CN111326351A - Cu for capacitor2Preparation method of O/NiO material - Google Patents
Cu for capacitor2Preparation method of O/NiO material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011889 copper foil Substances 0.000 claims abstract description 78
- 238000000151 deposition Methods 0.000 claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 32
- 239000007772 electrode material Substances 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000004070 electrodeposition Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000003990 capacitor Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims abstract description 17
- 229910018054 Ni-Cu Inorganic materials 0.000 claims abstract description 16
- 229910018481 Ni—Cu Inorganic materials 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000004769 chrono-potentiometry Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910007567 Zn-Ni Inorganic materials 0.000 claims description 8
- 229910007614 Zn—Ni Inorganic materials 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 16
- 239000011230 binding agent Substances 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract 2
- 229910052786 argon Inorganic materials 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 12
- 238000002484 cyclic voltammetry Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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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 invention discloses Cu for a capacitor2The preparation method of the O/NiO material comprises the following steps: (1) taking a copper foil as a substrate, and sequentially cleaning and drying; (2) preparing a deposition solution required by electrochemical deposition; (3) carrying out electrochemical deposition on the copper foil by using a time potential method under a three-electrode system, washing and drying; (4) performing low-temperature diffusion annealing on the obtained electrodeposition product under argon; (5) preparing a dealloying solution required by electrochemical dealloying; (6) performing electrochemical dealloying on the copper foil precursor of the Zn-Ni-Cu alloy layer in the step (4) by using a chronopotentiometry method under a three-electrode system to obtain nano-spherical Cu without the binding agent2And (3) O/NiO electrode material. The method has the advantages of short preparation time, high efficiency, no need of a binder for the active substance and the copper foil substrate, firm combination, controllable appearance of the composite material, high specific capacitance and longer cycle life.
Description
Technical Field
The invention relates to a composite material for a capacitor, in particular to Cu for the capacitor2A preparation method of an O/NiO material belongs to the field of preparation of electrode materials of super capacitors.
Background
With the rapid increase of energy demand in economic development, the problem of the gradual shortage of non-renewable resources such as petroleum, coal and natural gas is becoming more serious, and in order to deal with the increasingly serious energy and environmental crisis, the development and utilization of renewable energy and related technologies thereof are of great importance. To date, most renewable clean energy sources (e.g., wind, solar) are highly dependent on environmental conditions, making it difficult to achieve a controlled continuous supply of energy, and therefore, there is a pressing need for energy storage devices to store and convert these intermittent energy sources. In a plurality of energy storage devices, the super capacitor combines the energy storage characteristic of a battery with the discharge characteristic of a capacitor, and has the advantages of high power density (more than 10 times of the power density of a lithium ion battery), long service life (up to 10000 times), safety, environmental friendliness and the like, so that the super capacitor is widely concerned and has wide application prospects in the fields of mobile power supplies, standby power supplies, hybrid electric vehicle power supplies and the like.
The most important factor influencing the electrochemical performance of the supercapacitor is an electrode material, the performance of the electrode material directly determines the performance of the supercapacitor, and the electrode material can be divided into three types according to the physical and chemical properties of an active material on the electrode material: a carbon-based material, a transition metal compound, and a conductive polymer. Since the advent of the pseudocapacitor, the metal oxide with the advantages of low cost, high theoretical capacity, environmental friendliness and the like is the best choice for the electrode material of the pseudocapacitor, and the energy density can reach several times that of a carbon material. The material selection also starts from the first expensive and toxic ruthenium oxide (RuO)2) The method develops to the transition metal oxides such as nickel oxide, cobalt oxide, manganese oxide, cuprous oxide and the like which are commonly used at present.
