CN116815223A - Electrode and preparation method and application thereof - Google Patents
Electrode and preparation method and application thereof Download PDFInfo
- Publication number
- CN116815223A CN116815223A CN202311026656.6A CN202311026656A CN116815223A CN 116815223 A CN116815223 A CN 116815223A CN 202311026656 A CN202311026656 A CN 202311026656A CN 116815223 A CN116815223 A CN 116815223A
- Authority
- CN
- China
- Prior art keywords
- salt
- nickel
- metal substrate
- electrode
- electrode according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 claims abstract description 71
- 239000002184 metal Substances 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 126
- 239000000835 fiber Substances 0.000 claims description 26
- 150000002815 nickel Chemical class 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 150000001868 cobalt Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 150000002505 iron Chemical class 0.000 claims description 8
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 4
- XOTUNZWIDVULPE-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical group O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] XOTUNZWIDVULPE-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004146 energy storage Methods 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 239000011232 storage material Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000013068 control sample Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 229910003266 NiCo Inorganic materials 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000002203 pretreatment Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The application relates to the technical field of hydrogen energy material preparation, and discloses an electrode, a preparation method and application thereof, wherein the preparation method comprises the following steps: and (3) putting the metal substrate into heating equipment, heating at a low temperature under a calcining atmosphere, preserving heat, naturally cooling, washing with water and drying to obtain the activated metal substrate. And standing the activated metal substrate in a mixed solution of double metal salts, and growing a double hydroxide nano-sheet catalyst on the activated metal substrate in situ. The electrode prepared by the preparation method has better oxygen evolution activity than a control sample subjected to conventional pretreatment such as dilute acid and the like, and can work under high current density for a long time.
Description
Technical Field
The application relates to the technical field of hydrogen energy material preparation, and mainly relates to an electrode, a preparation method and application thereof.
Background
With the massive consumption of fossil energy, the energy shortage crisis becomes increasingly serious. Therefore, it is becoming urgent to find clean energy that can replace fossil energy. Hydrogen energy is considered to be one of the cleanest energy sources at present because of zero carbon emissions during use. There are various ways of obtaining hydrogen energy, and among them, the most promising way is to use renewable energy sources to generate electricity and then use electrolyzed water to produce hydrogen.
In the water electrolysis process, the process of generating oxygen from the anode end at the hydroxyl oxide involves four-electron transfer, and the electrolysis efficiency is extremely low relative to the cathode end, so that the method becomes a key step for restricting the water electrolysis reaction. In recent years, oxides, hydroxides, sulfides and phosphides of various transition metals can show good catalytic water and electricity oxygen analysis activity, and the hydroxide performance of the bimetal is particularly outstanding, the preparation method is relatively simple, the environmental pollution is less, and the important attention of researchers is paid. However, the cleaning of the surface of the metal substrate is more required due to the relatively mild hydroxide preparation conditions, and the substrate needs to be pretreated to remove organic matters or other impurities on the surface. The common cleaning mode of the metal substrate at present is to sequentially clean the metal substrate by using acetone, dilute acid and ethanol, so that organic matters and an oxide layer on the surface of the substrate can be better removed. However, this method wastes more solvent and makes it more difficult to perform a soak cleaning operation for a large area of metal substrate.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present application aims to provide an electrode, a preparation method and an application thereof, and aims to solve the problems that a large amount of acid and alkali are required in the existing pretreatment method of a metal substrate, and large-scale operation is difficult.
The technical scheme of the application is as follows:
a method of preparing an electrode, comprising the steps of:
s1, placing a metal substrate into heating equipment, heating at a low temperature under a calcining atmosphere, preserving heat, naturally cooling, washing with water, and drying to obtain an activated metal substrate;
s2, standing the activated metal substrate in a mixed solution of double metal salts, and growing a double hydroxide nano-sheet catalyst on the activated metal substrate in situ.
The metal substrate is subjected to low-temperature heating treatment in a calcining atmosphere, surface organic matters are removed, an oxide layer is reserved, and then the catalyst is soaked on the metal substrate at room temperature to grow the double hydroxide nano-sheet catalyst in situ.
