CN109243838B - Nickel-cobalt double hydroxide electrode material and preparation method thereof - Google Patents
Nickel-cobalt double hydroxide electrode material and preparation method thereof Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention relates to a preparation method of a nickel-cobalt double hydroxide electrode material, which comprises the following steps: dispersing cobalt salt and nickel salt in deionized water, and stirring to form a uniform mixed solution A; adding urea and ammonium fluoride into the mixed solution A, and stirring to obtain a mixed solution B, wherein the concentration of the ammonium fluoride in the mixed solution B is 0.02-0.04 mol/L; and placing the mixed solution B in a high-pressure reaction kettle for hydrothermal reaction. By implementing the preparation method, the problems of poor conductivity, unstable microstructure, poor multiplying power, low specific capacitance and short cycle life of the nickel-cobalt double hydroxide electrode material can be solved.
Description
Technical Field
The invention relates to the field of electrode materials, in particular to a nickel-cobalt double hydroxide electrode material and a preparation method thereof.
Background
Along with the use of a large amount of non-renewable energy sources, fossil energy sources are increasingly exhausted and the problem of air pollution is becoming serious, in order to realize sustainable development and utilization of energy sources, new energy sources and novel energy storage devices become one of the hotspots of research of people, the content of research and development of novel electroactive materials serving as the core of the novel energy storage devices is bound to become important, and the performance of each electrochemical performance of the novel electroactive materials directly becomes a limiting condition influencing the performance and popularization and application of each energy storage device.
At present, various novel energy storage devices such as lithium ion batteries, super capacitors and the like are researched and developedThe improvement mainly surrounds the active material used by the electrode, and the metal layered double hydroxide as a high-performance electrode active material with great potential is now a hot spot of controversial research of various novel energy storage devices. In new energy storage devices, metal layered double hydroxides have been used as an ideal positive electrode active material, and the chemical formula of the layered double hydroxide is generally denoted as M 1-x 2+ M x 3+ (OH) 2 x+ A x/n n- ·mH 2 O, wherein M 2+ /M 3+ Respectively represent 2/3 valence metal ions (such as Ni, Co, Mg, Cu, Zn, Al, Fe, Mn, etc.), A n- Is a charge-balancing anion, and mH 2 O is an interlayer water molecule.
The nickel-cobalt double hydroxide has high specific capacitance due to the combined action of reasonable mesoporous pore size distribution, high specific surface area, multiple valence states of two elements of nickel and cobalt, synergistic action of the two elements and the like, but the nickel and cobalt are the same as battery active materials such as other transition metal-based double hydroxides or hydroxides and the like, the conductivity and the multiplying power of the nickel-cobalt double hydroxide are poor due to the characteristics of semiconductors, and particularly under high multiplying power, the dynamics of the nickel-cobalt double hydroxide is controlled by a diffusion control process and a phase change process, so that the structure of the nickel-cobalt double hydroxide is not stable enough, the active materials are lost, and the cycle performance of an energy storage device is poor directly. Therefore, how to effectively solve the problems of poor conductivity, unstable microstructure, poor rate capability, unstable cycle and the like of the nickel-cobalt layered double hydroxide becomes an urgent research for novel energy storage devices.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a method for preparing a nickel-cobalt double hydroxide electrode material, so as to solve the problems of poor conductivity, unstable microstructure, poor rate capability, low specific capacitance and short cycle life of the nickel-cobalt double hydroxide electrode material.
The invention provides a preparation method of a nickel-cobalt double hydroxide electrode material, which comprises the following steps:
dispersing cobalt salt and nickel salt in deionized water, and stirring to form a uniform mixed solution A;
adding urea and ammonium fluoride into the mixed solution A, and stirring to obtain a mixed solution B, wherein the concentration of the ammonium fluoride in the mixed solution B is 0.02-0.04 mol/L;
and placing the mixed solution B in a high-pressure reaction kettle for hydrothermal reaction.
And further, placing the current collector and the mixed solution B in the high-pressure reaction kettle together for hydrothermal reaction, cooling the high-pressure reaction kettle to room temperature after the hydrothermal reaction, taking out, cleaning and drying the current collector, and obtaining the nickel-cobalt double hydroxide electrode material attached to the current collector.
