CN110706944B - Method for preparing 3D needle-shaped nickel-cobalt double-metal oxide nano-cluster by one-step electrodeposition method - Google Patents
Method for preparing 3D needle-shaped nickel-cobalt double-metal oxide nano-cluster by one-step electrodeposition method Download PDFInfo
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Abstract
The invention discloses a method for preparing a 3D needle-shaped nickel-cobalt bimetallic oxide nano-cluster by a one-step electrodeposition method, which takes pretreated foamed nickel as a substrate, and vertically grows needle-shaped Ni-Co bimetallic oxide on the surface of the substrate by a one-step constant-current electrodeposition method. Meanwhile, the pretreated foam nickel surface has a fine pore structure, so that the template has the function of a template, and has certain capacitance contribution when the loading capacity of active substances on a unit area can be improved, secondary removal is not needed, and the preparation method is simple and efficient. Also provides a novel research idea for the preparation of the linear electrode material and has certain universality.
Description
Technical Field
The invention belongs to the technical field of supercapacitors, and particularly relates to a method for preparing a 3D needle-shaped nickel-cobalt double-metal oxide nano-cluster by a one-step electrodeposition method.
Background
Spinel binary metal oxide NiCo2O4Low production cost, high theoretical specific capacitance (1370F/g), and rich redox electron pair (Ni)2+/Ni3+And Co2+/Co3+) And the like, and the device is widely concerned by people. The research shows that the form, the conductivity and the porosity of the electrode material can improve the electricity of the super capacitorChemical properties play a key role. The change of the material form is particularly important because the electrode material with the hierarchical/porous structure or the three-dimensional (3D) array structure can increase the specific surface area of the electrode material, improve the contact area between the electrode and the electrolyte, shorten the diffusion path of electrolyte ions, enhance the structural stability and the like. Therefore, compared with one-dimensional (1D) and two-dimensional (2D) structures, 3D acicular nickel cobalt double hydroxide (3D Ns-Ni-Co LDH, Needle-shaped 3D nickel-cobalt double hydroxide) has an effective ion and electron diffusion path and thus exhibits better capacitance performance. The shape and structure of the nano material can be controlled by adjusting some reaction methods and parameters, such as a common hydrothermal template-assisted method, and finally electrode materials with different shapes are prepared by adjusting conditions of the shape of the template, the concentration of reactants, the reaction time, the temperature and the like. However, when electrode materials with different morphologies are prepared by adopting a hydrothermal template auxiliary method, the morphology of a sample is difficult to control, the existence of the template can increase the dead volume of the electrode and reduce the capacitance performance of the material. Therefore, the template is removed twice, but this not only adds extra operation steps for experiments, but also causes secondary damage to the electrode structure easily due to multiple reactions.
The difficult problem of preparing 3D Ns-Ni-Co LDH by a template-assisted method is mainly solved by the following method at present: (1) the preparation method is directly used for preparation by a hydrothermal method, no additional template is needed for assistance, but the reaction process is uncontrollable, the appearance of a sample is difficult to reach a 3D needle-shaped nano cluster structure, and meanwhile, the requirement on a reaction container is harsh; (2) the use of a lower concentration of solvent to dissolve the template, although less damaging to the substrate, results in incomplete template removal and a greater effect on the capacitance of the substrate.
Disclosure of Invention
The invention aims to provide a method for preparing a 3D acicular nickel-cobalt double-metal oxide nano cluster by a one-step electrodeposition method.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. soaking a foamed nickel substrate in 2-5 mol/L acetone aqueous solution for 20-40 minutes at normal temperature, and then soaking in hydrochloric acid with the mass concentration of 2-10% for 20-40 minutes; and after soaking, repeatedly cleaning the foamed nickel substrate by using absolute ethyl alcohol and deionized water, and drying the cleaned foamed nickel substrate in vacuum at the temperature of 60-80 ℃.
