CN113604834B - NiCo-LDH/(Ni, Fe) (OH) with core-shell structure 2 Foamed nickel composite electrode - Google Patents
NiCo-LDH/(Ni, Fe) (OH) with core-shell structure 2 Foamed nickel composite electrode Download PDFInfo
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Abstract
The invention discloses NiCo-LDH/(Ni, Fe) (OH) with a core-shell structure 2 Foamed nickel composite electrode, which takes foamed nickel as a substrate and grows (Ni, Fe) (OH) on the surface of the foamed nickel substrate 2 The nano-protrusions are used as inner cores and loaded in (Ni, Fe) (OH) 2 NiCo layered double hydroxide on the surface of the nano protrusion is used as a shell. The composite electrode has excellent electrochemical performance, can effectively give consideration to good mechanical strength and stability, and has wide applicability; the preparation method is simple, mild in reaction condition, low in cost, environment-friendly and suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to NiCo-LDH/(Ni, Fe) (OH) with a core-shell structure 2 A foamed nickel composite electrode and a preparation method thereof.
Background
In recent years, with the rapid development of economic society, the increasing shortage of fossil energy and environmental pollution have prompted the search for sustainable, clean energy storage and conversion systems. Among them, an electrocatalysis system composed of a cathode and an anode is widely favored by scientists due to its characteristics of convenience and high efficiency, and becomes a star in the field of energy conversion. Two half reactions are involved in an electrocatalytic cracking water system: hydrogen Evolution Reaction (HER) at the cathode and Oxygen Evolution Reaction (OER) at the anode. HER is a two-electron process, however, OER is a four-electron redox reaction that needs to be performed at a higher overpotential, thus showing slow kinetics and becoming the major bottleneck for overall water splitting. The development of a high-activity catalyst, the acceleration of reaction kinetics and the reduction of overpotential thereof have extremely important significance for improving the energy conversion efficiency of the whole system.
Currently, iridium dioxide (IrO) 2 ) Ruthenium dioxide (RuO) 2 ) And platinum (Pt) are considered to be the most effective catalysts for OER and HER, but problems of high cost, poor stability, etc. have affected their commercial application in the field of catalysts. Therefore, further development of a catalyst with low cost, high catalytic performance and excellent stability is a problem to be solved urgently in the field of new energy. Transition metal materials such as Ni, Co, Fe, etc. are widely studied as oxygen and hydrogen evolution reaction catalysts due to their advantages of low cost, environmental friendliness, high catalytic activity, and durability. The bimetal hydroxide is the most studied in the field of the multi-metal hydroxide catalyst, wherein NiCo layered bimetal hydroxide has low cost, environmental protection and rich valence state. NiCo layered double hydroxides with suitable doping ratios have a great significance for the electrolysis of water.
The conductive substrate is combined with the material, so that the transmission efficiency of the electrolyte can be improved. And after the foamed nickel is etched, the surface of the foamed nickel becomes rough, the electrochemical active area is increased, and the sample loading is facilitated. The material is prepared into a nano structure, so that the material has the characteristics of large specific surface area and small structure size, and the 3D core-shell structure combines the advantages of 1D and 2D nano structures. The composite material with the 3D core-shell structure can improve the conductivity of the electrode, increase the specific surface area, increase the contact area with electrolyte and improve the performance of the material. And the operation process is simple and convenient and is easy to control. Although the core-shell structure provides good electrical conductivity, the electrodeposition process generally used to prepare the shell is too fast and poorly controlled. In addition, the materials selected are somewhat cost-prohibitive and exhibit OER catalytic properties that are not comparable to those of noble metals. Therefore, the method has important research and application significance for further exploring the transition metal nano core-shell structure electrode with excellent conductivity and low price and optimizing the preparation process of the transition metal nano core-shell structure electrode.
Disclosure of Invention
The invention mainly aims to provide a nuclear magnetic resonance imaging device aiming at the defects in the prior artShell structured NiCo layered double hydroxide/(Ni, Fe) (OH) 2 The electrode can show excellent electrochemical performance, mechanical strength and stability, and the related preparation method is simple and has lower cost; can be applied to the fields of new energy, catalysts and the like, and has higher practicability and economy.