In the preparation method of the electrode, in the step S1, the low-temperature heating temperature is 100-300 ℃, the temperature rising rate is 2-10 ℃ per minute, and the heat preservation time is 0.5-5 hours. Through the low-temperature heating process, organic matters or greasy dirt on the surface of the metal substrate can be oxidized and removed, and meanwhile, the temperature is controlled within 300 ℃ and the heating time is controlled within 5 hours, so that the metal substrate can be prevented from becoming brittle.
In the preparation method of the electrode, in the step S1, the metal substrate is a nickel-based substrate;
in the step S1, the calcining atmosphere is an air atmosphere or an inert atmosphere, and the air pressure is one atmosphere;
in step S1, the heating device is an oven, a muffle furnace, or a tube furnace.
The preparation method of the electrode comprises the step of preparing the nickel-based substrate by using foam nickel, nickel screen or nickel fiber felt.
In the preparation method of the electrode, in the step S2, the standing temperature is 20-30 ℃, and the standing time is 24-72 hours.
The preparation method of the electrode comprises the step of mixing the bimetal salt mixed solution with the water solution containing two non-noble metal salts.
The preparation method of the electrode comprises the step of mixing a bimetal salt mixed solution with an iron salt mixed solution or a nickel salt mixed solution with a cobalt salt mixed solution;
the nickel salt is nickel chloride hexahydrate, the cobalt salt is cobalt nitrate nonahydrate or cobalt chloride hexahydrate, and the ferric salt is ferrous chloride tetrahydrate or ferrous sulfate heptahydrate;
the molar ratio of the nickel salt to the ferric salt or the cobalt salt is (5-20): 1, and the mass ratio of the nickel salt to the water is 1: (20-100).
The preparation method of the electrode comprises the steps that nickel salt is nickel chloride hexahydrate, ferric salt is ferrous sulfate heptahydrate, and cobalt salt is cobalt chloride hexahydrate;
the molar ratio of the nickel salt to the iron salt or the cobalt salt is (9-11): 1, and the mass ratio of the nickel salt to the water is 1: (40-60).
An electrode, wherein the electrode is prepared by the preparation method of the electrode.
Use of an electrode as described above, wherein the electrode is used for the preparation of an energy storage material or for an electrolytic water oxygen evolution reaction.
The beneficial effects are that: in the scheme of the application, by optimizing the pretreatment mode of the metal substrate, the pretreatment method of the metal substrate which is simple to operate and does not need a solvent is adopted, so that the organic matters on the metal substrate can be fully removed and the metal substrate can be activated, and the double hydroxide nano-sheet catalyst can be grown on the metal substrate only by a simple soaking method. The electrode prepared by the preparation method has better oxygen evolution activity than a control sample subjected to conventional pretreatment such as dilute acid, can work under high current density for a long time, has great application prospect, and is expected to be applied to preparation of other electrode materials.
Drawings
FIG. 1 is a scanning electron microscope image of a NiFe LDH/a-Ni mat according to example 1 of the present application.
FIG. 2 is a scanning electron microscope image of the NiFe LDH/Ni felt of control 1 in example 1 of the present application.
FIG. 3 is a graph showing the electrochemical performance of NiFe LDH/a-Ni felt, niFe LDH/Ni felt and Ni felt of example 1 of the present application.
FIG. 4 is a graph comparing constant current test results under high current with NiFe LDH/a-Ni felt and NiFe LDH/Ni felt respectively as anodes and untreated Ni fiber felt as cathode in example 1 of the present application.
FIG. 5 is a graph showing the electrochemical performance of four regions of 10*10cm NiFe LDH/a-Ni felt in example 2 of the present application.
FIG. 6 is a scanning electron microscope image of 10*10cm NiFe LDH/a-Ni felt in example 2 of the present application.
FIG. 7 is a graph showing the electrochemical performance of NiCo LDH/a-Ni felt, niCo LDH/Ni felt and Ni felt in example 3 of the present application.
FIG. 8 is a graph comparing electrochemical performance of NiFe LDH/a-Ni networks, niFe LDH/Ni networks, and Ni networks in example 4 of the present application.