The preparation of the electrode material with high specific surface area is one of the ways to improve the electrochemical performance of the electrode material, and the nano-spherical electrode material has larger specific surface area, which means that the contact area of the electrode material and the electrolyte is increased, thereby shortening the electron transmission path, increasing the electron transfer efficiency and improving the electrochemical performance of the material. At present, an aluminum foil or a copper foil is used as a current collector of a commercial capacitor, carbon is used as a main active substance and a binding agent is coated on the current collector, the phenomenon of active substance flaking is serious in the preparation process, and the performances of energy density, specific capacitance and the like of the prepared electrode material are difficult to satisfy. Theoretically, metal oxides with higher energy density mainly directly grow on expensive three-dimensional substrates such as foamed nickel, carbon cloth and the like, the price of the substrates is dozens of times of that of aluminum foils and copper foils, and the practical application of the substrates is limited by the cost problem.
Disclosure of Invention
In view of the problems of the prior art, the present invention provides a Cu for capacitor2The preparation method of the O/NiO material solves the problem of poor bonding force between the active substance and the substrate, does not need a binder, and has controllable morphology. Meanwhile, the electrical property of the prepared electrode material is optimized, the manufacturing process is simplified, and the preparation efficiency is improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
cu for capacitor2The preparation method of the O/NiO material comprises the following steps:
(1) cutting T2 pure copper foil into pieces with area of 1 × 2cm2Washing the cut copper foil piece by using a sodium hydroxide solution with the mass fraction of 3.5%, dilute hydrochloric acid (6:1), deionized water and absolute ethyl alcohol in sequence, and then drying the copper foil piece in a vacuum drying oven at 70 ℃ for 9-12 h;
(2) preparing a deposition solution required by electrochemical deposition, namely fully mixing and stirring nickel salt, zinc salt, boric acid and deionized water, and then transferring a beaker to an ultrasonic disperser to carry out uniform ultrasonic oscillation for 5-10 min;
(3) and (3) starting an electrochemical workstation, putting the deposition solution obtained in the step (2) into a beaker, and carrying out electrochemical deposition on the copper foil by using a timed potential method under a three-electrode system with the copper foil as a working electrode, the platinum electrode as a counter electrode and the saturated calomel electrode as a reference electrode, wherein the deposition current is 0.02A, and the deposition time is 150-600 s. After the reaction is finished, repeatedly washing the copper foil with deionized water and absolute ethyl alcohol for more than three times, and drying the copper foil in a vacuum drying oven at the temperature of 70 ℃ for 10-12h to obtain a copper foil intermediate product with a Zn-Ni plating layer on the surface;
(4) and carrying out annealing treatment on the sample. After a sample is prepared by electrodeposition, the sample is placed into a program-controlled high-temperature furnace at 150 ℃ and is kept for 2 hours in a high-purity argon atmosphere for annealing, so that deposited substances are uniformly diffused, the bonding capacity between the deposited substances and the copper foil is enhanced, and the copper foil precursor with the surface being a Zn-Ni-Cu alloy layer is obtained.
(5) Preparing a dealloying liquid required by electrochemical dealloying, namely, fully mixing and stirring potassium chloride and deionized water, and then transferring a beaker to an ultrasonic disperser to perform uniform ultrasonic oscillation for 5-10 min;
(6) and performing electrochemical dealloying on the copper foil precursor with the surface being the Zn-Ni-Cu alloy layer by using a chronopotentiometry method under a three-electrode system. Washing, drying and high-temperature oxidation to obtain the nano spherical Cu without the binding agent2And (3) O/NiO electrode material.
Preferably, the zinc salt in step (2) is Zn (NO)3)2·6H2O, Ni salts being Ni (NO)3)2·6H2O。
Preferably, the electrolyte in the step (3) consists of 0.05mol/L of Zn (NO)3)2·6H2O, 0.5mol/L Ni (NO)3)2·6H2O and 0.5mol/L of H3BO3Dissolving in 50mL deionized water.
Preferably, the conditions of the heat-preserving treatment in the step (4) are raised to 150 ℃ at 3 ℃/min and heat-preserving for 2h under a high-purity argon atmosphere.
Preferably, the dealloying solution required for preparing electrochemical dealloying in step (5) is a 3.5 w.t.% KCl solution.
Preferably, the electrochemical dealloying condition of the chronopotentiometry in the step (6) is dealloying current of 0.02A and dealloying time of 150-.