In order to achieve the purpose, the invention adopts the technical scheme that:
NiCo-LDH (NiCo layered double hydroxide)/(Ni, Fe) (OH) with core-shell structure 2 Foam nickel composite electrode, which takes foam nickel as a substrate and comprises (Ni, Fe) (OH) grown on the surface of the foam nickel substrate 2 The nano-protrusion inner core and the NiCo layered double-metal hydroxide shell layer loaded on the surface of the nano-protrusion inner core; wherein (Ni, Fe) (OH) 2 The nano-projection core contains copper elementary substance.
In the scheme, the width of the nano-protrusions is 10-20 nm.
The NiCo-LDH/(Ni, Fe) (OH) with the core-shell structure 2 The preparation method of the foamed nickel composite electrode comprises the following steps:
1)(Ni，Fe)(OH) 2 the preparation method of foamed nickel electrode core comprises etching clean foamed nickel substrate in dilute acid solution, washing, soaking in water, dripping copper salt solution, reacting for a period of time, taking out, washing, drying, and forming Ni (OH) loaded with copper simple substance on the surface of foamed nickel substrate 2 The nano bump structure (the foam nickel is etched by hydrochloric acid to form a rough surface and then is soaked in water, hydroxide ions are contained in the water, and the nickel hydroxide is formed on the foam nickel in situ growth mode; then the obtained product is put into ferric salt solution for soaking treatment, and after washing and drying, (Ni, Fe) (OH) with a nano-projection structure is obtained 2 A foamed nickel core;
2) preparation of NiCo layered double hydroxide electrode Shell the resulting (Ni, Fe) (OH) with a Nanoprotrusion Structure 2 Mixing foamed nickel core with nickel salt, cobalt salt, urea and water, and adding waterThermal reaction, cooling to room temperature, washing and drying, reaction on (Ni, Fe) (OH) 2 Generating a NiCo layered double-metal hydroxide shell layer on the surface of the foamed nickel core to obtain the NiCo layered double-metal hydroxide/(Ni, Fe) (OH) with the core-shell structure 2 Foam nickel composite electrode.
In the scheme, the dilute acid solution in the step 1) can adopt dilute hydrochloric acid or dilute sulfuric acid and the like; the concentration is 1-3 mol/L.
In the scheme, the etching time is 0.5-3 h.
In the scheme, the concentration of the copper salt solution is 0.01-0.1 mol/L, the copper salt solution is dropwise added into water containing an etched foam nickel substrate in a split manner in the reaction process, and the mass ratio of the total content of introduced copper ions to the foam nickel substrate is 1 (10-1000).
In the scheme, the copper salt can be selected from copper sulfate, copper chloride, copper nitrate and the like.
In the scheme, the step 1) is soaked in water, copper salt is dropwise added during the soaking, and the reaction time is 6-36 h.
In the scheme, the concentration of the ferric salt solution is 0.1-0.3 mol/L; the iron salt can be selected from ferric nitrate, ferric chloride or ferric sulfate.
In the scheme, the soaking time of the iron salt is 0.5-2 h.
In the scheme, the molar ratio of the nickel salt, the cobalt salt and the urea in the step 2) is 1 (1-3) to 3-10.
In the scheme, the concentration range of the nickel salt in the step 2) is 0.0125-0.05 mol/L.
In the scheme, the hydrothermal reaction temperature is 120-180 ℃, and the reaction time is 6-18 h.
Preferably, the step (1) of ultrasonic cleaning comprises the following steps: cutting the foamed nickel into 2 x 5cm, and soaking in absolute ethyl alcohol and deionized water for ultrasonic cleaning for 10min each time.
NiCo layered double hydroxide/(Ni, Fe) (OH) prepared according to the above protocol 2 The foamed nickel composite electrode has a core-shell structure, is favorable for electron transmission rate, has excellent electrochemical performance,and has good mechanical strength and stability.