Detailed Description
The application provides an electrode, a preparation method and application thereof, and the application is further described in detail below in order to make the purpose, technical scheme and effect of the application more clear and definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
Before the present application, it was thought that impurities such as organic matters and oxide layers on the surface of a metal substrate affect a catalyst on the surface of the metal substrate, and therefore, the metal substrate is pretreated before the catalyst is prepared on the surface of the metal substrate, and impurities such as organic matters and oxide layers on the surface of the metal substrate are removed. The cleaning mode of the metal substrate commonly used at present is to sequentially clean the metal substrate by using acetone, dilute acid and ethanol, so that organic matters and an oxide layer on the surface of the metal substrate can be better removed. Further, prior to the date of the present application, hydroxide preparation conditions were generally considered to be relatively mild, and cleaning of the surface of the metal substrate was more required, and pretreatment of the metal substrate was required to remove organics or other impurities from the surface. It has been reported in the literature that the surface of a Ni-based substrate is liable to remain greasy dirt or organic matters in the production process, and the surface of the Ni-based substrate is liable to be hydrophobic, so that the Ni-based substrate cannot interact with the soaking liquid, and hydroxide is difficult to grow in situ.
However, for metal substrates requiring growth of hydroxide, the presence of an oxide layer is not necessarily an impediment to the growth of hydroxide. Therefore, the applicant proposes a new pretreatment method of a metal substrate for growing hydroxide, using a non-solvent method, only removing surface organics and leaving an oxide layer, which may be a more suitable pretreatment method of a metal substrate for preparing a large-area anode, which can improve the anode performance.
Specifically, the application provides a preparation method of an electrode, which comprises the following steps:
s1, placing the metal substrate into heating equipment, heating at a low temperature under a calcining atmosphere, preserving heat, naturally cooling, washing with water, and drying to obtain the activated metal substrate.
S2, standing the activated metal substrate in the mixed solution of the double metal salts, and growing the double hydroxide nano-sheet catalyst on the activated metal substrate in situ.
The metal substrate is subjected to low-temperature heating treatment in a calcining atmosphere, surface organic matters are removed, an oxide layer is reserved, and then the catalyst is soaked on the metal substrate at room temperature to grow the double hydroxide nano-sheet catalyst in situ.
Further, in step S1, the metal substrate is a nickel-based substrate. The metallic Ni is most stable in alkaline electrolyzed water, and therefore, in the scheme of the application, a nickel-based substrate is selected as the metallic substrate. The nickel-based substrate can be foam nickel, nickel screen or nickel fiber felt, preferably, the nickel-based substrate is nickel fiber felt, and the nickel fiber felt has the advantages of large specific surface area of foam nickel and high mechanical strength of the nickel screen, and is expected to replace the nickel screen to become a new generation electrode substrate.
In step S1, the metal substrate may be cut as needed to obtain a metal substrate of a suitable size before being heated at a low temperature. The pretreatment mode of the application only needs to use heating equipment with proper size, does not need to consider the corrosion resistance of the container, does not need to waste a large amount of acid liquor, and is economical and environment-friendly.
In the step S1, the low-temperature heating temperature is 100-300 ℃, the temperature rising rate is 2-10 ℃ per minute, and the heat preservation time is 0.5-5 hours. Through the low-temperature heating process, organic matters or greasy dirt on the surface of the metal substrate can be oxidized and removed, and meanwhile, the temperature is controlled within 300 ℃ and the heating time is controlled within 5 hours, so that the metal substrate can be prevented from becoming brittle. The calcination atmosphere may be an air atmosphere or an inert atmosphere, the inert atmosphere may be an argon atmosphere or the like, and the air pressure may be one atmosphere.
Preferably, the metal substrate is placed in the middle of the heating device, so that the actual heating temperature of the metal substrate is ensured to be the set temperature of the heating device as much as possible.
The heating device may be an oven, a muffle furnace or a tube furnace, only a tube furnace being selected if heating under an inert atmosphere is required. Preferably, the heating device may be a tube furnace.
In the step S1, when the water is used for cleaning and drying, the drying can be natural drying at room temperature, and the operation is simple.