2. Soaking the foamed nickel substrate subjected to vacuum drying in the step 1 in a pretreatment solution, and heating and reacting for 10-60 minutes at the temperature of 60-110 ℃, wherein the pretreatment solution contains 0.3-0.5 mmol/L of Ni (NO)3)2、0.5～1mmol/L Co(NO3)2、1.0～1.5mmol/L NH4NO3And a 1-5% volume concentration aqueous solution of dimethyl sulfoxide; and after the reaction is finished, repeatedly ultrasonically cleaning the foamed nickel substrate by using deionized water and absolute ethyl alcohol, and drying to obtain the pretreated foamed nickel substrate.
3. Soaking the foamed nickel substrate pretreated in the step 2 in electrolyte for 3-10 minutes, wherein the electrolyte contains 0.1-0.3 mol/L of Ni (NO)3)2、0.1～0.3mol/LCo(NO3)20.02-0.05 mol/L NiCl solution2A solution, 0.05-0.15 mol/L boric acid, 0.8-1.2 mmol/L o-sulfonylbenzoylimine and 0.01-0.05 mmol/L dimethyl sulfoxide; then directly growing needle-shaped nickel-cobalt double metal hydroxide on a foamed nickel substrate by a constant-current electrodeposition method, wherein the current density of constant-current electrodeposition is 10-60 mA/cm2The deposition time is 1-4 hours.
4. And (3) annealing the acicular nickel-cobalt bimetal hydroxide foamed nickel substrate grown in the step (3) for 2-5 hours at 250-400 ℃ in an air atmosphere to obtain the 3D acicular nickel-cobalt bimetal oxide nano cluster.
In the step 1, at normal temperature, preferably, the foamed nickel substrate is immersed in 3mol/L acetone aqueous solution for 30 minutes, and then immersed in hydrochloric acid with the mass concentration of 6% for 30 minutes; and after soaking, repeatedly cleaning the foamed nickel substrate by using absolute ethyl alcohol and deionized water, and drying the cleaned foamed nickel substrate at 70 ℃ for 3 hours in vacuum.
In the step 2, the foamed nickel substrate dried in vacuum in the step 1 is soaked in the pretreatment solution, and preferably heated and reacted at 90-100 ℃ for 30-40 minutes.
The steps are as followsIn step 2, the pretreatment solution preferably contains 0.35 to 0.40mmol/L of Ni (NO)3)2、0.7～0.8mmol/L Co(NO3)2、1.12～1.13mmol/L NH4NO3And 2-3% volume concentration dimethyl sulfoxide aqueous solution.
In the step 3, the electrolyte preferably contains 0.15 to 0.20mol/L of Ni (NO)3)2、0.15～0.20mol/LCo(NO3)20.03-0.04 mol/L NiCl solution2The solution is 0.08-0.10 mol/L boric acid, 0.9-1.0 mmol/L o-sulfonylbenzoylimine and 0.02-0.3 mmol/L dimethyl sulfoxide.
In the step 3, the current density of the constant-current electrodeposition is preferably 40-50 mA/cm2The deposition time is 2-3 hours.
In the step 4, the acicular nickel-cobalt bimetal hydroxide foamed nickel substrate grown in the step 3 is preferably annealed for 2-3 hours at 300-320 ℃ in an air atmosphere.
In the step 4, the temperature rise rate of annealing is preferably 1-5 ℃/min.
The invention has the following beneficial effects:
1. the 3D needle-shaped nickel-cobalt double-metal oxide nano-cluster is successfully prepared by the electrodeposition method for the first time, compared with the prior preparation process, the method has the advantages of novel thought, simple process, intuitive and controllable reaction process, no harsh requirement on a reaction vessel, and suitability for industrial mass production.
2. The key point of the invention is the pretreatment of the foamed nickel substrate, a layer of nickel-cobalt precursor with a three-dimensional pore channel structure is uniformly grown on the surface of the foamed nickel substrate through the pretreatment, and the pore channel of the product not only provides an active site and a place for the growth of the 3D needle-shaped nickel-cobalt double-metal oxide nano cluster, but also has certain capacitance contribution, does not need secondary template removal, and does not generate any structural damage to an electrode material.