Optionally, after the hydrothermal reaction, cooling the high-pressure reaction kettle to room temperature, centrifuging, filtering, and drying the reacted solution to obtain the powdery nickel-cobalt double hydroxide electrode material.
Further, the molar ratio of the cobalt salt to the nickel salt in the mixed solution a is x: (1-x), wherein 0< x < 1.
Further, the cobalt salt is Co (NO) 3 ) 2 ·6H 2 O、CoCl 2 ·6H 2 O、CoSO 4 ·6H 2 O or Co (Ac) 2 ·6H 2 O, the nickel salt is Ni (NO) 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 O、Co SO 4 ·6H 2 O or Co (Ac) 2 ·6H 2 O。
Further, the concentration of the urea in the mixed solution B is 0.1-0.17 mol/L.
Furthermore, the hydrothermal reaction temperature is 90-160 ℃, and the hydrothermal reaction time is 8-10 h.
Further, before the hydrothermal reaction step, cleaning the current collector: and respectively putting the current collector into acetone, absolute ethyl alcohol, hydrochloric acid and deionized water, ultrasonically cleaning and drying.
Further, the current collectors are dispersedly placed at the bottom of the high-pressure reaction kettle.
The second aspect of the invention provides a nickel cobalt double hydroxide electrode material, which is prepared by any one of the above preparation methods.
Due to the technical scheme, the nickel-cobalt double hydroxide electrode material provided by the embodiment of the invention has the following beneficial effects:
1) has more excellent specific surface area, thereby improving specific capacitance;
2) the structure stability is good, the structure is not easy to collapse after long-term recycling, so that the specific capacitance is improved, and the recycling service life is prolonged;
3) there are more electrically active contact points, improving their electrical conductivity.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the embodiment or the description of the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can also be derived from them without inventive effort.
FIG. 1 is a schematic diagram of step 5) of a nickel cobalt double hydroxide electrode material provided in examples and comparative examples of the present invention;
FIG. 2 is a schematic diagram of the synthesis of a nickel cobalt double hydroxide electrode material provided by the examples of the present invention and the comparative examples;
FIG. 3 is EIS test graphs of nickel cobalt double hydroxide electrode materials provided by the examples of the present invention and the comparative examples;
FIG. 4 shows a nickel-cobalt double hydroxide electrode material at 30A g provided in the examples and comparative examples of the present invention -1 Current density of (c) and a cycle profile of 3000 cycles of charge and discharge.
In the drawings:
1-high pressure reactor 2-current collector
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprising" and "having," as well as any variations thereof, are intended to cover non-exclusive inclusions.
The ammonium fluoride induced nickel cobalt double hydroxide electrode material is prepared by a hydrothermal synthesis technology, and the chemical reaction in a reaction kettle in the synthesis process mainly comprises the following steps:
CO(NH 2 ) 2 +H 2 O→2NH 3 +CO 2 (1)
CO 2 +H 2 O→CO 3 2- +2H + (2)
NH 3 +H 2 O→NH 4 + +OH - (3)
M2++xF-→MFx(x-2)- (4)
Ni 2+ +xF - →[NiFx] (x-2)- (5)
[NiFx] (x-2)- +nH 2 O→[NiF x-n (OH)n] (x-2)- +nHF (6)
2Ni 2+ +Co 2+ +4OH - +CO 3 2- +H 2 O→Ni 2 Co(CO 3 )(OH) 4 .H 2 O (7)
the technical solutions in the embodiments and the comparative examples of the present invention will be clearly and completely described below with reference to the drawings in the specification of the present invention. The materials and equipment used in the following examples and comparative examples are all conventional products commercially available.