In the step S2, the mixed solution of the bimetal salt is an aqueous solution containing two non-noble metal salts, and the anode catalyst is non-noble metal hydroxide with high valence state, so that the energy barrier of hydroxyl oxide can be reduced, and the overpotential required by electrolysis of water is reduced. The non-noble metal salt may be a nickel salt, an iron salt, or a cobalt salt. Further, the mixed solution of the bimetal salt may be a mixed solution of nickel salt and iron salt, a mixed solution of nickel salt and cobalt salt, or the like.
Wherein, the nickel salt can be nickel chloride hexahydrate, the cobalt salt can be cobalt nitrate nonahydrate or cobalt chloride hexahydrate, and the ferric salt can be ferrous chloride tetrahydrate or ferrous sulfate heptahydrate.
Preferably, the nickel salt is nickel chloride hexahydrate, the ferric salt is ferrous sulfate heptahydrate, the cobalt salt is cobalt chloride hexahydrate, and the three compounds are stable.
Wherein, the mole ratio of the nickel salt to the ferric salt or the cobalt salt is (5-20): 1, and the metal salt with the specific proportion can improve the catalysis performance of the double hydroxide. The mass ratio of the nickel salt to the water is 1: (20-100), by adopting the specific concentration, the moderate concentration of the metal salt can be ensured, the slow in-situ growth of hydroxide caused by over-thin concentration of the metal salt is avoided, and the influence on conductivity caused by over-thick hydroxide which is easy to grow due to over-thick concentration of the metal salt is avoided.
Preferably, the molar ratio of the nickel salt to the iron salt or the cobalt salt is (9-11): 1, the catalyst performance of the prepared double hydroxide is better by adopting the metal salt with the specific proportion.
Preferably, the mass ratio of nickel salt to water is 1: (40-60), and the prepared double hydroxide has better catalytic performance by adopting the concentration range of the metal salt.
In step S2, the standing temperature may be 20 to 30 ℃ and the standing time may be 24 to 72 hours.
In step S2, after the standing is completed, the metal substrate is taken out from the mixed solution of the bimetal salt, washed with water for several times, and naturally dried.
In the scheme of the application, by optimizing the pretreatment mode of the metal substrate, the pretreatment method of the metal substrate which is simple to operate and does not need a solvent is adopted, so that the organic matters on the metal substrate can be fully removed and the metal substrate can be activated, and the double hydroxide nano-sheet catalyst can be grown on the metal substrate only by a simple soaking method. The anode prepared by the preparation method has better oxygen evolution activity than a control sample subjected to conventional pretreatment such as dilute acid, can work under high current density for a long time, has great application prospect, and is expected to be applied to preparation of other electrode materials.
In the application, an electrode is also provided, and the anode is prepared by adopting the preparation method of the electrode.
In the application, the application of the electrode is also provided, and the electrode is used for preparing energy storage materials. Further, the electrode is used for electrolytic water oxygen evolution reaction.
Further description will be given below by way of specific examples.
Example 1
The first step: and (3) cutting the Ni fiber felt with the length of 2 x 5cm, placing the Ni fiber felt in a tube furnace, heating the Ni fiber felt to 200 ℃ from room temperature at a heating rate of 10 ℃ per minute without sealing, preserving heat for 1 hour, naturally cooling after the heat preservation is finished, cleaning the Ni fiber felt by using pure water, and naturally drying.
And a second step of: the pretreated Ni fiber mat was placed in 50ml of a solution in which 1.19g of NiCl had been previously dissolved 2 •6H 2 O and 0.15g FeSO 4 •7H 2 Soaking in O water solution at 25 deg.c for 24 hr, taking out Ni fiber felt, washing with pure water for 3 times, and natural drying to obtain NiFe LDH/a-Ni felt.
Control 1:
the first step: cutting 2 x 5cm Ni fiber felt, respectively ultrasonic treating in acetone, 6M HCl and ethanol for 10 min, cleaning with pure water, and naturally drying.
The second step was identical to the second step of example 1, yielding a NiFe LDH/Ni felt.
FIG. 1 is a scanning electron microscope image of the final product obtained in example 1. From FIG. 1 it is seen that the NiFe LDH/a-Ni felt is loaded with dense hydroxide nanoplatelets, approximately 50-150nm thick, grown substantially vertically.
FIG. 2 is a scanning electron micrograph of the end product of control 1 of example 1. It can be seen from FIG. 2 that the end product pretreated with conventional methods on a metal substrate also supports hydroxide nanoplatelets, but not as dense as NiFe LDH/a-Ni felt.