Compared with the prior art, the invention has the beneficial effects that:
1) the NiCo layered double hydroxide/(Ni, Fe) (OH) obtained by the invention 2 The/foamed nickel composite electrode has a core-shell structure, is beneficial to the transmission of electrons and improves the electrochemical performance; wherein in Ni (OH) 2 Copper salt solution is dripped in the reaction process of the nano-protrusions, and the conductivity of the obtained composite material can be improved by introducing a small amount of copper particles; while forming (Ni, Fe) (OH) by self-ion exchange 2 The introduced iron element is exchanged, the valence state distribution of nickel can be regulated and controlled, and the conductivity is further improved; the NiCo layered double hydroxide serving as a loaded shell layer increases the specific surface area, promotes the transmission of electrolyte without influencing the dissipation of gas, has good mechanical strength and synergistic effect with the core, and further improves the conductivity.
2) The composite electrode obtained by the invention has excellent electrochemical performance, can effectively give consideration to good mechanical strength and stability, and has wide applicability; the preparation process does not need to introduce any chemical adhesive, so that the transmission of electrons is not influenced, the excellent electrochemical performance is further shown, and the NiCo layered double hydroxide directly grown on the inner core by utilizing a hydrothermal growth method can promote the formation of good mechanical strength between the inner core and the shell and shows good stability.
3) The preparation method provided by the invention is simple, mild in reaction conditions and environment-friendly; compared with precious metal materials, the preparation raw materials are low in cost, easy to obtain and suitable for popularization and application.
Drawings
FIG. 1 is a schematic view of a process for preparing a composite electrode according to the present invention;
FIG. 2 is a schematic diagram of the mechanism of the composite electrode of the present invention, in which sample (1) is nickel foam and sample (2) is Ni (OH) 2 A nickel foam electrode; sample (3) is (Ni, Fe) (OH) 2 A nickel foam electrode; sample (4) was NiCo-LDH/(Ni, Fe) (OH) 2 A nickel foam electrode;
FIG. 3 shows an embodiment of the composite electrode of the present inventionTopography for example 1; wherein (a) is (Ni, Fe) (OH) 2 Foam nickel electrode, and (b) NiCo-LDH/(Ni, Fe) (OH) 2 A nickel foam electrode;
FIG. 4 is a graph of electrochemical performance of the composite electrode of the present invention; wherein (a) is the LSV polarization curves of example 1 and comparative example, and the solid line is NiCo-LDH/(Ni, Fe) (OH) obtained in example 1 2 A/foamed nickel electrode, wherein the dotted line represents the NiCo-LDH/foamed nickel electrode obtained in the comparative example; (b) the results of the stability test of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, all reagents used were commercially available chemical reagents or products unless otherwise specified.
Example 1
NiCo layered double hydroxide/(Ni, Fe) (OH) 2 The preparation process flow schematic diagram of the foamed nickel composite electrode is shown in figure 1, and the specific preparation method comprises the following steps:
1)(Ni，Fe)(OH) 2 cutting the foamed nickel into a rectangle with the size of 2 x 5cm and the mass of 0.3g (the error is between 0.01 g), ultrasonically cleaning the cut foamed nickel for 10min by using ethanol and deionized water in sequence, preparing 30ml of hydrochloric acid solution with the concentration of 3mol/L, and soaking the cleaned foamed nickel in the hydrochloric acid solution with the concentration of 3mol/L for 1h to etch the surface; the etched foam nickel is washed by a large amount of water and soaked in 30mL of water for 12h to form Ni (OH) 2 /foamed nickel, wherein 1mL of copper sulfate solution (0.05mol/L) is added into water in portions (at intervals of about half an hour) within 12 hours, taken out, dried at room temperature for 24 hours and weighed; the resulting Ni (OH) 2 Soaking foamed nickel in 0.1M ferric nitrate solution at room temperature for 1h to perform ion exchange to form (Ni, Fe) (OH) with nano-protrusion structure 2 A foamed nickel core (containing a copper simple substance) is dried at room temperature for standby;
2) NiCo layered double hydroxide/(Ni, Fe))(OH) 2 Preparation of a foamed nickel electrode shell: dissolving nickel nitrate, cobalt nitrate and urea in a molar ratio of 1:2:5, wherein the nickel salt is 1mmol, in 30ml of water, stirring for 30min to obtain a uniform reaction solution, and mixing the (Ni, Fe) (OH) prepared in the step 1) 2 Putting the foamed nickel core and the reaction solution into a 100ml hydrothermal kettle, putting the kettle into a 120 ℃ oven for heat preservation reaction for 6h, cooling to room temperature, washing with ethanol and deionized water alternately, and drying at 60 ℃ to obtain NiCo layered double hydroxide/(Ni, Fe) (OH) 2 Foam nickel composite electrode (Ni (OH) 2 And (Ni, Fe) (OH) 2 Is amorphous, has small and small Cu content, and is mostly formed by Ni (OH) 2 Coating).
