a role in morphology regulation, and urea is used for providing hydroxide ions. In addition, the invention also limits the process conditions in the preparation process, such as calcination temperature, hydrothermal temperature, heating rate and the addition ratio of the raw materials (such as the amounts of zinc source, cobalt source, nickel source, gallium source and water), because a plurality of experimental conditions are tried in the earlier stage through a single factor controlled variable method, the optimal limiting conditions are summarized, and the electrochemical performance advantage and the ideal high specific capacitance of the composite material can be fully exerted. If the nickel foam is not in the process condition range defined by the invention, if the calcination temperature is too high, the nickel foam substrate becomes brittle, the composite material cannot be well supported, and the structural stability of the composite material is not facilitated; too low a calcination temperature does not allow sufficient oxidation of the ZnCo layered double hydroxide to ZnCo 2O4 and is detrimental to the formation of high surface area active sites.
Compared with the prior art, the invention has the following advantages:
(1) The NiGa-LDH@ZnCo 2O4 @NF composite material prepared by the method has a unique core-shell layered nano structure, znCo 2O4 in the composite material has higher conductivity, the ion diffusion length can be shortened as an active center, a large number of active sites can be provided by a large specific surface area NiGa-LDH nano sheet, and the NiGa-LDH nano sheet and ZnCo 2O4 are subjected to in-situ growth and recombination so as to improve the electrochemical performance of the composite material;
(2) The NiGa-LDH@ZnCo 2O4 @NF composite material prepared by the method can be used as a working electrode in a supercapacitor, and a cyclic voltammogram of the composite material has obvious redox peak pairs, so that the composite material has good reversibility and stability;
(3) The specific capacitance of the NiGa-LDH@ZnCo 2O4 @NF composite material prepared by the method can reach 2600F/g at the highest, has high energy density, and can be used as a working electrode for a super capacitor;
(4) The preparation method is two-step hydrothermal, is simple and easy to operate, adopts low-cost and pollution-free raw materials, is nontoxic and pollution-free in solvent generated in the preparation process, is environment-friendly, has good electrochemical performance in the super capacitor, and can realize large-scale industrialized popularization.
Drawings
FIG. 1 is a cyclic voltammogram of the NiGa-LDH@ZnCo 2O4 @NF composite material obtained in example 1 at different sweep speeds;
FIG. 2 is a GCD plot of the NiGa-LDH@ZnCo 2O4 @NF composite material obtained in example 1 at different current densities.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise specified, the raw materials or processing techniques are indicated as being conventional commercially available raw material products or conventional processing techniques in the art.
Example 1:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
firstly, 1mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-1) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-1 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2600F/g under the condition of 2mol/L KOH solution and 1A/g current density.
FIG. 1 is a CV chart of the NiGa-LDH@ZnCo 2O4 @NF composite material prepared in the embodiment at different scanning speeds of 5, 10, 15, 20, 30, 40 and 50mV/s respectively. As can be seen from the graph, at voltages ranging from-0.1 to 0.7V, there is a symmetrical redox peak, and as the sweep rate increases, the redox peak and the reduction peak move to the right and left, respectively. The phenomenon shows that the prepared NiGa-LDH@ZnCo 2O4 @NF composite material has good reversibility and stability.
FIG. 2 is a GCD curve of NiGa-LDH@ZnCo 2O4 @NF composite material prepared in this example at current densities of 1,2, 5, 10A/g. The GCD curve has an obvious charge-discharge platform, which is probably caused by reversible adsorption and desorption of hydroxide ions, and the specific capacitance of the composite material can reach 2600F/g under the current density of 1A/g; furthermore, the specific capacitance of the electrode material gradually decreases with increasing current density, mainly due to the increased polarization of the material and the reduced activity to participate in the electrochemical reaction at higher current densities.
The concrete application process of NGZC-1 composite material as working electrode of super capacitor is:
Grinding NGZC-1 composite material, uniformly mixing with carbon black and polytetrafluoroethylene (NGZC-1 composite material, carbon black and polytetrafluoroethylene in a mass ratio of 8:1:1), and pressing on a foam nickel sheet to obtain the positive electrode of the supercapacitor. And similarly, uniformly mixing the activated carbon, carbon black and polytetrafluoroethylene (the mass ratio is 8:1:1), and then pressing on a foam nickel sheet to obtain a negative electrode material, and assembling the negative electrode material and NGZC-1 positive electrode material into the simple supercapacitor. Electrochemical testing is carried out by using a Chenhua CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method by using a two-electrode system, and 2mol/L KOH is used as electrolyte solution. The specific capacitance and the cycle stability of the super capacitor are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the super capacitor reaches 198.7F/g under the condition of 2mol/L KOH solution and 1A/g current density.