3. The invention can uniformly prepare NiCo2O4The Ni-Co precursor with the nano-wire and multi-pore channel network structure plays a role of a template, and Ni/Co ions are preferentially deposited to pores under the action of constant currentIn the channel, until the nanowire structure is formed, the anisotropic structure of the channel promotes the nanowires to approach each other, and finally the nanocluster-shaped 3D structure is formed.
4. The 3D acicular nickel-cobalt double-metal oxide nano-cluster prepared by the method improves the loading capacity of active substances on a unit area on the basis of not reducing the capacitive performance of the electrode, and increases the specific capacitance value and the cycle stability of the electrode.
Drawings
FIG. 1 is a scanning electron micrograph of the nickel foam after pretreatment in example 1 (wherein (b) is a partially enlarged view of (a)).
Fig. 2 is a scanning electron micrograph of the 3D acicular nickel cobalt bimetallic oxide nanoclusters obtained in example 1 (where (b) is a partial enlargement of (a)).
Fig. 3 is an X-ray diffraction pattern of the 3D acicular nickel cobalt double metal oxide nanoclusters obtained in example 1.
Fig. 4 is a scanning electron micrograph of the 3D acicular nickel cobalt bimetallic oxide nanoclusters obtained in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples, but the scope of the present invention is not limited to the following examples.
Example 1
1. Cutting the foamed nickel into square sheets with the specification of 1cm multiplied by 0.25cm, then placing the cut foamed nickel into 3mol/L acetone aqueous solution to be soaked for 30min at normal temperature, then placing the soaked foamed nickel into hydrochloric acid with the mass concentration of 6% to be soaked for 30min, repeatedly cleaning the foamed nickel for a plurality of times by using absolute ethyl alcohol and deionized water after soaking, and placing the cleaned foamed nickel in a vacuum drying oven at 70 ℃ to be dried for 3 hours.
2. Soaking the foamed nickel dried in the step 1 in 20mL of pretreatment solution containing 0.375mmol/L Ni (NO)3)2、0.75mmol/L Co(NO3)2、1.125mmol/L NH4NO3Heating the aqueous solution of dimethyl sulfoxide with the volume concentration of 2.5 percent in an oil bath at 100 ℃ for reaction for 30min, and repeatedly ultrasonically cleaning the sample number by using deionized water and absolute ethyl alcohol after the reaction is finishedNext, the sample was then dried in an oven at 60 ℃ for 2h to give a pretreated nickel foam.
3. Soaking the foamed nickel pretreated in the step 2 in 50mL of electrolyte for 5min, wherein the electrolyte contains 0.17mol/L of Ni (NO)3)2、0.17mol/L Co(NO3)2、0.033mol/L NiCl20.1mol/L boric acid, 0.83mmol/L o-sulfonylbenzoylimine and 0.025mmol/L dimethyl sulfoxide, and performing constant current electrodeposition at a current density of 50mA/cm2Depositing for 3h, and directly growing needle-shaped nickel-cobalt double metal hydroxide on the foamed nickel.
4. Cleaning the acicular nickel-cobalt double-metal hydroxide foamed nickel grown in the step 3 with deionized water and absolute ethyl alcohol in a 40W ultrasonic cleaning instrument for 5min each time, repeatedly cleaning for 3 times, and then placing the cleaned sample in an oven at 80 ℃ for drying for 3 h; after drying, heating to 300 ℃ at the speed of 1 ℃/min in the air atmosphere, preserving heat for 2h, carrying out high-temperature annealing treatment on the sample, taking out the sample to be recovered to the room temperature, washing the sample for 5min each time in a 40W ultrasonic cleaning instrument by using deionized water and absolute ethyl alcohol, repeatedly washing for 3 times, and then placing the washed sample in an oven at 80 ℃ for drying for 3h to obtain the 3D needle-shaped nickel-cobalt double-metal oxide nano-cluster.