The synthetic principle of the composite electrode described in this embodiment is schematically shown in fig. 2: firstly, adopting a room-temperature etching in-situ growth process, taking foamed nickel (1) as a conductive substrate and a nickel source, etching by hydrochloric acid to form a rough surface, then soaking the rough surface in water, simultaneously dropwise adding a copper salt solution, and growing a nickel hydroxide protruding structure (2) containing copper particles in situ on the foamed nickel; then soaking the (Ni, Fe) (OH) into a ferric salt solution to react to obtain (Ni, Fe) (OH) with a nano-projection structure 2 And/foaming a nickel inner core (3), and finally adding the nickel inner core into a precursor solution of the NiCo layered double hydroxide to react to obtain a NiCo layered double hydroxide shell layer, thus obtaining a final product (4).
FIG. 3 is a scanning electron microscope image of the product obtained in this embodiment, which shows that the width of the nano-protrusions is 10-20 nm, and the width of the formed core-shell structure is about 30-50 nm.
FIG. 4 shows the results of electrochemical performance tests on the product obtained in this example, which shows that the voltage of 1.584V can reach 20 mA cm -2 The current density.
Example 2
NiCo layered double hydroxide/(Ni, Fe) (OH) 2 The preparation method of the foamed nickel composite electrode comprises the following steps:
1)(Ni，Fe)(OH) 2 the preparation method of foamed nickel electrode core comprises cutting foamed nickel into 2 × 5cm rectangle with mass of 0.3g (error of 0.01 g), and sequentially adding ethanol and deionized waterUltrasonic cleaning is carried out for 10min, 30ml of 1mol/L hydrochloric acid solution is prepared, and the cleaned foamed nickel is soaked in 1M hydrochloric acid solution for 2h to etch the surface; the etched foam nickel is washed by a large amount of water and soaked in 30mL of water for 6h to form Ni (OH) 2 The nickel foam is prepared by adding 1mL of copper sulfate solution (0.01 mol/L) into water in portions (about half an hour at intervals) within 6h, taking out, drying at room temperature for 24h, and weighing; the resulting Ni (OH) 2 Soaking foamed nickel in 0.2M ferric nitrate solution at room temperature for 2h for ion exchange to form (Ni, Fe) (OH) with nano-protrusion structure 2 A foamed nickel core (containing a copper simple substance) is dried at room temperature for standby;
2) NiCo layered double hydroxide/(Ni, Fe) (OH) 2 Preparation of a foamed nickel electrode shell: dissolving nickel nitrate, cobalt nitrate and urea in a molar ratio of 1:1:5, wherein the nickel salt is 1mmol, in 30ml of water, stirring for 30min to obtain a uniform reaction solution, and mixing the (Ni, Fe) (OH) prepared in the step 1) 2 Putting the foamed nickel core and the reaction solution into a 100ml hydrothermal kettle, putting the kettle into a baking oven with the temperature of 140 ℃, carrying out heat preservation reaction for 6h, cooling the kettle to the room temperature, washing the kettle by using ethanol and deionized water alternately, and drying the kettle at the temperature of 60 ℃ to obtain NiCo layered double hydroxide/(Ni, Fe) (OH) 2 Foam nickel composite electrode.
