CN114420467B - Component regulation and control method of ternary layered metal hydroxide electrode material - Google Patents
Component regulation and control method of ternary layered metal hydroxide electrode material Download PDFInfo
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Abstract
The invention discloses a component regulation and control method of a ternary layered metal hydroxide electrode material, which comprises the following steps: preparing soluble metal salt and a component regulator into mixed electrolyte, immersing a conductive substrate serving as a working electrode into the mixed electrolyte, and performing constant potential deposition to obtain a ternary layered metal hydroxide electrode material growing on the surface of the conductive substrate in situ; the component regulator comprises a component containing F ‑ 、C 2 O 4 2‑ 、NH 3 、EDTA 4‑ 、CN ‑ Or NCS ‑ The complexing agent of (1). Wherein, the component regulator can form coordination balance with different metal ions, regulate the concentration of different metal free ions in the mixed electrolyte, and further regulate K sp The deposition balance of different metal ions is balanced, thereby breaking the solubility product constant K in the electrodeposition process sp And limiting, and preparing the ternary layered metal hydroxide electrode material with adjustable components, thereby achieving the purpose of controlling the relative content of metal ions in the electrode material.
Description
Technical Field
The invention relates to the field of preparation of energy storage materials, in particular to a component regulation method of a ternary layered metal hydroxide electrode material.
Background
The super capacitor as an energy storage device has the advantages of high power density, high charging and discharging speed, low maintenance cost, environmental friendliness and the like. The performance of the capacitor greatly depends on the performance of the electrode material, and therefore, the development of high-performance electrode materials is a hot research spot. Commonly used electrode materials include carbon materials, transition metal compounds, conductive polymers, and the like. Among them, the transition metal compound utilizes the rapid oxidation-reduction reaction on the surface of the electrode to realize energy storage, and has the advantage of high specific capacitance, thus being widely concerned by researchers.
Layered Double Hydroxides (LDH) have the advantages of high specific surface area, adjustable chemical composition, high redox activity and the like, and are electrode materials with good performance. However, in the continuous charge and discharge process, the host laminates of the LDH materials are periodically deformed due to the valence change of metal ions, so that the laminates and the crystal structure are damaged, and the specific capacitance is reduced. This disruption of the intrinsic structure leads to poor cycling performance of LDHs, greatly limiting the application of LDH materials.
The research work reported at present adopts the introduction of metal elements without electrochemical activity into an LDH laminate structure to achieve the purposes of stabilizing the laminate structure and improving the cycling stability of the material. The document (Significant roll of Al in Ternary layer Double Hydroxides for Enhancing Electrochemical Performance of Flexible asymmetry supercapacitors, adv Funct Mater 29 (2019) 1903879.) reports that NiCoAl-LDH is grown in situ on the surface of carbon cloth by a hydrothermal method, changes of the morphology and properties of the material are researched by changing the content of aluminum elements, and as a result, the microstructure of LDH gradually transits from nano wires to nano sheets along with the increase of the content of aluminum ions. More importantly, the content of aluminium ions has a very large influence on the performance of the LDH. The increase of the content of aluminum ions can improve the cycling stability of the material and reduce the specific capacitance. Therefore, it is an important issue how to regulate the composition of ternary LDHs so that the electrodes exhibit the best overall performance. Although the components of the metal ions can be controlled by controlling the feeding ratio of the metal salt in the hydrothermal method, the method needs to be carried out under the conditions of high temperature and high pressure, and has the defects of large energy consumption, long time consumption and the like.
The literature (Zhang Y, wei S.Mg-Co-Al-LDH nanoparticles with an active electrochemical performance for superparameter [ J ]. Journal of nanoparameter Research,2019,21) reports that MgCoAl ternary LDH nanoparticles are prepared by a coprecipitation method, the material synthesized by the method needs to be prepared into an electrode by a slurry coating method, the addition of an adhesive is not beneficial to the rate capability of the electrode, and the preparation process is complex.