And performing SEM and XRD characterization on the prepared 3D acicular nickel-cobalt double-metal oxide nano-cluster so as to research the appearance and structural characteristics of the sample, wherein the characterization result is shown in detail in figures 1-3. From the partial enlarged view (fig. 1(b)) of the pretreated nickel foam, it can be seen that a layer of Ni-Co precursor with a porous network structure is uniformly grown on the surface of the nickel foam through oil bath treatment, and the size of the pore channel is from several nanometers to tens of nanometers. As can be seen from the observation of FIG. 2(b), NiCo was deposited by a constant current electrodeposition2O4The nanowire array uniformly and vertically grows on the surface of the substrate, the length of the nanowire is about 200-300 nm, and the diameter of the nanowire is about dozens of nanometers to dozens of nanometers. At the same time, local NiCo is observed2O4The nanowires are close together in an interweaving manner to form nano clusters which are distributed uniformly, the orientation and distribution of the channels in the figure 1(b) are consistent, and the analysis shows that the Ni-Co precursor of the multi-channel network structure acts as a moldUnder the action of the plate, Ni/Co ions are preferentially deposited in the pore canal under the action of constant current until a nanowire structure is formed. As can be seen from FIG. 3, except the characteristic diffraction peaks representing the nickel foam at three positions of 44.5 °, 51.8 ° and 76.4 ° of 2 θ, the other four positions of 31.1 °, 36.6 °, 59.1 ° and 64.9 ° are matched with PDF standard card (JCPDS:20-0781), and are respectively assigned to NiCo with spinel structure2O4The (220), (311), (511), and (440) crystal planes of (a). The nanowire prepared in this example is a spinel NiCo structure2O4。
Comprehensive analysis shows that the 3D acicular nickel-cobalt double-metal oxide nanoclusters are successfully prepared by the method.
Example 2
1. Cutting the foamed nickel into square sheets with the specification of 1cm multiplied by 0.25cm, then placing the cut foamed nickel into 3mol/L acetone aqueous solution to be soaked for 30min at normal temperature, then placing the soaked foamed nickel into hydrochloric acid with the mass concentration of 6% to be soaked for 30min, repeatedly cleaning the foamed nickel for a plurality of times by using absolute ethyl alcohol and deionized water after soaking, and placing the cleaned foamed nickel in a vacuum drying oven at 70 ℃ to be dried for 3 hours.
2. Soaking the foamed nickel dried in the step 1 in 20mL of pretreatment solution, wherein the pretreatment solution contains 0.375mmol/LNi (NO)3)2、0.75mmol/L Co(NO3)2、1.125mmol/L NH4NO3And heating the aqueous solution of dimethyl sulfoxide with the volume concentration of 2.5% in an oil bath at 100 ℃ for 10min for reaction, repeatedly ultrasonically cleaning the sample for several times by using deionized water and absolute ethyl alcohol after the reaction is finished, and drying the sample in an oven at 60 ℃ for 2h to obtain the pretreated foamed nickel.
3. Soaking the foamed nickel pretreated in the step 2 in 50mL of electrolyte for 5min, wherein the electrolyte contains 0.17mol/L of Ni (NO)3)2、0.17mol/L Co(NO3)2、0.033mol/LNiCl20.1mol/L boric acid, 0.83mmol/L o-sulfonylbenzoylimine and 0.025mmol/L dimethyl sulfoxide, and performing constant current electrodeposition at a current density of 50mA/cm2Depositing for 3h, and directly growing acicular nickel-cobalt-gold on the foamed nickelWhich is a hydroxide.
4. Cleaning the acicular nickel-cobalt double-metal hydroxide foamed nickel grown in the step 3 with deionized water and absolute ethyl alcohol in a 40W ultrasonic cleaning instrument for 5min each time, repeatedly cleaning for 3 times, and then placing the cleaned sample in an oven at 80 ℃ for drying for 3 h; after drying, heating to 300 ℃ at the speed of 1 ℃/min in the air atmosphere, preserving heat for 2h, carrying out high-temperature annealing treatment on the sample, taking out the sample to be recovered to the room temperature, washing the sample for 5min each time in a 40W ultrasonic cleaner by using deionized water and absolute ethyl alcohol, repeatedly washing for 3 times, and then placing the washed sample in an oven at 80 ℃ for drying for 3h to obtain the 3D needle-shaped nickel-cobalt double-metal oxide nano-cluster (see figure 4).