Example 3
NiCo layered double hydroxide/(Ni, Fe) (OH) 2 The specific preparation method of the foamed nickel composite electrode comprises the following steps:
1)(Ni，Fe)(OH) 2 cutting the foamed nickel into a rectangle with the size of 2 x 5cm and the mass of 0.3g (the error is between 0.01 g), ultrasonically cleaning the foamed nickel for 10min by using ethanol and deionized water in sequence, preparing 30ml of 2mol/L hydrochloric acid solution, and soaking the cleaned foamed nickel in the 2M hydrochloric acid solution for 2.5h to etch the surface; rinsing the etched foamed nickel with a large amount of water, and soaking in 30mL of water for 24h to form Ni (OH) 2 The nickel foam is prepared by adding 1mL of copper sulfate solution (0.08 mol/L) into water in batches (with the interval of about half an hour) within 24h, taking out, drying at room temperature for 24h, and weighing; the resulting Ni (OH) 2 Soaking foamed nickel in 0.3M ferric nitrate solution at room temperature for 1h,ion-exchanging the resulting solution to form (Ni, Fe) (OH) having a nano-projection structure 2 A foamed nickel core (containing a copper simple substance) is dried at room temperature for standby;
2) NiCo layered double hydroxide/(Ni, Fe) (OH) 2 Preparation of a foamed nickel electrode shell: dissolving nickel nitrate, cobalt nitrate and urea in a molar ratio of 1:2:6, wherein the nickel salt is 1mmol, in 30ml of water, stirring for 30min to obtain a uniform reaction solution, and mixing the (Ni, Fe) (OH) prepared in the step 1) 2 Putting the foamed nickel core and the reaction solution into a 100ml hydrothermal kettle, putting the kettle into a 120 ℃ oven for heat preservation reaction for 12h, cooling to room temperature, washing with ethanol and deionized water alternately, and drying at 60 ℃ to obtain NiCo layered double hydroxide/(Ni, Fe) (OH) 2 A foamed nickel composite electrode.
Example 4
NiCo layered double hydroxide/(Ni, Fe) (OH) 2 The preparation method of the foamed nickel composite electrode comprises the following steps:
1)(Ni，Fe)(OH) 2 cutting foamed nickel into a rectangle with the size of 2 x 5cm and the mass of 0.3g (the error is between 0.01 g), ultrasonically cleaning the foamed nickel for 10min by using ethanol and deionized water in sequence, preparing 30ml of 1.5mol/L hydrochloric acid solution, and soaking the cleaned foamed nickel in the 1.5M hydrochloric acid solution for 1h to etch the surface; rinsing the etched foamed nickel with a large amount of water, and soaking in 30mL of water for 18h to form Ni (OH) 2 The nickel foam is prepared by adding 1mL of copper sulfate solution (0.02mol/L) into water in portions (about half an hour at intervals) within 18h, taking out, drying at room temperature for 24h, and weighing; the resulting Ni (OH) 2 Soaking foamed nickel in 0.15M ferric nitrate solution at room temperature for 1.5 hr for ion exchange to form (Ni, Fe) (OH) with nano-bump structure 2 A foamed nickel core (containing a copper simple substance) is dried at room temperature for standby;
2) NiCo layered double hydroxide/(Ni, Fe) (OH) 2 Preparation of a foamed nickel electrode shell: dissolving nickel nitrate, cobalt nitrate and urea in a molar ratio of 1:1.5:3, wherein the nickel salt is 1mmol, in 30ml of water, stirring for 30min to obtain a uniform reaction solution, and mixing the (Ni, Fe) (OH) prepared in the step 1) 2 Putting the foamed nickel core and the reaction solution into a 100ml hydrothermal kettle, putting the kettle into a 160 ℃ oven for heat preservation reaction for 18h, cooling to room temperature, washing with ethanol and deionized water alternately, and drying at 60 ℃ to obtain NiCo layered double hydroxide/(Ni, Fe) (OH) 2 A foamed nickel composite electrode.