Chinese patent publication No. CN112542328a discloses a method for preparing a composite electrode material of ternary layered metal hydroxide @ polyaniline, comprising: and depositing polyaniline on the porous conductive substrate by an electrochemical method to prepare a polyaniline substrate, and soaking the polyaniline substrate in mixed electrolyte to prepare the ternary layered metal hydroxide @ polyaniline composite electrode material. In the invention, the mixed electrolyte comprises a growth regulator which is used for regulating and controlling the appearance of the ternary layered metal hydroxide; the polyaniline has rich functional groups, and the coordination action is only limited to the coordination action between imino, cationic amino and other nitrogen-containing groups on the surface of the polyaniline layer and the growth elements of the ternary layered metal hydroxide, so that the nucleation of the ternary layered metal hydroxide is promoted. The invention needs two electrochemical deposition steps, and the process is more complicated.
Disclosure of Invention
The invention provides a component regulation and control method of a ternary layered metal hydroxide electrode material, which realizes the electrochemical preparation of the ternary layered metal hydroxide with adjustable components, has simple steps and mild conditions, and can prolong the cycling stability of an electrode to a certain extent on the premise of keeping higher specific capacitance of the prepared electrode material.
The technical scheme is as follows:
a component regulation and control method of a ternary layered metal hydroxide electrode material is provided, the ternary layered metal hydroxide electrode material is prepared by an electrochemical method, and the method comprises the following steps:
preparing a mixed electrolyte from soluble metal salt and a component regulator, immersing a conductive substrate serving as a working electrode into the mixed electrolyte, and performing constant potential deposition to obtain the ternary layered metal hydroxide electrode material;
the component regulator comprises a component containing F - 、C 2 O 4 2- 、NH 3 、EDTA 4- 、CN - Or NCS - The complexing agent of (1).
The inventor researches and discovers that the deposition process of LDH is influenced by K sp And (5) limiting. Can be prepared by adding component regulator, with K sp Smaller metal ions form a coordination function to enable K sp The concentration of free ions of smaller metal ions in the solution is reduced, the deposition balance is shifted to the left, and the metal ions can be deposited under the higher concentration of hydroxide radicals, so that the aim of controlling the relative content of the metal ions in the deposited product is fulfilled.
The soluble metal salt comprises electrochemical active metal salt and electrochemical inert metal salt, wherein the cation of the electrochemical active metal salt is Co 2+ 、Ni 2+ 、Cr 3+ 、Mn 2+ Or Fe 3+ The cation of the electrochemically inert metal salt is Zn 2+ 、Al 3+ 、Mg 2+ Or Sc 3+ One kind of (1).
The invention takes mixed solution prepared by electrochemical active metal salt, electrochemical inert metal salt and component regulator as mixed electrolyte, wherein, the specific kind and dosage of the component regulator are selected according to the non-electrochemical active metal ion for deposition. The component regulator can form coordination balance with different metal ions, regulate the concentration of different metal free ions in the mixed electrolyte, and further regulate K sp The deposition balance of different metal ions is balanced, thereby breaking the product constant K of solubility in the electrodeposition process sp And limiting, developing a component regulation and control method of the ternary layered metal hydroxide electrode material prepared by an electrochemical method, and preparing the ternary layered metal hydroxide electrode material with adjustable components.
The conductive substrate comprises carbon cloth, metal mesh or foam metal. The conductive substrate has a higher specific surface area, can improve the loading capacity of active substances, and is beneficial to improving the electrochemical performance of an electrode material.
Preferably, the concentration of each electrochemically active metal salt in the mixed electrolyte is 0.01-0.1 mol L -1 The concentration of the electrochemical inert metal salt is 0.01-0.1 mol L -1 The concentration molar ratio of the electrochemically active metal salt to the electrochemically inert metal salt is 1-100.
Preferably, in the mixed electrolyte, the concentration of the component regulator is 0.01-0.2 mol L -1 。
More preferably, the electrochemically active metal salt is Ni (NO) 3 ) 2 、Co(NO 3 ) 2 、Fe(NO 3 ) 3 、Mn(NO 3 ) 2 Or Cr (NO) 3 ) 3 Wherein the electrochemically inert metal salt is Al (NO) 3 ) 3 、Zn(NO 3 ) 2 、Sc(NO 3 ) 3 Or Mg (NO) 3 ) 2 The component regulator is one of NaF and Na 2 C 2 O 4 NaCN, naNCS or Na 4 EDTA。
Preferably, the mixed electrolyte also comprises an additive, and the additive comprises KNO 3 The concentration is 0.05 to 0.2mol L -1 (ii) a Addition of additives for ensuring NO in solution 3 - Can be stably reduced by electrolysis to generate OH - 。
Preferably, the process parameters in the potentiostatic deposition process are as follows: -0.9 to-1.5V, 3 to 30min. The deposition time is too long, so that the stacking of the nanosheet structure is caused, the structure is irregular, the specific surface area is reduced, and the rate capability is reduced; too short a deposition time results in too low a loading, reduced discharge time and reduced specific capacitance.
The invention also provides a ternary layered metal hydroxide electrode material with adjustable components, which is prepared by the component regulation method of the ternary layered metal hydroxide electrode material.
The ternary layered metal hydroxide electrode material takes two variable valence metals as an electroactive center and one non-variable valence metal as a structural stable center, and the three metals jointly form a reticular lamellar structure which is connected with each other. Under the auxiliary action of the component regulator, a small amount of monovalent metal is regulated and controlled to enter the electrode material, so that the cycling stability of the electrode can be improved on the premise of not excessively damaging the electrochemical performance of the electrode.
The invention also provides application of the ternary layered metal hydroxide electrode material in an energy storage device.
The energy storage device is a super capacitor, the ternary layered metal hydroxide electrode material is used as a cathode to assemble the asymmetric super capacitor, and the specific capacitance and the cycle performance of the capacitor can be greatly improved due to the excellent specific capacitance and cycle performance of the electrode.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention uses the electrochemical method to prepare the ternary layered metal hydroxide electrode material, and has the advantages of mild preparation conditions, simple steps, easy operation and short reaction time.
(2) In the traditional method for preparing LDH by an electrochemical method, a third component of electrochemical inert ions and a component regulator are introduced, and the deposition balance of metal ions is regulated by regulating and controlling the components and the concentration of an electrolyte and utilizing the coordination between different metal ions and the regulator, so that different Ks are ensured sp The metal ions form metal hydroxide together with reasonable composition, so that the electrochemical preparation of the ternary layered metal hydroxide with adjustable components is realized, and the aim of controlling the relative content of the metal ions in the electrode material is fulfilled.
(3) The method can lead the prepared electrode material to prolong the cycling stability of the electrode to a certain extent on the premise of keeping higher specific capacitance by regulating and controlling the components and the content of the electrode material, thereby achieving the best comprehensive electrochemical performance.
Drawings
FIG. 1 is a constant current charging and discharging curve diagram of NiCoAl ternary layered metal hydroxide grown on the surface of carbon cloth prepared in example 1 under different current densities.
FIG. 2 is a scanning electron microscope image of the NiCoAl ternary layered metal hydroxide electrode material prepared in example 1 at 10000 times.
FIG. 3 is a scanning electron microscope image of the NiCoAl ternary layered metal hydroxide electrode material prepared in example 1 at 50000 times.
FIG. 4 is an XRD diffraction pattern of the NiCoAl ternary layered metal hydroxide electrode material prepared in example 1.
FIG. 5 is a scanning electron microscope image of the NiCoAl ternary layered metal hydroxide electrode material prepared in example 1 after 10000 cycles of cycling.
Detailed Description
The invention is further elucidated with reference to the figures and the examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
To 80mL of deionized water was added 0.59g of Ni (NO) 3 ) 2 、0.29g Co(NO 3 ) 2 、0.34g Al(NO 3 ) 3 、0.80g KNO 3 0.34g of NaF was dissolved by stirring. And (3) taking carbon cloth as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and depositing for 10 minutes under the condition of-1V by adopting a constant potential deposition method to obtain the NiCoAl ternary layered metal hydroxide electrode material. The electron energy spectrum test shows that the mass fraction of Al is 9.59%.
The NiCoAl ternary layered metal hydroxide growing on the surface of the carbon cloth is directly used as an electrode material, and a constant current charge-discharge curve is tested under different current densities, and the result is shown in figure 1. It can be found that the charge-discharge curves of the material have obvious platforms, and the material reflects the energy storage mechanism of the ternary layered metal hydroxide battery type capacitor, namely Ni 2+ 、Co 2+ Reversible redox reaction of (2). The electrode material is calculated to be 1A g by the graph 1 -1 The specific capacitance of the time is as high as 1542.2F g -1 And at 10A g -1 The specific time capacitance is kept at 984.8F g -1 And has excellent rate performance. 10000 cycles are circulated, and the specific capacitance retention rate is 54.1 percent.
SEM photographs of the NiCoAl ternary layered metal hydroxide electrode material prepared in this embodiment are shown in fig. 2 and fig. 3, and it can be seen from the drawings that the NiCoAl ternary layered metal hydroxide exhibits an irregular nanosheet structure, the ternary layered metal hydroxide nanosheets are mutually overlapped to form a loose porous network structure, the thickness of the nanosheet is about 50-100 nm, and a protrusion formed by stacking the nanosheets can be observed on the surface of the active material layer.
The XRD diffraction pattern of the NiCoAl ternary layered metal hydroxide electrode material is shown in figure 4. The diffraction peaks with diffraction angles of 11.12 degrees, 33.98 degrees and 60.72 degrees respectively correspond to the characteristic crystal planes (003), (012) and (110) of hydrotalcite, and the successful synthesis of the NiCoAl ternary layered metal hydroxide is illustrated.
The SEM photograph of the NiCoAl ternary layered metal hydroxide electrode material after 10000 cycles of cycling is shown in FIG. 5. From the figure, it can be found that before and after the cycle, the shape of the ternary layered metal hydroxide is not changed greatly, the loose porous active material layer is not changed greatly, but part of the active material falls off.
Example 2
To 80mL of deionized water was added 0.59g of Ni (NO) 3 ) 2 、0.29g Co(NO 3 ) 2 、0.34g Al(NO 3 ) 3 、0.83g KNO 3 0.20g of NaF was dissolved by stirring. Carbon cloth is used as a working electrode, a platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode; and depositing for 10 minutes under the condition of-1V by adopting a constant potential deposition method to obtain the NiCoAl ternary layered metal hydroxide electrode material. The electron energy spectrum test shows that the mass fraction of Al is 24.2%.
The NiCoAl ternary layered metal hydroxide growing on the surface of the carbon cloth is of a shell structure formed by irregular particles, and the thickness of the shell is about 500 nm.
The NiCoAl ternary layered metal hydroxide electrode material is 1A g -1 The specific capacitance is 1240F g -1 And at 10A g -1 The specific capacitance is maintained at 668F g -1 . 10000 cycles are circulated, and the specific capacitance retention rate is up to 60.7 percent.
Example 3
To 80mL of deionized water was added 0.59g of Ni (NO) 3 ) 2 、0.29g Co(NO 3 ) 2 、0.34g Al(NO 3 ) 3 、0.83g KNO 3 0.25g of NaF was dissolved by stirring. And (3) taking carbon cloth as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and depositing for 30 minutes under the condition of-1V by adopting a constant potential deposition method to obtain the NiCoAl ternary layered metal hydroxide electrode material. The electron energy spectrum test shows that the mass fraction of Al is 11.1%.
The NiCoAl ternary layered metal hydroxide growing on the surface of the carbon cloth presents a porous shell layer formed by sheet stacking.
The NiCoAl ternary layered metal hydroxide electrode material is prepared from 1A g -1 The time specific capacitance is 1532F g -1 And at 10A g -1 The specific capacitance is kept to 1061F g -1 The rate capability is excellent. 10000 cycles are circulated, and the specific capacitance retention rate is 57 percent.
Example 4
To 80mL of deionized water was added 0.44g of Ni (NO) 3 ) 2 、0.44g Co(NO 3 ) 2 、0.51g Al(NO 3 ) 3 、0.83g KNO 3 And 0.35g of NaF, and the mixture was dissolved by stirring. The cleaned foamed nickel is used as a working electrode, a platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode; and depositing for 30 minutes under the condition of-1.5V by adopting a constant potential deposition method to obtain the NiCoAl ternary layered metal hydroxide electrode material. The electron energy spectrum test shows that the mass fraction of Al is 8.6%.
The NiCoAl ternary layered metal hydroxide growing on the surface of the foamed nickel is in a shell structure formed by overlapping nano sheets, and the thickness of the shell is about 1 mu m.
The NiCoAl ternary layered metal hydroxide electrode material is 1A g -1 The specific capacitance is 1630F g -1 And at 10A g -1 The specific capacitance is 1043F g -1 The multiplying power performance is better. 10000 cycles are circulated, and the specific capacitance retention rate is up to 50 percent.
Example 5
To 80mL of deionized water was added 0.58g of Ni (NO) 3 ) 2 、0.77g Fe(NO 3 ) 3 、0.60g Zn(NO 3 ) 2 、0.83g KNO 3 、0.20g Na 2 C 2 O 4 And stirring for dissolving. Carbon cloth is used as a working electrode, a platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode; and depositing for 10 minutes under the condition of-1.0V by adopting a constant potential deposition method to obtain the NiFeZn ternary layered metal hydroxide electrode material. The electron energy spectrum test shows that the mass fraction of Zn is 2.3%.
The NiFeZn ternary layered metal hydroxide growing on the surface of the carbon cloth is in a shell structure formed by irregular particles, and the thickness of the shell is about 500 nm.
The NiFeZn ternary layered metal hydroxide electrode material is 1A g -1 The specific capacitance is 1260F g -1 And at 10A g -1 The specific time capacitance is kept to 653F g -1 . 10000 cycles are circulated, and the specific capacitance retention rate is up to 51.8 percent.
Example 6
To 80mL of deionized water was added 0.73g of Ni (NO) 3 ) 2 、0.36g Mn(NO 3 ) 2 、0.39g Zn(NO 3 ) 3 、0.83g KNO 3 0.30g of NaCN, and the mixture was dissolved by stirring. Taking carbon cloth as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode; and applying a constant voltage of-1.0V for 10 minutes to obtain the NiMnZn ternary layered metal hydroxide electrode material. The electron spectrum showed a mass fraction of Zn of 2.1%.
The NiMnZn ternary layered metal hydroxide growing on the surface of the carbon cloth is in a shell structure formed by irregular particles, and the thickness of the shell is about 500 nm.
The NiMnZn ternary layered metal hydroxide electrode material is prepared in the range of 1A g -1 The specific capacitance is 1360F g -1 And at 10A g -1 The specific time capacitance is kept to 763F g -1 . 10000 cycles are circulated, and the specific capacitance retention rate is up to 58.1 percent.
Example 7
To 80mL of deionized water was added 1.17g of Ni (NO) 3 ) 2 、0.59g Co(NO 3 ) 3 、0.37g Sc(NO 3 ) 3 、0.83g KNO 3 、2.2g Na 4 EDTA, stirring and dissolving. Carbon cloth as working electricityA platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode; and depositing for 10 minutes under the condition of-1.0V by adopting a constant potential deposition method to obtain the NiCoSc ternary layered metal hydroxide electrode material. The electron energy spectrum test shows that the mass fraction of Sc is 10.3%.
The NiCosC ternary layered metal hydroxide growing on the surface of the carbon cloth is in a shell structure formed by irregular particles, and the thickness of the shell is about 350 nm.
The NiCoSc ternary layered metal hydroxide electrode material is 1A g -1 The specific capacitance is 1450F g -1 And at 10A g -1 The specific time capacitance is kept to 972F g -1 . 10000 cycles are circulated, and the specific capacitance retention rate is up to 59.8%.
Example 8
To 80mL of deionized water was added 0.59g of Co (NO) 3 ) 2 、0.77g Fe(NO 3 ) 3 、0.47g Mg(NO 3 ) 2 、0.81g KNO 3 0.26NaNCS, and dissolved with stirring. And (3) taking foamed nickel as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and depositing for 15 minutes under the condition of-1.0V by adopting a constant potential deposition method to obtain the CoFeMg ternary layered metal hydroxide electrode material. The electron energy spectrum test shows that the mass fraction of Mg is 2.7%.
The microcosmic appearance of the CoFeMg ternary layered metal hydroxide growing on the surface of the foamed nickel is a loose shell.
The CoFeMg ternary layered metal hydroxide electrode material is 1A g -1 The specific capacitance is 1523F g -1 And at 10A g -1 The specific capacitance is kept to 1066F g -1 . 10000 cycles are circulated, and the specific capacitance retention rate is up to 52.7 percent.
Comparative example 1
To 80mL of deionized water was added 0.59g of Ni (NO) 3 ) 2 、0.29g Co(NO 3 ) 2 、0.34g Al(NO 3 ) 3 And 0.82g KNO 3 And stirring to dissolve. Using carbon cloth as a working electrode, adopting a constant potential deposition method, depositing for 15 minutes under the condition of-1V, taking out the working electrode after finishing, and cleaning for several times by using deionized water to obtain the carbon cloth-based composite materialNiCoAl-LDH @ carbon cloth electrode material;
the NiCoAl-LDH @ carbon cloth composite electrode material is prepared in the range of 1A g -1 The specific capacitance is only 961F g -1 At 10A g -1 The specific capacitance is only 602F g -1 The specific capacitance retention rate is 73.5% when the electrode is circulated for 10000 circles, although the cycle performance is excellent, al element is easy to deposit because complex ions are not added, and the content of Al in a composite system is up to 40%, so that the specific capacitance of the electrode is low.
Comparative example 2
To 80mL of deionized water was added 0.59g of Ni (NO) 3 ) 2 、0.29g Co(NO 3 ) 2 And 0.81g KNO 3 And stirring to dissolve. Taking carbon cloth as a working electrode, adopting a constant potential deposition method, depositing for 10 minutes under the condition of-1.0V, taking out the working electrode after finishing deposition, and cleaning for a plurality of times by using deionized water to obtain a NiCo-LDH @ carbon cloth electrode material;
the NiCo-LDH @ carbon cloth composite electrode material is prepared in a way that 1A g -1 The specific capacitance reaches 1530F g -1 At 10A g -1 The specific capacitance remains 1156F g -1 The specific capacitance is high and the rate capability is good. But the cycle performance is poor, and the specific capacitance retention rate is only 38.5% at 2000 cycles.
Comparative example 3
0.15g CoSO was added to 50mL deionized water 4 、0.31g NiSO 4 、0.21g Al(NO 3 ) 3 And 1.153g of urea were dissolved with stirring. The carbon cloth washed in advance is added into the solution and is fully immersed. And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to react for 12 hours at 110 ℃. After the reaction is finished, taking out the carbon cloth after the temperature is reduced to room temperature, washing the carbon cloth for a plurality of times by using deionized water, and finally drying the carbon cloth in vacuum to obtain the carbon cloth with the surface growing the layered double hydroxide, namely the NiCoAl ternary layered metal hydroxide @ carbon cloth composite electrode material;
the constant current charge and discharge curve of the layered double hydroxide electrode material prepared in the comparative example 3 under different current densities is similar to that of fig. 1. The performance of the composite electrode was similar to that of example 1, as in 1A g -1 The specific capacitance reaches 1605F g -1 And at 10A g -1 The specific capacitance is still as high as 1155F g -1 And the specific capacitance retention rate can reach 78% after 10000 cycles of circulation, but the hydrothermal method has rigorous preparation conditions, the temperature is as high as 110 ℃, and the preparation time is as long as 12 hours.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A component regulation and control method of a ternary layered metal hydroxide electrode material is characterized by comprising the following steps:
preparing a mixed electrolyte from soluble metal salt and a component regulator, immersing a conductive substrate serving as a working electrode into the mixed electrolyte, and performing constant potential deposition to obtain the ternary layered metal hydroxide electrode material;
the component regulator comprises a component containing F - 、C 2 O 4 2- 、NH 3 、EDTA 4- 、CN - Or NCS - The complexing agent of (1);
the soluble metal salt comprises electrochemical active metal salt and electrochemical inert metal salt, wherein the cation of the electrochemical active metal salt is Co 2+ 、Ni 2+ 、Cr 3+ 、Mn 2+ Or Fe 3+ The cation of the electrochemically inert metal salt is Zn 2+ 、Al 3+ 、Mg 2+ Or Sc 3+ One kind of (1).
2. The method as claimed in claim 1, wherein the conductive substrate comprises carbon cloth, metal mesh or metal foam.
3. Compositional formulation of the ternary layered metal hydroxide electrode material of claim 1The control method is characterized in that the concentration of each electrochemical active metal salt in the mixed electrolyte is 0.01-0.1 mol L -1 The concentration of the electrochemical inert metal salt is 0.01-0.1 mol L -1 The concentration molar ratio of the electrochemically active metal salt to the electrochemically inert metal salt is 1-100.
4. The method for regulating and controlling the composition of the ternary layered metal hydroxide electrode material according to claim 1, wherein the concentration of the composition regulator in the mixed electrolyte is 0.01 to 0.2mol L -1 。
5. The method for controlling the composition of a ternary layered metal hydroxide electrode material according to claim 1, wherein the electrochemically active metal salt is Ni (NO) 3 ) 2 、Co(NO 3 ) 2 、Fe(NO 3 ) 3 、Mn(NO 3 ) 2 Or Cr (NO) 3 ) 3 Wherein the electrochemically inert metal salt is Al (NO) 3 ) 3 、Zn(NO 3 ) 2 、Sc(NO 3 ) 3 Or Mg (NO) 3 ) 2 The component regulator is one of NaF and Na 2 C 2 O 4 NaCN, naNCS or Na 4 EDTA。
6. The method for controlling the composition of a ternary layered metal hydroxide electrode material as claimed in claim 1, wherein the mixed electrolyte further comprises an additive comprising KNO 3 。
7. The method for regulating and controlling the composition of the ternary layered metal hydroxide electrode material according to claim 1, wherein the process parameters in the constant potential deposition process are as follows: -0.9 to-1.5V, 3 to 30min.
8. The ternary layered metal hydroxide electrode material with adjustable components, which is prepared by the method for regulating and controlling the components of the ternary layered metal hydroxide electrode material according to any one of claims 1 to 7.
9. The use of the compositionally tunable ternary layered metal hydroxide electrode material of claim 8 in an energy storage device.
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| CN113314350A (en) * | 2021-06-22 | 2021-08-27 | 重庆交通大学 | Ternary nickel-cobalt-iron double hydroxide electrode material, preparation method and supercapacitor |
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| Accelerated oxygen evolution kinetics on NiFeAllayered double hydroxide electrocatalysts with defect sites prepared by electrodeposition;Huixi Li etc;《international journal of hydrogen energy》;20191015;第44卷;第128557页试验部分 * |
| Hierarchical nanosheets of ternary CoNiFe layered double hydroxide for supercapacitors and oxygen evolution reaction;R.C. Rohit etc;《Journal of Alloys and Compounds》;20201125;第863卷;全文 * |
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