Preferably, the conditions of the oxidation treatment in step (6) are raised to 200 ℃ at 3 ℃/min and kept in air for 2 h.
Compared with the prior art, the preparation method has the beneficial effects that:
the method for preparing the electrode material has the advantages of short sample preparation time, high efficiency, simple experimental instrument and controllable product appearance in the electrodeposition process. The electrode material with the nano spherical morphology and uniform growth can be prepared by the method, the electrode material is integrated with a copper foil substrate structure, a binder is not needed, the specific surface area is large, and more active sites are provided for the oxidation-reduction reaction while the surface stress generated by the metal oxide in the electrochemical cycle is released, so that the high performance and the long cycle life are provided for equipment. When the prepared electrode material is used for a super capacitor, the specific capacitance is high, the rate capability is good, the cycle life is long, and the application prospect is very wide.
Drawings
FIG. 1 is Cu2Scanning electron microscope images of the O/NiO composite electrode, wherein (a-c) are SEM images of morphology evolution after deposition, annealing and dealloying oxidation respectively; (d-h) is an SEM photograph of examples 1-5; (i) TEM, HRTEM and SAED images of example 2;
FIG. 2 is Cu2Electrochemical performance test chart of the O/NiO composite material, (a-d) are CV and GCD curves of examples 1-5; (e-f) are CV and GCD curves of example 2 at different sweep rates and current densities.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1:
cu for capacitor2The preparation method of the O/NiO material is characterized by comprising the following steps of:
(1) cutting T2 pure copper foil into pieces with area of 1 × 2cm2Washing the cut copper foil piece by using a sodium hydroxide solution with the mass fraction of 3.5%, dilute hydrochloric acid (6:1), deionized water and absolute ethyl alcohol in sequence, and then drying the copper foil piece in a vacuum drying oven at 70 ℃ for 9-12 h;
(2) formulation of the deposition required for electrochemical depositionLiquid, 0.05mol/L Zn (NO)3)2·6H2O, 0.5mol/L Ni (NO)3)2·6H2O and 0.5mol/L of H3BO3Dissolving in 50mL deionized water, mixing, stirring, transferring beaker into ultrasonic disperser, and ultrasonic vibrating for 5-10 min;
(3) and (3) starting an electrochemical workstation, putting the deposition solution obtained in the step (2) into a beaker, and carrying out electrochemical deposition on the copper foil by using a timed potential method under a three-electrode system with the copper foil as a working electrode, the platinum electrode as a counter electrode and the saturated calomel electrode as a reference electrode, wherein the deposition current is 0.02A, and the deposition time is 150 s. After the reaction is finished, sequentially using deionized water and absolute ethyl alcohol to repeatedly wash for more than three times, and drying for 10-12h in a vacuum drying oven at the temperature of 70 ℃, thus obtaining the copper foil precursor with the surface being the Zn-Ni plating layer;
(4) and carrying out annealing treatment on the sample. After a sample is prepared by electrodeposition, the sample is placed into a program-controlled high-temperature furnace at 150 ℃ and is kept for 2 hours in a high-purity argon atmosphere for annealing, so that deposited substances are uniformly diffused, the bonding capacity between the deposited substances and the copper foil is enhanced, and the copper foil precursor with the surface being a Zn-Ni-Cu alloy layer is obtained.
(5) Preparing a dealloying solution required by electrochemical dealloying, namely adding 96.5g of deionized water into 3.5g of potassium chloride, fully mixing and stirring, and then transferring a beaker into an ultrasonic disperser to perform uniform ultrasonic oscillation for 5-10 min;
(6) performing electrochemical dealloying on a copper foil precursor with a Zn-Ni-Cu alloy layer on the surface under a three-electrode system by using a chronopotentiometric method, wherein the area of the copper foil precursor is 1 x 2cm2Current density of 20mA cm-2And the electrochemical dealloying time is 300 s. Washing, drying and high-temperature oxidation to obtain the nano spherical Cu without the binding agent2And (3) O/NiO electrode material.