Example 5
NiCo layered double hydroxide/(Ni, Fe) (OH) 2 The preparation method of the foamed nickel composite electrode comprises the following steps:
1)(Ni，Fe)(OH) 2 cutting foamed nickel into a rectangle with the size of 2 x 5cm and the mass of 0.3g (the error is between 0.01 g), ultrasonically cleaning the foamed nickel for 10min by using ethanol and deionized water in sequence, preparing 30ml of 2.5mol/L hydrochloric acid solution, and soaking the cleaned foamed nickel in the 2.5M hydrochloric acid solution for 3 hours to etch the surface; the etched foam nickel is washed by a large amount of water and soaked in 30mL of water for 36h to form Ni (OH) 2 The nickel foam is prepared by adding 1mL of copper sulfate solution (0.10mol/L) into water in batches (with the interval of about half an hour) within 36h, taking out, drying at room temperature for 24h, and weighing; the resulting Ni (OH) 2 Soaking foamed nickel in 0.10M ferric nitrate solution at room temperature for 2h for ion exchange to form (Ni, Fe) (OH) with nano-protrusion structure 2 A foamed nickel core (containing a copper simple substance) is dried at room temperature for standby;
2) NiCo layered double hydroxide/(Ni, Fe) (OH) 2 Preparation of a foamed nickel electrode shell: dissolving nickel nitrate, cobalt nitrate and urea in a molar ratio of 1:2:10, wherein the nickel salt is 1mmol, in 30ml of water, stirring for 30min to obtain a uniform reaction solution, and mixing the (Ni, Fe) (OH) prepared in the step 1) 2 Putting the foamed nickel core and the reaction solution into a 100ml hydrothermal kettle, putting the kettle into a 180 ℃ oven for heat preservation reaction for 16h, cooling to room temperature, washing with ethanol and deionized water alternately, and drying at 60 ℃ to obtain NiCo layered double hydroxide/(Ni, Fe) (OH) 2 Foam nickel composite electrode.
Example 6
NiCo layered double hydroxide/(Ni, Fe) (OH) 2 The preparation method of the/foamed nickel composite electrode comprises the following stepsThe method comprises the following steps:
1)(Ni，Fe)(OH) 2 cutting the foamed nickel into a rectangle with the size of 2 x 5cm and the mass of 0.3g (the error is between 0.01 g), ultrasonically cleaning the foamed nickel for 10min by using ethanol and deionized water in sequence, preparing 30ml of hydrochloric acid solution with the concentration of 3mol/L, and soaking the cleaned foamed nickel in the hydrochloric acid solution with the concentration of 3M for 1.5h to etch the surface; the etched foam nickel is washed by a large amount of water and soaked in 30mL of water for 22h to form Ni (OH) 2 The nickel foam is prepared by adding 1mL of copper sulfate solution (0.07 mol/L) into water in portions (about half an hour at intervals) within 22h, taking out, drying at room temperature for 24h, and weighing; the resulting Ni (OH) 2 Soaking foamed nickel in 0.25M ferric nitrate solution at room temperature for 0.5h for ion exchange to form (Ni, Fe) (OH) with nano-projection structure 2 A foamed nickel core (containing a copper simple substance) is dried at room temperature for standby;
2) NiCo layered double hydroxide/(Ni, Fe) (OH) 2 Preparation of a foamed nickel electrode shell: dissolving nickel nitrate, cobalt nitrate and urea in a molar ratio of 1:3:3, wherein the nickel salt is 1mmol, in 30ml of water, stirring for 30min to obtain a uniform reaction solution, and mixing the (Ni, Fe) (OH) prepared in the step 1) 2 Putting the foamed nickel core and the reaction solution into a 100ml hydrothermal kettle, putting the kettle into a 160 ℃ oven for heat preservation reaction for 8h, cooling to room temperature, washing with ethanol and deionized water alternately, and drying at 60 ℃ to obtain NiCo layered double hydroxide/(Ni, Fe) (OH) 2 A foamed nickel composite electrode.
Comparative example
A NiCo layered double hydroxide/foamed nickel composite electrode is specifically prepared by the following steps:
preparation of NiCo layered double hydroxide/foamed nickel electrode shell: cutting foamed nickel into a rectangle with the size of 2 x 5cm and the mass of 0.3g (the error is between 0.01 g), ultrasonically cleaning the cut foamed nickel for 10min by using ethanol and deionized water in sequence, dissolving nickel nitrate, cobalt nitrate and urea in 30ml of water according to the molar ratio of 1:2:10 (the using amount of nickel salt is 1mmol), stirring the solution for 30min to obtain a uniform reaction solution, placing the treated foamed nickel and the reaction solution in a 100ml hydrothermal kettle, placing the kettle in a 120 ℃ oven for heat reaction for 12h, cooling the kettle to room temperature, alternately washing the product by using ethanol and deionized water, and drying the product at 60 ℃ to obtain the NiCo layered double metal hydroxide/foamed nickel electrode. The test results are shown in dashed lines in fig. 4 a.