Example 3
1. Cutting the foamed nickel into square sheets with the specification of 1cm multiplied by 0.25cm, then placing the cut foamed nickel into 3mol/L acetone aqueous solution to be soaked for 30min at normal temperature, then placing the soaked foamed nickel into hydrochloric acid with the mass concentration of 6% to be soaked for 30min, repeatedly cleaning the foamed nickel for a plurality of times by using absolute ethyl alcohol and deionized water after soaking, and placing the cleaned foamed nickel in a vacuum drying oven at 70 ℃ to be dried for 3 hours.
2. Soaking the foamed nickel dried in the step 1 in 20mL of pretreatment solution containing 0.375mmol/L Ni (NO)3)2、0.75mmol/L Co(NO3)2、1.125mmol/L NH4NO3And heating the aqueous solution of dimethyl sulfoxide with the volume concentration of 2.5% in an oil bath at 100 ℃ for reaction for 60min, repeatedly ultrasonically cleaning the sample for several times by using deionized water and absolute ethyl alcohol after the reaction is finished, and drying the sample in an oven at 60 ℃ for 2h to obtain the pretreated foamed nickel.
3. Soaking the foamed nickel pretreated in the step 2 in 50mL of electrolyte for 5min, wherein the electrolyte contains 0.17mol/L of Ni (NO)3)2、0.17mol/L Co(NO3)2、0.033mol/LNiCl20.1mol/L boric acid, 0.83mmol/L o-sulfonylbenzoylimine and 0.025mmol/L dimethyl sulfoxide, and performing constant current electrodeposition at a current density of 50mA/cm2Depositing for 1h in the foamNeedle-like nickel-cobalt double metal hydroxide is directly grown on the nickel.
4. Cleaning the acicular nickel-cobalt double-metal hydroxide foamed nickel grown in the step 3 with deionized water and absolute ethyl alcohol in a 40W ultrasonic cleaning instrument for 5min each time, repeatedly cleaning for 3 times, and then placing the cleaned sample in an oven at 80 ℃ for drying for 3 h; after drying, heating to 300 ℃ at the speed of 1 ℃/min in the air atmosphere, preserving heat for 2h, carrying out high-temperature annealing treatment on the sample, taking out the sample to be recovered to the room temperature, washing the sample for 5min each time in a 40W ultrasonic cleaning instrument by using deionized water and absolute ethyl alcohol, repeatedly washing for 3 times, and then placing the washed sample in an oven at 80 ℃ for drying for 3h to obtain the 3D needle-shaped nickel-cobalt double-metal oxide nano-cluster.