The activities of the NiFe LDH/a-Ni felt, the NiFe LDH/Ni felt and the Ni fiber felt in the electrolysis water oxygen evolution are tested, and the results are shown in figure 3, three curves are divided into an electrochemical performance curve of the NiFe LDH/a-Ni felt, the NiFe LDH/Ni felt and the Ni fiber felt from top to bottom, and the activities of the NiFe LDH/a-Ni felt in the electrolysis water oxygen evolution are better than those of the NiFe LDH/Ni felt and are further better than those of a Ni fiber felt substrate without growing a hydroxide catalyst from figure 3. Wherein, electrochemical test conditions: 95℃and 30% by weight KOH. The working electrode is hydroxide, the reference electrode is Hg/HgO, and the counter electrode is a platinum sheet electrode. Firstly, performing cyclic voltammetry test on a working electrode to achieve an activation effect, wherein the scanning range is 0.8-1.7V vs RHE, the scanning speed is 0.1V/s, and the test is stopped until the electrode is stable. And then testing the electrochemical activity of the electrode by using a linear sweep voltammetry, wherein the sweep speed is 5mV/s, and the sweep range is 1.2-1.7V vs RHE.
Constant current tests were carried out under high current with NiFe LDH/a-Ni felt and NiFe LDH/Ni felt as anodes and untreated Ni fiber felt as cathodes, and the results are shown as 4, wherein the two curves are respectively the curves of the NiFe LDH/Ni felt and the NiFe LDH/a-Ni felt from top to bottom, and the performance of the NiFe LDH/a-Ni felt is not attenuated when the NiFe LDH/a-Ni felt is used for more than 24 hours under high current density, which indicates that the NiFe LDH/a-Ni felt has good chemical stability. Wherein, constant current test conditions: 95℃and 30% by weight KOH. The working electrode is hydroxide, and the counter electrode is untreated Ni felt. The current was set to 0.6A and tested for 160 hours.
Example 2
A first step of; 10 x 10cm Ni fiber mat was cut and placed in a tube furnace, the remaining steps being identical to example 1.
And a second step of: the pretreated Ni fiber mat was placed at 500 ml to dissolve 5.95g of NiCl in advance 2 •6H 2 O and 0.75g FeSO 4 •7H 2 Soaking in O water solution at 25 deg.c for 24 hr, taking out Ni fiber felt, washing with pure water for 3 times, and natural drying.
The electrochemical properties of 4 sites in the large-area electrode were tested, and the results of the performance tests of the electrodes obtained in example 1 and example 2 were found to be substantially similar, and were up to 1200mAcm at 1.7V -2 As shown in fig. 5, electrochemical performance curves were obtained at 4 sites, respectively. Wherein the electrochemical test conditions and procedure were the same as in example 1.
FIG. 6 is a scanning electron microscope image of the final product obtained in example 2, with the exception that the degree of densification of the double hydroxide nanoplatelet catalyst at the electrode surface was slightly different from that of the electrode obtained in example 1 and example 2.
Example 3
The first step: consistent with the first step in example 1.
And a second step of: the pretreated Ni fiber mat was placed in 50ml of a solution in which 1.19g of NiCl had been previously dissolved 2 •6H 2 O and 0.119g CoCl 2 •6H 2 Soaking in O water solution at 25 deg.c for 24 hr, taking out Ni fiber felt, washing with pure water for 3 times, and natural drying to obtain NiCo LDH/a-Ni felt.
Control 2: the first step: cutting 2 x 5cm Ni fiber felt, respectively ultrasonic treating in acetone, 6M HCl and ethanol for 10 min, cleaning with pure water, and naturally air drying.
The second step was identical to the second step of example 3, yielding a NiCo LDH/Ni felt.