Example one
The embodiment of the invention provides a preparation method of a nickel-cobalt double hydroxide electrode material, which comprises the following steps:
1) selecting a proper amount of current collector 2 such as a nickel net as an attaching substrate of an active material;
2) sequentially and respectively putting the nickel screen into a beaker filled with acetone, absolute ethyl alcohol, hydrochloric acid and deionized water, ultrasonically stirring for 5-30 minutes, and then drying for later use;
3) 1mmol of CoCl was weighed 2 ·6H 2 O and 2mmol of NiCl 2 ·6H 2 O, adding the mixture into 60mL of deionized water, and ultrasonically stirring for 20-40 minutes to obtain a uniform mixed solution A of cobalt salt and nickel salt;
4) adding 6mmol of urea and 1.5mmol of ammonium fluoride into the mixed solution A, and ultrasonically stirring for more than 30 minutes to obtain a mixed solution B, wherein the concentration of the urea in the mixed solution B is 0.1mol/L, and the concentration of the ammonium fluoride is 0.025mol/L (neglecting the volumes of the urea and the ammonium fluoride when calculating the concentrations);
5) putting the nickel screen obtained in the step 2) and the mixed solution B into a high-pressure reaction kettle 1 together, wherein the nickel screen is dispersedly placed at the bottom of the high-pressure reaction kettle 1 as shown in figure 1, and the mixed solution B is subjected to hydrothermal reaction for 8-10h at 90-160 ℃;
6) cooling the high-pressure reaction kettle 1 to room temperature, taking out the nickel screen, cleaning ions and adsorbed solvent attached to the surface of the nickel screen by using deionized water, and drying the nickel screen to obtain the nickel-cobalt double hydroxide electrode material attached to the surface of the nickel screen, wherein the nickel-cobalt double hydroxide electrode material is in a compact nano linear shape as shown in the attached figure 2.
And (4) performance testing: in this embodiment, a three-electrode system is adopted to perform an electrochemical performance test on a prepared nickel-cobalt double hydroxide electrode material, a nickel mesh on which the nickel-cobalt double hydroxide electrode material is attached is used as a working electrode, a mercury oxide electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, 6mol/L KOH is used as an electrolyte, and an EIS test and a test are performed at room temperatureThe curve is shown in figure 3; and are respectively 2 A.g -1 And 30A. g -1 The working electrode was subjected to a constant current charge-discharge test at a current density of 2 A.g -1 The specific capacitance was tested at the current density of (2); at 30 A.g -1 The current density of the battery is 3000 times, and the cycle curve is shown in figure 4.
Example two
The second embodiment of the invention provides a preparation method of a nickel-cobalt double hydroxide electrode material, which comprises the following steps:
1) selecting a proper amount of current collector 2 such as nickel mesh or nickel foam as an attaching substrate of an active material;
2) sequentially and respectively putting the nickel screen into a beaker filled with acetone, absolute ethyl alcohol, hydrochloric acid and deionized water, ultrasonically stirring for 5-30 minutes, and then drying for later use;
3) 1mmol of CoCl was weighed 2 ·6H 2 O and 2mmol of NiCl 2 ·6H 2 Adding O into 60mL of deionized water, and ultrasonically stirring for 20-40 minutes to obtain a uniform mixed solution A of cobalt salt and nickel salt;
4) adding 6mmol of urea and 2.25mmol of ammonium fluoride into the mixed solution A, and ultrasonically stirring for more than 30 minutes to obtain a mixed solution B, wherein the concentration of the urea in the mixed solution B is 0.1mol/L, and the concentration of the ammonium fluoride is 0.0375mol/L (neglecting the volume of the urea and the ammonium fluoride when calculating the concentration)
5) Putting a nickel net and the mixed solution B into a high-pressure reaction kettle 1 together, wherein the nickel net and the mixed solution B are dispersedly placed at the bottom of the high-pressure reaction kettle 1 as shown in figure 1, and the mixed solution B is subjected to hydrothermal reaction for 8-10h at 90-160 ℃;
6) cooling the high-pressure reaction kettle 1 to room temperature, taking out the nickel screen, cleaning ions and adsorbed solvent attached to the surface of the nickel screen with deionized water, and drying the nickel screen to obtain the nickel-cobalt double hydroxide electrode material attached to the surface of the nickel screen, wherein the nickel-cobalt double hydroxide electrode material is in a compact nano-layered shape as shown in figure 2;
and (3) performance testing: in this example, the nickel-cobalt double hydroxide electrode prepared by using three-electrode systemPerforming electrochemical performance test on the electrode material, performing EIS test at room temperature by using a nickel mesh attached with the nickel-cobalt double hydroxide electrode material as a working electrode, a mercury oxide electrode as a reference electrode, a platinum sheet as a counter electrode and 6mol/L KOH as electrolyte, wherein the test curve is shown in attached figure 3; and are respectively 2 A.g -1 And 30A. g -1 The working electrode was subjected to a constant current charge-discharge test at a current density of 2 A.g -1 The specific capacitance was tested at the current density of (2); at 30 A.g -1 The current density of the battery is 3000 times, and the cycle curve is shown in figure 4.
Comparative example 1
The invention provides a preparation method of a nickel-cobalt double hydroxide electrode material, which comprises the following steps:
1) selecting a proper amount of current collector 2 such as nickel mesh or nickel foam as an attaching substrate of an active material;
2) sequentially and respectively putting the nickel screen into a beaker filled with acetone, absolute ethyl alcohol, hydrochloric acid and deionized water, ultrasonically stirring for 5-30 minutes, and then drying for later use;
3) 1mmol of CoCl was weighed 2 ·6H 2 O and 2mmol of NiCl 2 ·6H 2 Adding O into 60mL of deionized water, and ultrasonically stirring for 20-40 minutes to obtain a uniform mixed solution A of cobalt salt and nickel salt;
4) adding 6mmol of urea into the mixed solution A, and ultrasonically stirring for more than 30 minutes to obtain a mixed solution B, wherein the concentration of the urea in the mixed solution B is 0.1mol/L (neglecting the volume of the urea when calculating the concentration)
5) Putting a nickel net and the mixed solution B into a high-pressure reaction kettle 1 together, wherein the nickel net and the mixed solution B are dispersedly placed at the bottom of the high-pressure reaction kettle 1 as shown in figure 1, and the mixed solution B is subjected to hydrothermal reaction for 8-10h at 90-160 ℃;
6) cooling the high-pressure reaction kettle 1 to room temperature, taking out the nickel screen, cleaning ions and adsorbed solvent attached to the surface of the nickel screen with deionized water, and drying the nickel screen to obtain the nickel-cobalt double hydroxide electrode material attached to the surface of the nickel screen, wherein the nickel-cobalt double hydroxide electrode material is in a nanometer flower shape as shown in the attached drawing 2;
and (3) performance testing: in the first comparative example, a three-electrode system is adopted to perform electrochemical performance test on the prepared nickel-cobalt double hydroxide electrode material, a nickel mesh attached with the nickel-cobalt double hydroxide electrode material is used as a working electrode, a mercury oxide electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, 6mol/L KOH is used as electrolyte, and an EIS test is performed at room temperature, wherein a test curve is shown in figure 3; and are respectively 2 A.g -1 And 30A. g -1 The working electrode was subjected to a constant current charge-discharge test at a current density of 2 A.g -1 The specific capacitance was tested at the current density of (2); at 30 A.g -1 The current density of the battery is 3000 times, and the cycle curve is shown in figure 4.
Comparative example No. two
The invention provides a preparation method of a nickel cobalt double hydroxide electrode material, which comprises the following steps:
1) selecting a proper amount of current collector 2 such as nickel mesh or nickel foam as an attaching substrate of the active material;
2) sequentially and respectively putting the nickel screen into a beaker filled with acetone, absolute ethyl alcohol, hydrochloric acid and deionized water, ultrasonically stirring for 5-30 minutes, and then drying for later use;
3) 1mmol of CoCl was weighed 2 ·6H 2 O and 2mmol of NiCl 2 ·6H 2 Adding O into 60mL of deionized water, and ultrasonically stirring for 20-40 minutes to obtain a uniform mixed solution A of cobalt salt and nickel salt;
4) adding 6mmol of urea and 0.75mmol of ammonium fluoride into the mixed solution A, and ultrasonically stirring for more than 30 minutes to obtain a mixed solution B, wherein the concentration of the urea in the mixed solution B is 0.1mol/L, and the concentration of the ammonium fluoride is 0.0125mol/L (neglecting the volume of the urea and the ammonium fluoride when calculating the concentration)
5) Putting a nickel net and the mixed solution B into a high-pressure reaction kettle 1 together, wherein the nickel net and the mixed solution B are dispersedly placed at the bottom of the high-pressure reaction kettle 1 as shown in figure 1, and the mixed solution B is subjected to hydrothermal reaction for 8-10h at 90-160 ℃;
6) cooling the high-pressure reaction kettle 1 to room temperature, taking out the nickel screen, cleaning ions and adsorbed solvent attached to the surface of the nickel screen with deionized water, and drying the nickel screen to obtain the nickel-cobalt double hydroxide electrode material attached to the surface of the nickel screen, wherein the nickel-cobalt double hydroxide electrode material is in a sparse nanowire shape as shown in the attached drawing 2;
and (3) performance testing: in the second comparative example, a three-electrode system is adopted to perform electrochemical performance test on the prepared nickel-cobalt double hydroxide electrode material, a nickel mesh attached with the nickel-cobalt double hydroxide electrode material is used as a working electrode, a mercury oxide electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, 6mol/L KOH is used as electrolyte, and an EIS test is performed at room temperature, wherein a test curve is shown in figure 3; and are respectively 2 A.g -1 And 30A. g -1 The working electrode was subjected to a constant current charge-discharge test at a current density of 2 A.g -1 The specific capacitance was tested at the current density of (2); at 30 A.g -1 The current density of (3) is 3000 times, and the cycle curve is shown in figure 4.
Comparative example No. three
The third comparative example of the invention provides a preparation method of a nickel-cobalt double hydroxide electrode material, which comprises the following steps:
1) selecting a proper amount of current collector 2 such as nickel mesh or nickel foam as an attaching substrate of an active material;
2) sequentially and respectively putting the nickel screen into a beaker filled with acetone, absolute ethyl alcohol, hydrochloric acid and deionized water, ultrasonically stirring for 5-30 minutes, and then drying for later use;
3) 1mmol of CoCl was weighed 2 ·6H 2 O and 2mmol of NiCl 2 ·6H 2 Adding O into 60mL of deionized water, and ultrasonically stirring for 20-40 minutes to obtain a uniform mixed solution A of cobalt salt and nickel salt;
4) adding 6mmol of urea and 3mmol of ammonium fluoride into the mixed solution A, and ultrasonically stirring for more than 30 minutes to obtain a mixed solution B, wherein the concentration of the urea in the mixed solution B is 0.1mol/L, and the concentration of the ammonium fluoride is 0.05mol/L (neglecting the volume of the urea and the ammonium fluoride when calculating the concentration)
5) Putting a nickel net and the mixed solution B into a high-pressure reaction kettle 1 together, wherein the nickel net and the mixed solution B are dispersedly placed at the bottom of the high-pressure reaction kettle 1 as shown in figure 1, and the mixed solution B is subjected to hydrothermal reaction for 8-10h at 90-160 ℃;
6) cooling the high-pressure reaction kettle 1 to room temperature, taking out the nickel screen, cleaning ions and adsorbed solvent attached to the surface of the nickel screen with deionized water, and drying the nickel screen to obtain the nickel-cobalt double hydroxide electrode material attached to the surface of the nickel screen, wherein the nickel-cobalt double hydroxide electrode material is in a sparse nano-layered shape as shown in the attached drawing 2;
and (4) performance testing: in the third comparative example, a three-electrode system is adopted to perform electrochemical performance test on the prepared nickel-cobalt double hydroxide electrode material, a nickel mesh attached with the nickel-cobalt double hydroxide electrode material is used as a working electrode, a mercury oxide electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, 6mol/L KOH is used as electrolyte, and an EIS test is performed at room temperature, wherein a test curve is shown in an attached drawing 3; and are respectively 2 A.g -1 And 30A. g -1 The working electrode was subjected to a constant current charge-discharge test at a current density of 2A · g -1 The specific capacitance was tested at the current density of (2); at 30 A.g -1 The current density of (3) is 3000 times, and the cycle curve is shown in figure 4.
Table 1 shows the amounts of ammonium fluoride added, 2A g, in the above examples and comparative examples, respectively -1 Specific capacitance at a current density of (1) and 30 A.g -1 Capacity retention at a current density of (a).
TABLE 1
| Item | Ammonium fluoride/mmol | Specific capacitance/F.g -1 | Capacity retention ratio/%) |
| Example one | 1.5 | 1210 | 90 |
| Example two | 2.25 | 955 | 99 |
| Comparative example 1 | 0 | 936 | 88 |
| Comparative example No. two | 0.75 | 1440 | 40 |
| Comparative example No. three | 3 | 481 | 97 |
The specific capacitance and capacity retention test data of the examples and comparative examples in table 1 show that the nickel cobalt double hydroxide electrode materials of the examples I and II are superior to the electrode material of the comparative example I in single performance, and the nickel cobalt double hydroxide electrode materials of the examples are superior to the electrode materials of all the comparative examples in comprehensive performance.
As can be seen from the EIS curve of fig. 3, the impedances of the first and second examples are significantly lower than the measured impedance values of the samples of the comparative example. It can be seen from the semi-circle of the middle frequency region and the oblique line of the low frequency region of the EIS curve that the nickel-cobalt double hydroxide electrode materials prepared in the first and second examples are excellent in charge transfer and ion diffusion capabilities.
According to the combination of surface morphology analysis and performance test data, the nickel-cobalt double hydroxide electrode material prepared by reasonably adding ammonium fluoride has more excellent specific surface area, structural stability and electroactive contact point, so that the specific capacitance, the cycle service life and the conductivity of the nickel-cobalt double hydroxide electrode material are improved.
It should be noted that the nickel cobalt double hydroxide electrode material of the present invention may exist in a form of being attached to the surface of a nickel mesh, or may exist in a form of a powder sample, and the preparation method of the powder sample includes performing a centrifugal treatment on the solution after the reaction in the reaction kettle in step 6) of the above examples and comparative examples to obtain a wet powder sample, then placing the wet powder sample into an oven, drying at 60 ℃ overnight to obtain a dry powder sample of the nickel cobalt double hydroxide electrode material, and pressing the prepared powder sample on the surface of a cleaned nickel mesh, thereby performing an electrochemical test. It can be deduced that the powder samples of the nickel cobalt double hydroxide electrode material have similar electrochemical properties to the nickel cobalt double hydroxide electrode material attached to the surface of the nickel mesh, and a detailed description thereof will not be given here.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show several embodiments of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (8)
1. A preparation method of a nickel-cobalt double hydroxide electrode material is characterized by comprising the following steps:
dispersing cobalt salt and nickel salt in deionized water, and stirring to form a uniform mixed solution A;
the molar ratio of the cobalt salt to the nickel salt in the mixed solution A is 1: 2;
adding urea and ammonium fluoride into the mixed solution A, and stirring to obtain a mixed solution B, wherein the concentration of the ammonium fluoride in the mixed solution B is 0.02-0.04 mol/L; the concentration of urea in the mixed solution B is 0.1-0.17 mol/L;
and placing the mixed solution B in a high-pressure reaction kettle for hydrothermal reaction for 8-10 h.
2. The method for preparing a nickel cobalt double hydroxide electrode material according to claim 1, wherein a current collector and the mixed solution B are jointly placed in the high-pressure reaction kettle for hydrothermal reaction, after the hydrothermal reaction, the high-pressure reaction kettle is cooled to room temperature, and the current collector is taken out, cleaned and dried to obtain the nickel cobalt double hydroxide electrode material attached to the current collector.
3. The method for preparing a nickel cobalt double hydroxide electrode material according to claim 1, wherein after the hydrothermal reaction, the high-pressure reaction kettle is cooled to room temperature, and the solution after the reaction is centrifuged, filtered and dried to obtain the nickel cobalt double hydroxide electrode material in a powder form.
4. The method of claim 1, wherein the cobalt salt is Co (NO) 3 ) 2 ·6H 2 O、CoCl 2 ·6H 2 O、CoSO 4 ·6H 2 O or Co (Ac) 2 ·6H 2 O, the nickel salt is Ni (NO) 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 O、CoSO 4 ·6H 2 O or Co (Ac) 2 ·6H 2 O。
5. The method for preparing a nickel cobalt double hydroxide electrode material according to claim 1, wherein the hydrothermal reaction temperature is 90-160 ℃.
6. The method for preparing a nickel cobalt double hydroxide electrode material according to claim 2, further comprising, before the hydrothermal reaction step, cleaning the current collector: and respectively placing the current collector in acetone, absolute ethyl alcohol, hydrochloric acid and deionized water, carrying out ultrasonic cleaning and drying.
7. The method for preparing a nickel cobalt double hydroxide electrode material according to claim 2, characterized in that the current collector (2) is dispersedly placed at the bottom of the autoclave (1).
8. A nickel cobalt double hydroxide electrode material, characterized in that the nickel cobalt double hydroxide electrode material is prepared by the method of any one of claims 1 to 7.
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| CN111439789A (en) * | 2020-03-13 | 2020-07-24 | 长春大学 | Preparation method of nickel-cobalt double hydroxide energy storage electrode material |
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