The above embodiments are only examples for clearly illustrating the present invention and are not intended to limit the present invention. Other variants and modifications will be apparent to those skilled in the art in light of the foregoing description, which are not necessarily exhaustive of all embodiments and are therefore intended to be within the scope of the invention.
Claims (10)
1. NiCo-LDH/(Ni, Fe) (OH) with core-shell structure 2 The foamed nickel composite electrode is characterized in that foamed nickel is used as a substrate, and (Ni, Fe) (OH) obtained by growing on the surface of the foamed nickel substrate 2 The nano-protrusions are used as inner cores and loaded in (Ni, Fe) (OH) 2 NiCo layered double hydroxide on the surface of the nano protrusion is taken as a shell; wherein (Ni, Fe) (OH) 2 The nano-projection inner core contains copper elementary substance;
the preparation method comprises the following steps:
1）(Ni，Fe)(OH) 2 the preparation method of foamed nickel electrode core comprises etching clean foamed nickel substrate in dilute acid solution, washing, soaking in water, dripping copper salt solution, reacting for a period of time, taking out, washing, drying, and forming Ni (OH) loaded with copper simple substance on the surface of foamed nickel substrate 2 A nano-projection structure; then the obtained reaction product is placed in ferric salt solution for soaking treatment, and after washing and drying, (Ni, Fe) (OH) with a nano-projection structure is obtained 2 A foamed nickel core;
2) preparation of NiCo layered double hydroxide electrode Shell 2 The foamed nickel core is uniformly mixed with nickel salt, cobalt salt, urea and water to carry out hydrothermal reaction, and the mixture is washed and dried after being cooled to room temperature to obtain the NiCo layered double hydroxide/(Ni, Fe) (OH) with the core-shell structure 2 A foamed nickel composite electrode.
2. The composite electrode according to claim 1, wherein the width of the nano-protrusions is 10 to 20 nm.
3. NiCo-LDH/(Ni, Fe) (OH) having a core-shell structure as set forth in claim 1 or 2 2 The preparation method of the foamed nickel composite electrode is characterized by comprising the following steps of:
1）(Ni，Fe)(OH) 2 the preparation method of foamed nickel electrode core comprises etching clean foamed nickel substrate in dilute acid solution, washing, soaking in water, dripping copper salt solution, reacting for a period of time, taking out, washing, drying, and forming Ni (OH) loaded with copper simple substance on the surface of foamed nickel substrate 2 A nano-projection structure; then the obtained reaction product is placed in ferric salt solution for soaking treatment, and after washing and drying, (Ni, Fe) (OH) with a nano-projection structure is obtained 2 A foamed nickel core;
2) preparation of NiCo layered double hydroxide electrode Shell 2 The foamed nickel core is uniformly mixed with nickel salt, cobalt salt, urea and water to carry out hydrothermal reaction, and the mixture is washed and dried after being cooled to room temperature to obtain the NiCo layered double hydroxide/(Ni, Fe) (OH) with the core-shell structure 2 A foamed nickel composite electrode.
4. The method according to claim 3, wherein the dilute acid solution in step 1) is dilute hydrochloric acid or dilute sulfuric acid; the concentration is 1-3 mol/L; the etching time is 0.5-3 h.
5. The preparation method according to claim 3, wherein the concentration of the copper salt solution is 0.01 to 0.1 mol/L; dropwise adding in the reaction process in several times, wherein the mass ratio of the total content of the introduced copper ions to the foamed nickel substrate is 1 (10-1000).
6. The preparation method of claim 3, wherein the step 1) of soaking in water is performed while copper salt is added dropwise, and the reaction time is 6-36 h.
7. The preparation method according to claim 3, wherein the concentration of the ferric salt solution is 0.1-0.3 mol/L.
8. The preparation method of claim 3, wherein the soaking time of the iron salt in the step 1) is 0.5-2 h.
9. The preparation method of claim 3, wherein the molar ratio of the nickel salt, the cobalt salt and the urea in the step 2) is 1 (1-3) to (3-10), wherein the concentration of the nickel salt is 0.0125-0.05 mol/L.
10. The preparation method according to claim 3, wherein the hydrothermal reaction is carried out at 120-180 ℃ for 6-18 h.
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