Claims (8)
1. A method for preparing 3D needle-shaped nickel-cobalt double-metal oxide nano-clusters by a one-step electrodeposition method is characterized by comprising the following steps:
(1) soaking a foamed nickel substrate in 2-5 mol/L acetone aqueous solution for 20-40 minutes at normal temperature, and then soaking in hydrochloric acid with the mass concentration of 2-10% for 20-40 minutes; repeatedly cleaning the foamed nickel substrate with absolute ethyl alcohol and deionized water after soaking, and drying the cleaned foamed nickel substrate in vacuum at the temperature of 60-80 ℃;
(2) soaking the foamed nickel substrate subjected to vacuum drying in the step (1) in a pretreatment solution, and heating and reacting for 10-60 minutes at the temperature of 60-110 ℃, wherein the pretreatment solution contains 0.3-0.5 mmol/L of Ni (NO)3)2、0.5～1mmol/L Co(NO3)2、1.0～1.5mmol/L NH4NO3And a 1-5% volume concentration aqueous solution of dimethyl sulfoxide; after the reaction is finished, repeatedly ultrasonically cleaning the foamed nickel substrate by using deionized water and absolute ethyl alcohol, and drying to obtain a pretreated foamed nickel substrate;
(3) soaking the foamed nickel substrate pretreated in the step (2) in electrolyte for 3-10 minutes, wherein the electrolyte contains 0.1-0.3 mol/L of Ni (NO)3)2、0.1～0.3mol/LCo(NO3)20.02-0.05 mol/L NiCl solution20.05 to 0.15mol/L boric acid,0.8-1.2 mmol/L o-sulfonylbenzoylimine and 0.01-0.05 mmol/L dimethyl sulfoxide; then directly growing needle-shaped nickel-cobalt double metal hydroxide on a foamed nickel substrate by a constant-current electrodeposition method, wherein the current density of constant-current electrodeposition is 10-60 mA/cm2The deposition time is 1-4 hours;
(4) and (4) annealing the acicular nickel-cobalt bimetal hydroxide foamed nickel substrate grown in the step (3) for 2-5 hours at 250-400 ℃ in an air atmosphere to obtain the 3D acicular nickel-cobalt bimetal oxide nano cluster.
2. The method of preparing 3D acicular nickel cobalt bimetallic oxide nanoclusters by the one-step electrodeposition method of claim 1, wherein: in the step (1), at normal temperature, firstly, soaking a foamed nickel substrate in 3mol/L acetone aqueous solution for 30 minutes, and then soaking in hydrochloric acid with the mass concentration of 6% for 30 minutes; and after soaking, repeatedly cleaning the foamed nickel substrate by using absolute ethyl alcohol and deionized water, and drying the cleaned foamed nickel substrate at 70 ℃ for 3 hours in vacuum.
3. The method of preparing 3D acicular nickel cobalt bimetallic oxide nanoclusters by the one-step electrodeposition method of claim 1, wherein: in the step (2), the foamed nickel substrate dried in the step (1) in vacuum is soaked in a pretreatment solution, and is heated and reacted for 30-40 minutes at the temperature of 90-100 ℃.
4. The method of preparing 3D acicular nickel cobalt bimetallic oxide nanoclusters by the one-step electrodeposition method according to claim 1 or 3, wherein: in the step (2), the pretreatment solution contains 0.35-0.40 mmol/L Ni (NO)3)2、0.7～0.8mmol/L Co(NO3)2、1.12～1.13mmol/L NH4NO3And 2-3% volume concentration dimethyl sulfoxide aqueous solution.
5. The method of preparing 3D acicular nickel cobalt bimetallic oxide nanoclusters by the one-step electrodeposition method of claim 1, wherein: in the step (3), the electrolyte contains 0.15-0.20mol/L Ni(NO3)2、0.15～0.20mol/LCo(NO3)20.03-0.04 mol/L NiCl solution2The solution is 0.08-0.10 mol/L boric acid, 0.9-1.0 mmol/L o-sulfonylbenzoylimine and 0.02-0.3 mmol/L dimethyl sulfoxide.
6. The method of preparing 3D acicular nickel cobalt bimetallic oxide nanoclusters by the one-step electrodeposition method according to claim 1 or 5, wherein: in the step (3), the current density of the constant-current electrodeposition is 40-50 mA/cm2The deposition time is 2-3 hours.
7. The method of preparing 3D acicular nickel cobalt bimetallic oxide nanoclusters by the one-step electrodeposition method of claim 1, wherein: in the step (4), the acicular nickel-cobalt bimetal hydroxide foamed nickel substrate grown in the step (3) is annealed for 2-3 hours at 300-320 ℃ in an air atmosphere.
8. The method of preparing 3D acicular nickel cobalt double metal oxide nanoclusters by the one-step electrodeposition method according to claim 1 or 7, wherein: in the step (4), the annealing temperature rise rate is 1-5 ℃/min.
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| CN112820552B (en) * | 2020-12-31 | 2022-06-28 | 延边大学 | Nickel-iron bimetal hydroxide material and preparation method and application thereof |
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