Cu obtained as described above was prepared by the present example2The micro-morphology of the O/NiO composite electrode can be observed by a scanning electron microscope, and the O/NiO composite electrode is of an irregular spherical structure and is shown in figure 1.
The electrochemical performance test method comprises the following steps: cu to be prepared2O/NiO complexesThe composite material is used as an electrode and the electrochemical performance of the composite material is tested, the electrochemical performance of a working electrode is tested in a three-electrode system, an electrolyte is 1M KOH solution, a platinum sheet is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, the three-electrode system is connected to an electrochemical workstation (Shanghai Chenghua, CHI660E), the electrochemical performance of the electrode is tested by using Cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) technologies, and the cyclic stability test is carried out on a blue-cell test system, as shown in FIG. 2.
The material prepared by the method can be obtained by the series of electrochemical performance test methods, and the current density of the material is 1mA/cm2When the concentration reaches 487.7mF/cm2And 5000 circles of charge and discharge are cycled, and the cycle efficiency is 78.4%.
Example 2:
(1) cutting T2 pure copper foil into pieces with area of 1 × 2cm2Washing the cut copper foil piece by using a sodium hydroxide solution with the mass fraction of 3.5%, dilute hydrochloric acid (6:1), deionized water and absolute ethyl alcohol in sequence, and then drying the copper foil piece in a vacuum drying oven at 70 ℃ for 9-12 h;
(2) preparing a deposition solution required by electrochemical deposition, and 0.05mol/L of Zn (NO)3)2·6H2O, 0.5mol/L Ni (NO)3)2·6H2O and 0.5mol/L of H3BO3Dissolving in 50mL deionized water, mixing, stirring, transferring beaker into ultrasonic disperser, and ultrasonic vibrating for 5-10 min;
(3) and (3) starting an electrochemical workstation, putting the deposition solution obtained in the step (2) into a beaker, and carrying out electrochemical deposition on the copper foil by using a timed potential method under a three-electrode system with the copper foil as a working electrode, the platinum electrode as a counter electrode and the saturated calomel electrode as a reference electrode, wherein the deposition current is 0.02A, and the deposition time is 300 s. After the reaction is finished, sequentially using deionized water and absolute ethyl alcohol to repeatedly wash for more than three times, and drying for 10-12h in a vacuum drying oven at the temperature of 70 ℃, thus obtaining the copper foil precursor with the surface being the Zn-Ni plating layer;
(4) and carrying out annealing treatment on the sample. After a sample is prepared by electrodeposition, the sample is placed into a program-controlled high-temperature furnace at 150 ℃ and is kept for 2 hours in a high-purity argon atmosphere for annealing, so that deposited substances are uniformly diffused, the bonding capacity between the deposited substances and the copper foil is enhanced, and the copper foil precursor with the surface being a Zn-Ni-Cu alloy layer is obtained.
(5) Preparing a dealloying solution required by electrochemical dealloying, namely adding 96.5g of deionized water into 3.5g of potassium chloride, fully mixing and stirring, and then transferring a beaker into an ultrasonic disperser to perform uniform ultrasonic oscillation for 5-10 min;
(6) performing electrochemical dealloying on a copper foil precursor with a Zn-Ni-Cu alloy layer on the surface under a three-electrode system by using a chronopotentiometric method, wherein the area of the copper foil precursor is 1 x 2cm2Current density of 20mA cm-2And the electrochemical dealloying time is 300 s. Washing, drying and high-temperature oxidation to obtain the nano spherical Cu without the binding agent2And (3) O/NiO electrode material.
Cu obtained as described above was prepared by the present example2The micro-morphology of the O/NiO composite electrode can be observed by a scanning electron microscope, and the O/NiO composite electrode is of a regular spherical structure and is shown in figure 1.
The electrochemical performance test method comprises the following steps: cu to be prepared2The electrochemical performance of the working electrode is tested in a three-electrode system, the electrolyte is 1M KOH solution, a platinum sheet is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, the three-electrode system is connected to an electrochemical workstation (Shanghai Chenghua, CHI660E), the electrochemical performance of the electrode is tested by using Cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) technologies, and the cyclic stability test is performed on a blue-electricity battery test system, as shown in FIG. 2.