The activities of NiCo LDH/a-Ni felt, niCo LDH/Ni felt and Ni fiber felt in electrolytic water oxygen evolution were tested, and the results are shown in FIG. 7, wherein three curves are divided into an electrochemical performance curve of NiCo LDH/a-Ni felt, niCo LDH/Ni felt and Ni fiber felt from top to bottom, and as can be seen from FIG. 7, the activities of NiCo LDH/a-Ni felt in electrolytic water oxygen evolution are superior to those of NiCo LDH/Ni felt and are also superior to those of Ni fiber felt without growing hydroxide catalyst. Wherein, electrochemical test conditions: 95℃and 30% by weight KOH. The working electrode is hydroxide, the reference electrode is Hg/HgO, and the counter electrode is a platinum sheet electrode. Firstly, performing cyclic voltammetry test on a working electrode to achieve an activation effect, wherein the scanning range is 0.8-1.7V vs RHE, the scanning speed is 0.1V/s, and the test is stopped until the electrode is stable. And then testing the electrochemical activity of the electrode by using a linear sweep voltammetry, wherein the sweep speed is 5mV/s, and the sweep range is 1.2-1.7V vs RHE.
Example 4
The first step: the Ni net with 2 x 5cm thick monofilaments of 500 nm is cut and placed in a tube furnace, the Ni net is not sealed, the temperature is raised to 200 ℃ from room temperature at a heating rate of 10 ℃ per minute, the heat is preserved for 1 hour, natural cooling is carried out after the heat preservation is finished, pure water is used for cleaning the Ni net, and natural drying is carried out.
And a second step of: consistent with the second step of example 1, a NiFe LDH/a-Ni network was obtained.
Control 3: the first step: 2 x 5cm thick 500 nm thick Ni mesh was cut, respectively sonicated in acetone, 6M HCl and ethanol for 10 min, and finally washed with pure water only and naturally dried.
The second step was identical to the second step of example 4, yielding a NiFe LDH/Ni network.
The activities of the NiFe LDH/a-Ni net, the NiFe LDH/Ni net and the Ni net in the electrolytic water oxygen evolution are tested, the results are shown in figure 8, three curves are divided into an electrochemical performance curve of the NiFe LDH/a-Ni net, the NiFe LDH/Ni net and the Ni net from top to bottom, and the activities of the NiFe LDH/a-Ni net in the electrolytic water oxygen evolution are superior to those of the NiFe LDH/Ni net and are further superior to those of a Ni net substrate without growing a hydroxide catalyst, so that the substrate pretreatment method is applicable to various Ni-based substrates.
It will be understood that the application is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be within the scope of this application.
Claims (10)
1. A method of preparing an electrode comprising the steps of:
s1, placing a metal substrate into heating equipment, heating at a low temperature under a calcining atmosphere, preserving heat, naturally cooling, washing with water, and drying to obtain an activated metal substrate;
s2, standing the activated metal substrate in a mixed solution of double metal salts, and growing a double hydroxide nano-sheet catalyst on the activated metal substrate in situ.
2. The method of manufacturing an electrode according to claim 1, wherein in step S1, the low-temperature heating is performed at a temperature of 100 to 300 degrees celsius, the temperature rise rate is 2 to 10 degrees celsius/minute, and the holding time is 0.5 to 5 hours.
3. The method of manufacturing an electrode according to claim 1, wherein in step S1, the metal substrate is a nickel-based substrate;
in the step S1, the calcining atmosphere is an air atmosphere or an inert atmosphere, and the air pressure is one atmosphere;
in step S1, the heating device is an oven, a muffle furnace, or a tube furnace.
4. A method of preparing an electrode according to claim 3, wherein the nickel-based substrate is nickel foam, nickel mesh or nickel fiber felt.
5. The method of manufacturing an electrode according to claim 1, wherein in step S2, the standing temperature is 20 to 30 ℃ and the standing time is 24 to 72 hours.
6. The method for producing an electrode according to claim 1, wherein the mixed solution of the bimetal salt is an aqueous solution containing two non-noble metal salts.
7. The method for producing an electrode according to claim 6, wherein the mixed solution of a bimetal salt is a mixed solution of a nickel salt and an iron salt or a mixed solution of a nickel salt and a cobalt salt;
the nickel salt is nickel chloride hexahydrate, the cobalt salt is cobalt nitrate nonahydrate or cobalt chloride hexahydrate, and the ferric salt is ferrous chloride tetrahydrate or ferrous sulfate heptahydrate;
the molar ratio of the nickel salt to the ferric salt or the cobalt salt is (5-20): 1, and the mass ratio of the nickel salt to the water is 1: (20-100).