Example 2:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
Firstly, 0.5mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-2) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-2 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2469.3F/g under the condition of 2mol/L KOH solution and 2A/g current density.
Example 3:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
Firstly, 2mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-3) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-3 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2258.1F/g under the condition of 2mol/L KOH solution and 5A/g current density.
Example 4:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
Firstly, 1mmol Zn(NO3)2·6H2O、1mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-4) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-4 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2364.5F/g under the condition of 2mol/L KOH solution and 1A/g current density.
Example 5:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
firstly, 1mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 100 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-5) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-5 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2183.7F/g under the condition of 2mol/L KOH solution and 10A/g current density.
Example 6:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
firstly, 1mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 140 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-6) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-6 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2146F/g under the condition of 2mol/L KOH solution and 2A/g current density.
Example 7:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
Firstly, 1mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 350 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-7) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-7 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2059.3F/g under the condition of 2mol/L KOH solution and 1A/g current density.
Example 8:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
firstly, 1mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor in air atmosphere at 450 ℃ for 2 hours, and heating up at a rate of 2 ℃ for -1 minutes to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-8) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-8 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2154F/g under the condition of 2mol/L KOH solution and 1A/g current density.
Example 9:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
firstly, 1mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 1mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-9) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-9 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 1985.2F/g under the condition of 2mol/L KOH solution and 2A/g current density.
Example 10:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
firstly, 1mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、2mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-10) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-10 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 1835.7F/g under the condition of 2mol/L KOH solution and 5A/g current density.
Example 11:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
firstly, 1mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 8 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-11) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-11 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 1859F/g under the condition of 2mol/L KOH solution and 1A/g current density.
Example 12:
A NiGa-LDH@ZnCo 2O4 @NF composite material and a preparation method and application thereof comprise the following steps:
firstly, 1mmol Zn(NO3)2·6H2O、2mmol Co(NO3)2·6H2O、2mmol NH4F mmol of urea and 5mmol of urea are added into 40mL of water, stirred and uniformly dispersed by ultrasound to obtain a mixed solution I;
Transferring the mixed solution I and 8mm multiplied by 1cm foam nickel which is sequentially treated by acetone, ethanol and water into a 50mL polytetrafluoroethylene lining stainless steel autoclave, performing hydrothermal reaction for 6 hours at 120 ℃, naturally cooling to room temperature, washing 3 times by deionized water, vacuum drying at 60 ℃ for 12 hours to obtain ZnCo 2O4 @NF precursor, calcining the precursor at 400 ℃ for 2 hours in an air atmosphere, and heating at a rate of 2 ℃ for -1 min to finally obtain ZnCo 2O4 @NF material;
Thirdly, mixing 2mmol of Ni (NO 3)2·6H2O、1mmol Ga(NO3)3·xH2 O, 12mmol of urea and 30mL of water, fully stirring and dispersing uniformly to completely dissolve the Ni and the urea to obtain a mixed solution II;
And fourthly, transferring the mixed solution II and ZnCo 2O4 @NF material into a 50mL polytetrafluoroethylene lining stainless steel autoclave for hydrothermal reaction, carrying out hydrothermal reaction at 120 ℃ for 12 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the NiGa-LDH@ZnCo 2O4 @NF composite material. The NiGa-LDH@ZnCo 2O4 @NF composite material (recorded as NGZC-12) is used as a working electrode.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: NGZC-12 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2259.4F/g under the condition of 2mol/L KOH solution and 1A/g current density.
Example 13:
In comparison with example 1, the same applies for the most part, except that in this example, 2mmol Co (NO 3)2·6H2 O) was changed to 1.5mmol Co (NO 3)2·6H2 O).
Example 14:
Most of the same was made as in example 1, except that in this example, 40mL of water in the first step was changed to 35mL of water.
Example 15:
Most of the same was made as in example 1, except that in this example, 40mL of water in the first step was changed to 45mL of water.
Example 16:
The procedure is largely the same as in example 1 except that in this example, the hydrothermal reaction at 120℃in the second step is changed to the hydrothermal reaction at 120℃for 5.5 hours.
Example 17:
The procedure is largely the same as in example 1 except that in this example, the hydrothermal reaction at 120℃for 6h in the second step is changed to the hydrothermal reaction at 120℃for 6.5h.
Example 18:
In the second step, "calcination at a temperature of 400℃in an air atmosphere for 2 hours, the temperature increase rate of 2℃min -1" was changed to "calcination at a temperature of 400℃in an air atmosphere for 1.5 hours, the temperature increase rate of 1.5℃min -1", as compared with example 1, the same applies to the most part.
Example 19:
In the second step, "calcination at a temperature of 400℃in an air atmosphere for 2 hours at a temperature increase rate of 2℃min -1" was changed to "calcination at a temperature of 400℃in an air atmosphere for 2.5 hours at a temperature increase rate of 2.5℃min -1", as compared with example 1, the same applies to the most part.
Example 20:
In comparison with example 1, the same applies for the most part, except that in this example, 2mmol Ni (NO 3)2·6H2 O) was changed to 1.5mmol Ni (NO 3)2·6H2 O).
Example 21:
In comparison with example 1, the same was achieved in the vast majority, except that in this example, 1mmol Ga (NO 3)3·xH2 O) was changed to 1.5mmol Ga (NO 3)3·xH2 O).
Example 22:
most of the same was made as in example 1, except that in this example, 30mL of water in the third step was changed to 25mL of water.
Example 23:
Most of the same was made as in example 1, except that in this example, 30mL of water in the third step was changed to 35mL of water.
Example 24:
in comparison with example 1, the same applies for the most part except that in this example, the hydrothermal treatment in the fourth step at 120℃was changed to the hydrothermal treatment at 110℃for 10 hours.
Example 25:
In comparison with example 1, the same applies for the most part except that in this example, the hydrothermal treatment in the fourth step at 120℃was changed to the hydrothermal treatment at 130℃for 10 hours.
Example 26:
In this example, NGZC-1 composite material obtained in example 1 was used as working electrode of supercapacitor, and the specific application process was the same as that of example 1 except that in this example, the mass ratio of nfs@nco-1 composite material, carbon black, polytetrafluoroethylene was adjusted to 8:0.8:0.8.
Example 27:
In this embodiment, the nfs@nco-1 composite material obtained in embodiment 1 is used as a working electrode of a supercapacitor, and the specific application process is mostly the same as that of embodiment 1, except that in this embodiment, the mass ratio of the nfs@nco-1 composite material, carbon black, and polytetrafluoroethylene is adjusted to 8:1.2:1.2.
Comparative example 1:
Compared with example 1, most of the materials were the same except that the introduction of nickel foam was omitted, resulting in a NiGa-LDH@ZnCo 2O4 material.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: the NiGa-LDH@ZnCo 2O4 material is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 1369.2F/g under the condition of 2mol/L KOH solution and 1A/g current density. From this, the specific capacitance of the NiGa-LDH@ZnCo 2O4 material without the foam nickel is far smaller than that of the NiGa-LDH@ZnCo 2O4 composite material in example 1, which shows that the electrochemical performance of the composite material can be greatly improved by the introduction of the foam nickel.
Comparative example 2:
Compared with example 1, most of the materials are the same except that the foam nickel is changed into carbon fiber cloth with the same volume, and the NiGa-LDH@ZnCo 2O4 @carbon fiber cloth material is obtained.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: the NiGa-LDH@ZnCo 2O4 @carbon fiber cloth material is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 1968.3F/g under the condition of 2mol/L KOH solution and 1A/g current density. From this, it is known that the specific capacitance of the NiGa-ldh@znco 2O4 @carbon fiber cloth material is smaller than that of the NiGa-ldh@znco 2O4 @nf composite material in example 1, which indicates that the three-dimensional conductive skeleton foam nickel substrate can fully exert the electrochemical properties of the composite material more than the two-dimensional planar carbon fiber cloth substrate.
Comparative example 3:
in comparison to example 1, the vast majority of the same was obtained, except that no gallium source was added, resulting in a Ni (OH) 2@ZnCo2O4 @NF material.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: the Ni (OH) 2@ZnCo2O4 @NF material is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 2194F/g under the condition of 2mol/L KOH solution and 1A/g current density. From this, it is shown that the specific capacitance of Ni (OH) 2@ZnCo2O4 @NF material without gallium source is smaller than that of NiGa-LDH@ZnCo 2O4 @NF composite material in example 1, indicating that doping of Ga element can improve electrochemical properties of binary metal hydroxide.
Comparative example 4:
Compared with example 1, most of the materials are the same except that the addition of a nickel source and a gallium source is omitted, namely the obtained material is ZnCo 2O4 @NF.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: the ZnCo 2O4 @NF material is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 1347.8F/g under the condition of 2mol/L KOH solution and 1A/g current density. From this, the specific capacitance of the obtained material ZnCo 2O4 @NF is far smaller than that of the NiGa-LDH@ZnCo 2O4 @NF composite material in example 1, indicating that the recombination of layered double hydroxide LDH is beneficial to improving the specific capacitance of ZnCo 2O4 @NF.
Comparative example 5:
compared with example 1, the material obtained was NiGa-LDH@NF, except that the addition of zinc source, cobalt source and urea was omitted.
Electrochemical testing is carried out by using a Cinna CHI760e electrochemical workstation through a cyclic voltammetry and constant current charging and discharging method and a three-electrode system: the NiGa-LDH@NF material is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test shows that the composite material has excellent oxidation-reduction capability. The specific capacitance of the composite material reaches 1639.4F/g under the condition of 2mol/L KOH solution and 1A/g current density. From this, the specific capacitance of the obtained material NiGa-LDH@NF is far smaller than that of the NiGa-LDH@ZnCo 2O4 @NF composite material in example 1, which shows that the electrochemical performance of the single-component material can be greatly improved by compounding the ternary metal oxide as a precursor with the layered double hydroxide LDH.
In the above embodiments, according to actual needs, the water added in the first step may be arbitrarily adjusted within a range of 35 to 45mL, and similarly, the water added in the third step may be arbitrarily adjusted within a range of 25 to 35 mL.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (4)
1. The preparation method of the NiGa-LDH@ZnCo 2O4 @NF composite material is characterized by comprising the following steps of:
(1) Dispersing a zinc source, a cobalt source, ammonium fluoride and urea in water to obtain a solution A;
(2) Adding foam nickel into the obtained solution A, and obtaining ZnCo 2O4 @NF material through hydrothermal treatment, washing, drying and calcining;
(3) Dispersing a nickel source, a gallium source and urea in water to obtain a solution B;
(4) Soaking the ZnCo 2O4 @NF material in the solution B, and then carrying out hydrothermal treatment, washing and drying to obtain a target product;
In the step (3), the nickel source is Ni (NO 3)2·6H2 O, the gallium source is Ga (NO 3)3·xH2 O;
ni (NO 3)2·6H2O、Ga(NO3)3·xH2 O, urea and water are added in the ratio of (1-2) mmol to (12) mmol (25-35) mL;
In the step (4), the hydrothermal temperature is 110-130 ℃ and the hydrothermal time is 8-12h;
In the step (1), the zinc source is Zn (NO 3)2·6H2 O, and the cobalt source is Co (NO 3)2·6H2 O;
The addition amount ratio of Zn (NO 3)2·6H2O、Co(NO3)2·6H2 O, ammonium fluoride, urea and water is (0.5-2) mmol (1-2) mmol, 2mmol, 5mmol (35-45) mL;
In the step (2), the size of the foam nickel is 1cm multiplied by 8mm, and the volume of the corresponding added solution A is 35-45mL;
In the step (2), the hydrothermal temperature is 100-140 ℃ and the hydrothermal time is 5.5-6.5h;
in the step (2), calcination is carried out under the air atmosphere, the calcination temperature is 350-450 ℃, the heat preservation time is 1.5-2.5h, and the heating rate is 1.5-2.5 ℃/min.
2. A NiGa-ldh@znco 2O4 @nf composite material, characterized in that it is prepared by the preparation method according to claim 1.
3. The use of a NiGa-ldh@znco 2O4 @nf composite material as claimed in claim 2, wherein the composite material is used as a working electrode for a supercapacitor, the specific application process being:
After grinding the NiGa-LDH@ZnCo 2O4 @NF composite material, uniformly mixing the ground NiGa-LDH@ZnCo 2O4 @NF composite material with carbon black and polytetrafluoroethylene, and then pressing the mixture on a foam nickel sheet to obtain the working electrode.
4. The application of the NiGa-LDH@ZnCo 2O4 @NF composite material according to claim 3, wherein the mass ratio of the NiGa-LDH@ZnCo 2O4 @NF composite material, carbon black and polytetrafluoroethylene is 8: (0.8-1.2): (0.8-1.2).
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| Characterization of self-assembled films of NiGa layered double hydroxide nanosheets and their electrochemical properties;Ozge Altuntasoglu etc.;《Journal of Solid State Chemistry》;第181卷;3257-3263 * |
| Constructing ZnCo2O4@LDH Core-shell hierarchical structure for high performance supercapacitor electrodes;白雪等;《Ceramics International》;第45卷;14943-14952 * |
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