The material prepared by the method can be obtained by the series of electrochemical performance test methods, and the current density of the material is 1mA/cm2Can reach 2255.5mF/cm25000 circles of charge and discharge are cycled, and the cycle efficiency is 94.5 percent.
Example 3:
(1) cutting T2 pure copper foil into pieces with area of 1 × 2cm2Using 3.5% by mass of hydrogen hydroxide in this orderWashing the cut copper foil with sodium solution, dilute hydrochloric acid (6:1), deionized water and absolute ethyl alcohol, and then drying the copper foil in a vacuum drying oven at 70 ℃ for 9-12 h;
(2) preparing a deposition solution required by electrochemical deposition, and 0.05mol/L of Zn (NO)3)2·6H2O, 0.5mol/L Ni (NO)3)2·6H2O and 0.5mol/L of H3BO3Dissolving in 50mL deionized water, mixing, stirring, transferring beaker into ultrasonic disperser, and ultrasonic vibrating for 5-10 min;
(3) and (3) starting an electrochemical workstation, putting the deposition solution obtained in the step (2) into a beaker, and carrying out electrochemical deposition on the copper foil by using a timed potential method under a three-electrode system with the copper foil as a working electrode, the platinum electrode as a counter electrode and the saturated calomel electrode as a reference electrode, wherein the deposition current is 0.02A, and the deposition time is 450 s. After the reaction is finished, sequentially using deionized water and absolute ethyl alcohol to repeatedly wash for more than three times, and drying for 10-12h in a vacuum drying oven at the temperature of 70 ℃, thus obtaining the copper foil precursor with the surface being the Zn-Ni plating layer;
(4) and carrying out annealing treatment on the sample. After a sample is prepared by electrodeposition, the sample is placed into a program-controlled high-temperature furnace at 150 ℃ and is kept for 2 hours in a high-purity argon atmosphere for annealing, so that deposited substances are uniformly diffused, the bonding capacity between the deposited substances and the copper foil is enhanced, and the copper foil precursor with the surface being a Zn-Ni-Cu alloy layer is obtained.
(5) Preparing a dealloying solution required by electrochemical dealloying, namely adding 96.5g of deionized water into 3.5g of potassium chloride, fully mixing and stirring, and then transferring a beaker into an ultrasonic disperser to perform uniform ultrasonic oscillation for 5-10 min;
(6) performing electrochemical dealloying on a copper foil precursor with a Zn-Ni-Cu alloy layer on the surface under a three-electrode system by using a chronopotentiometric method, wherein the area of the copper foil precursor is 1 x 2cm2Current density of 20mA cm-2And the electrochemical dealloying time is 300 s. Washing, drying and high-temperature oxidation to obtain the nano spherical Cu without the binding agent2And (3) O/NiO electrode material.
Cu obtained as described above was prepared by the present example2O/NiThe micro-morphology of the O composite electrode can be observed by a scanning electron microscope, and the O composite electrode is of a block stacked structure, as shown in figure 1.
The electrochemical performance test method comprises the following steps: cu to be prepared2The electrochemical performance of the working electrode is tested in a three-electrode system, the electrolyte is 1M KOH solution, a platinum sheet is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, the three-electrode system is connected to an electrochemical workstation (Shanghai Chenghua, CHI660E), the electrochemical performance of the electrode is tested by using Cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) technologies, and the cyclic stability test is performed on a blue-electricity battery test system, as shown in FIG. 2.
The material prepared by the method can be obtained by the series of electrochemical performance test methods, and the current density of the material is 1mA/cm2Can reach 1675mF/cm25000 circles of charge and discharge are cycled, and the cycle efficiency is 86.7 percent.
Example 4:
(1) cutting T2 pure copper foil into pieces with area of 1 × 2cm2Washing the cut copper foil piece by using a sodium hydroxide solution with the mass fraction of 3.5%, dilute hydrochloric acid (6:1), deionized water and absolute ethyl alcohol in sequence, and then drying the copper foil piece in a vacuum drying oven at 70 ℃ for 9-12 h;
(2) preparing a deposition solution required by electrochemical deposition, and 0.05mol/L of Zn (NO)3)2·6H2O, 0.5mol/L Ni (NO)3)2·6H2O and 0.5mol/L of H3BO3Dissolving in 50mL deionized water, mixing, stirring, transferring beaker into ultrasonic disperser, and ultrasonic vibrating for 5-10 min;
(3) and (3) starting an electrochemical workstation, putting the deposition solution obtained in the step (2) into a beaker, and carrying out electrochemical deposition on the copper foil by using a timed potential method under a three-electrode system with the copper foil as a working electrode, the platinum electrode as a counter electrode and the saturated calomel electrode as a reference electrode, wherein the deposition current is 0.02A, and the deposition time is 300 s. After the reaction is finished, sequentially using deionized water and absolute ethyl alcohol to repeatedly wash for more than three times, and drying for 10-12h in a vacuum drying oven at the temperature of 70 ℃, thus obtaining the copper foil precursor with the surface being the Zn-Ni plating layer;
(4) and carrying out annealing treatment on the sample. After a sample is prepared by electrodeposition, the sample is placed into a program-controlled high-temperature furnace at 150 ℃ and is kept for 2 hours in a high-purity argon atmosphere for annealing, so that deposited substances are uniformly diffused, the bonding capacity between the deposited substances and the copper foil is enhanced, and the copper foil precursor with the surface being a Zn-Ni-Cu alloy layer is obtained.
(5) Preparing a dealloying solution required by electrochemical dealloying, namely adding 96.5g of deionized water into 3.5g of potassium chloride, fully mixing and stirring, and then transferring a beaker into an ultrasonic disperser to perform uniform ultrasonic oscillation for 5-10 min;
(6) performing electrochemical dealloying on a copper foil precursor with a Zn-Ni-Cu alloy layer on the surface under a three-electrode system by using a chronopotentiometric method, wherein the area of the copper foil precursor is 1 x 2cm2Current density of 20mA cm-2The electrochemical dealloying time is 150 s. Washing, drying and high-temperature oxidation to obtain the nano spherical Cu without the binding agent2And (3) O/NiO electrode material.
Cu obtained as described above was prepared by the present example2The micro-morphology of the O/NiO composite electrode can be observed by a scanning electron microscope, and the O/NiO composite electrode is a continuous spherical structure which is formed, and is shown in figure 1.
The electrochemical performance test method comprises the following steps: cu to be prepared2The electrochemical performance of the working electrode is tested in a three-electrode system, the electrolyte is 1M KOH solution, a platinum sheet is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, the three-electrode system is connected to an electrochemical workstation (Shanghai Chenghua, CHI660E), the electrochemical performance of the electrode is tested by using Cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) technologies, and the cyclic stability test is performed on a blue-electricity battery test system, as shown in FIG. 2.
The material prepared by the method can be obtained by the series of electrochemical performance test methods, and the current density of the material is 1mA/cm2Can reach 907.5mF/cm2Charge and discharge in cycles5000 cycles, and the circulation efficiency is 68.1%.
Example 5:
(1) cutting T2 pure copper foil into pieces with area of 1 × 2cm2Washing the cut copper foil piece by using a sodium hydroxide solution with the mass fraction of 3.5%, dilute hydrochloric acid (6:1), deionized water and absolute ethyl alcohol in sequence, and then drying the copper foil piece in a vacuum drying oven at 70 ℃ for 9-12 h;
(2) preparing a deposition solution required by electrochemical deposition, and 0.05mol/L of Zn (NO)3)2·6H2O, 0.5mol/L Ni (NO)3)2·6H2O and 0.5mol/L of H3BO3Dissolving in 50mL deionized water, mixing, stirring, transferring beaker into ultrasonic disperser, and ultrasonic vibrating for 5-10 min;
(3) and (3) starting an electrochemical workstation, putting the deposition solution obtained in the step (2) into a beaker, and carrying out electrochemical deposition on the copper foil by using a timed potential method under a three-electrode system with the copper foil as a working electrode, the platinum electrode as a counter electrode and the saturated calomel electrode as a reference electrode, wherein the deposition current is 0.02A, and the deposition time is 300 s. After the reaction is finished, sequentially using deionized water and absolute ethyl alcohol to repeatedly wash for more than three times, and drying for 10-12h in a vacuum drying oven at the temperature of 70 ℃, thus obtaining the copper foil precursor with the surface being the Zn-Ni plating layer;
(4) and carrying out annealing treatment on the sample. After a sample is prepared by electrodeposition, the sample is placed into a program-controlled high-temperature furnace at 150 ℃ and is kept for 2 hours in a high-purity argon atmosphere for annealing, so that deposited substances are uniformly diffused, the bonding capacity between the deposited substances and the copper foil is enhanced, and the copper foil precursor with the surface being a Zn-Ni-Cu alloy layer is obtained.
(5) Preparing a dealloying solution required by electrochemical dealloying, namely adding 96.5g of deionized water into 3.5g of potassium chloride, fully mixing and stirring, and then transferring a beaker into an ultrasonic disperser to perform uniform ultrasonic oscillation for 5-10 min;
(6) performing electrochemical dealloying on a copper foil precursor with a Zn-Ni-Cu alloy layer on the surface under a three-electrode system by using a chronopotentiometric method, wherein the area of the copper foil precursor is 1 x 2cm2Current density of 20mA cm-2The electrochemical dealloying time is 450 s. Washing, drying and high-temperature oxidation to obtain the nano spherical Cu without the binding agent2And (3) O/NiO electrode material.
Cu obtained as described above was prepared by the present example2The micro-morphology of the O/NiO composite electrode can be observed by a scanning electron microscope, and the O/NiO composite electrode is a collapsed spherical structure, and is shown in figure 1.
The electrochemical performance test method comprises the following steps: cu to be prepared2The electrochemical performance of the working electrode is tested in a three-electrode system, the electrolyte is 1M KOH solution, a platinum sheet is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, the three-electrode system is connected to an electrochemical workstation (Shanghai Chenghua, CHI660E), the electrochemical performance of the electrode is tested by using Cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) technologies, and the cyclic stability test is performed on a blue-electricity battery test system, as shown in FIG. 2.
The material prepared by the method can be obtained by the series of electrochemical performance test methods, and the current density of the material is 1mA/cm2Can reach 1167mF/cm2And 5000 circles of charge and discharge are cycled, and the cycle efficiency is 82.6 percent.
In summary, as can be seen from the above embodiments and the related drawings, in fig. 1, (a-c) is a graph clearly showing the morphology evolution in the manufacturing process of example 2, and in fig. 1, a shows an SEM of the Zn-Ni alloy film electrodeposited on the copper foil, after annealing at 150 ℃, fine spherical particles are formed on the surface of the Zn-Ni-Cu alloy film, and particles of different particle sizes are irregularly bonded together to form nanospheres after dealloying and oxidation.
As can be seen from the electrochemical performance test chart of FIG. 2, the (a, c) graphs describe cyclic voltammetry (cv) graphs of the electrode material at different deposition times and dealloying times, the potential window of the electrode material is about-0.3-0.5V, and the wider potential window of the electrode material is shown.
The (b, d) graph is a constant current charge-discharge test graph of the electrode material at different deposition time and dealloying time, and the longer the discharge time of the GCD curve is under the condition that the current density and the potential window are the same, the higher the specific capacitance of the material is.
(e-f) are cyclic voltammetry test charts of the electrode material of example 2 at different scanning speeds and galvanostatic charge-discharge test charts of the electrode material at different current densities. A pair of distinct redox peaks can be observed for each CV curve, indicating that the capacitance of the electrode material is mainly derived from Cu2Pseudo capacitance generated in the oxidation-reduction process of O/NiO. With the continuous increase of the scanning rate, the CV curve still has a more obvious oxidation reduction peak, which indicates that the material has better rate performance. The charging curve and the discharging curve have certain symmetry, which shows that the electrode material has good stability and high reversibility. Each charge-discharge curve has a pair of platforms, and the pseudocapacitance characteristics are represented.
Claims (7)
1. Cu for capacitor2The preparation method of the O/NiO material is characterized by comprising the following steps of:
(1) cutting T2 pure copper foil into pieces with area of 1 × 2cm2Washing the cut copper foil piece by using sodium hydroxide (3.5 w.t.%), dilute hydrochloric acid (6:1), deionized water and absolute ethyl alcohol in sequence, and then drying the copper foil piece in a vacuum drying oven at 70 ℃ for 9-12 hours;
(2) preparing a deposition solution required by electrochemical deposition, namely fully mixing and stirring nickel salt, zinc salt, boric acid and deionized water, and then transferring a beaker to an ultrasonic disperser to carry out uniform ultrasonic oscillation for 5-10 min;
(3) starting an electrochemical workstation, placing the deposition solution obtained in the step (2) in a beaker, and carrying out electrochemical deposition on the copper foil by using a timed potential method under a three-electrode system with the copper foil as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, wherein the deposition current is 0.02A, and the deposition time is 150-600 s; after the reaction is finished, sequentially using deionized water and absolute ethyl alcohol to repeatedly wash for more than three times, and drying for 10-12h in a vacuum drying oven at the temperature of 70 ℃, thus obtaining the copper foil precursor with the surface being the Zn-Ni plating layer;
(4) annealing the sample, after the sample is prepared by electrodeposition, putting the sample into a program-controlled high-temperature furnace, heating to 150 ℃, and keeping the temperature for 2 hours in a high-purity argon atmosphere for annealing, so that the deposited substance is uniformly diffused, the bonding capability between the deposited substance and the copper foil is enhanced, and the copper foil precursor with the surface being a Zn-Ni-Cu alloy layer is obtained;
(5) preparing a dealloying liquid required by electrochemical dealloying, namely, fully mixing and stirring potassium chloride and deionized water, and then transferring a beaker to an ultrasonic disperser to perform uniform ultrasonic oscillation for 5-10 min;
(6) electrochemical dealloying is carried out on the copper foil precursor with the surface being Zn-Ni-Cu alloy layer under a three-electrode system by using a chronopotentiometric method, and nano-spherical binderless Cu is obtained after washing, drying and high-temperature oxidation2And (3) O/NiO electrode material.
2. Cu for capacitors as claimed in claim 12The preparation method of the O/NiO material is characterized in that the zinc salt in the step (2) is Zn (NO)3)2·6H2O, Ni salts being Ni (NO)3)2·6H2O。
3. Cu for capacitors as claimed in claim 22The preparation method of the O/NiO material is characterized in that the electrolyte in the step (3) is prepared from 0.05mol/L of Zn (NO)3)2·6H2O, 0.5mol/L Ni (NO)3)2·6H2O and 0.5mol/L of H3BO3Dissolving in 50mL deionized water.
4. Cu for capacitor according to claim 1 or 22The preparation method of the O/NiO material is characterized in that the heat preservation treatment in the step (4) is carried out under the conditions that the temperature is raised to 150 ℃ at the speed of 3 ℃/min and the heat is preserved for 2 hours in a high-purity argon atmosphere.
5. Cu for capacitor according to claim 1 or 22The preparation method of the O/NiO material is characterized in that the dealloying solution required by the electrochemical dealloying prepared in the step (5) is 3.5 w.t.% KCl solution.
6. Cu for capacitor according to claim 1 or 22The preparation method of the O/NiO material is characterized in that the electrochemical dealloying condition of the chronopotentiometry in the step (6) is that the dealloying current is 0.02A, and the dealloying time is 150-450 s.
7. Cu for capacitor according to claim 1 or 22The preparation method of the O/NiO material is characterized in that the oxidation treatment in the step (6) is carried out under the conditions that the temperature is increased to 200 ℃ at the speed of 3 ℃/min and the temperature is kept in the air for 2 h.
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