8. The method of producing an electrode according to claim 7, wherein the nickel salt is nickel chloride hexahydrate, the iron salt is ferrous sulfate heptahydrate, and the cobalt salt is cobalt chloride hexahydrate;
the molar ratio of the nickel salt to the iron salt or the cobalt salt is (9-11): 1, and the mass ratio of the nickel salt to the water is 1: (40-60).
9. An electrode characterized in that it is prepared by the method for preparing an electrode according to any one of claims 1 to 8.
10. Use of an electrode according to claim 9, wherein the electrode is used for the preparation of energy storage materials or for electrolytic water oxygen evolution reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311026656.6A CN116815223A (en) | 2023-08-15 | 2023-08-15 | Electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311026656.6A CN116815223A (en) | 2023-08-15 | 2023-08-15 | Electrode and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116815223A true CN116815223A (en) | 2023-09-29 |
Family
ID=88120552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311026656.6A Pending CN116815223A (en) | 2023-08-15 | 2023-08-15 | Electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116815223A (en) |
-
2023
- 2023-08-15 CN CN202311026656.6A patent/CN116815223A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110201670B (en) | Ferronickel double-metal hydroxide/foamed nickel catalyst based on ferric trichloride/urea eutectic solvent, and preparation method and application thereof | |
| CN108796535B (en) | Copper-cobalt-molybdenum/nickel foam porous electrode material with trimetal, and preparation method and application thereof | |
| CN110639534B (en) | Oxygen evolution electrocatalytic material and preparation method and application thereof | |
| CN108671944B (en) | Nickel-molybdenum oxide @ nickel-molybdenum sulfide @ foamed nickel composite nano material and preparation method and application thereof | |
| CN111825127B (en) | Preparation method and application of metallic nickel-based nanomaterial | |
| CN111617780B (en) | Nitrogen-doped nickel-molybdenum-based composite sulfide for stable hydrogen production by water electrolysis and preparation method thereof | |
| CN111663152B (en) | Preparation method and application of foam nickel-loaded amorphous phosphorus-doped nickel molybdate bifunctional electrocatalytic electrode | |
| WO2023143578A1 (en) | Porous nickel-molybdenum-cobalt hydrogen evolution electrode, preparation method therefor and application thereof | |
| CN114438545A (en) | Bimetal doped Ni3S2Preparation method of oxygen evolution electrocatalyst | |
| CN110694665A (en) | Preparation method and application of manganese and nitrogen doped octa-sulfur-nonacobalt electrocatalyst | |
| CN111229267B (en) | Supported phosphorus-doped metal oxyhydroxide nanosheet material and preparation method and application thereof | |
| CN111495406A (en) | Method for preparing boron and nitrogen doped cobalt molybdenum sulfur oxide/carbon composite material | |
| CN113684497A (en) | Foam copper loaded nickel-molybdenum-phosphorus-based composite material and preparation method and application thereof | |
| CN110408947B (en) | Nickel-cobalt oxide electrode material of composite silver oxide and preparation method and application thereof | |
| CN115261915B (en) | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof | |
| CN117004983A (en) | Cobalt-iron bimetal organic hybridization electrode material and preparation and application thereof | |
| CN114892206B (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN110137523B (en) | Hydrogen-making hydrazine hydrate fuel cell device | |
| CN114059082B (en) | N, P co-doped NF@NiMoO 4 Hollow nanowire composite material and preparation method and application thereof | |
| CN114457349B (en) | Carbon-coated nickel-molybdenum-cobalt hydrogen evolution electrode and preparation method and application thereof | |
| CN116815223A (en) | Electrode and preparation method and application thereof | |
| CN115323390A (en) | Foam nickel loaded nitrogen-phosphorus co-doped NiMo-based composite catalyst and preparation method and application thereof | |
| CN113862726A (en) | Preparation method and application of molybdenum-selenium double-element doped porous sheet layered nickel phosphide material | |
| CN111118564A (en) | Nickel-nickel oxide ultrathin nanosheet material and electrodeposition preparation method and application thereof | |
| CN113403641B (en) | Electrocatalytic material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |