CN111899989B - Preparation method and application of high-stability aluminum-doped alpha-phase NiCo-LDHs electrode material - Google Patents
Preparation method and application of high-stability aluminum-doped alpha-phase NiCo-LDHs electrode material Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- 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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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- 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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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- 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 discloses a preparation method and application of a high-stability aluminum-doped alpha-phase NiCo-LDHs electrode material, wherein the alpha-phase structure shows high electrochemical activity, and Al is used for simultaneously3+The positive effect of (2) ensures excellent stability of the material structure. The experimental method is a complex conversion method, and comprises the steps of dissolving a nickel source, a cobalt source and an aluminum source, adding the dissolved nickel source, cobalt source and aluminum source into a mixed solution of ammonium chloride and ammonia water for complexing, then centrifugally collecting a complex, adding the complex into a prepared thiourea solution, centrifugally dispersing, and then putting the solution into a hydrothermal kettle for hydrothermal reaction to obtain a target product. The invention adopts the complex as a precursor and adopts a two-step method for synthesis, solves the problem of uneven phases of conventional Al-doped products, has simple method and low cost, and can be used as a super capacitor electrode material with high specific capacity and excellent cycling stability.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage, and particularly relates to a preparation method and application of a high-stability aluminum-doped alpha-phase NiCo-LDHs electrode material.
Background
At present, the energy problem is a major problem faced by human beings, and a super capacitor as a novel green energy storage device has a wide application prospect in the fields of new energy technologies, electric automobiles and the like. The nickel-cobalt-based electrode material of the super capacitor has high theoretical specific capacity, is environment-friendly and low in cost, and is taken as one of the pseudo-capacitor electrode materials with the most potential application. However, in the energy storage process with high specific capacity, oxidation-reduction reaction needs to be carried out for underpotential chemisorption desorption, and structural collapse is easy to occur in the use process, so that the cycle stability is poor, which is one of the important reasons that the nickel-cobalt-based material is difficult to commercialize at present.
NiCo-LDHs are divided into alpha phase andthe alpha phase has high electrochemical activity but is difficult to stably exist, and tends to be converted into the beta phase in the using process; while the beta phase is stable, but has low electrochemical activity, it is difficult to provide high energy density for energy storage devices. J. the NiCo-LDHs and GO composite material prepared by Yang et al has the specific capacity of 750C g-1However, the specific capacity is only kept 80% after 5000 circles of cycling stability. The simple nickel-cobalt-based material is difficult to keep stable in structure in long-term cyclic use, and the introduction of a third metal element to construct a new crystal structure frame is an effective strategy for improving the cyclic stability. Al (Al)3+High valence state, small radius and high polarity, and can be introduced into nickel-cobalt system (such as nickel-cobalt double hydroxide) to prevent structure collapse and stabilize structure. For example, Xuaorui Gao et Al in situ grow NiCo on carbon cloth by Al doping2The three-electrode cycling stability of the Al-LDH can reach 12000-turn retention 97.3%, and although the high cycling stability is maintained, the specific capacity of the Al-LDH is only 569C g-1. Therefore, the research on the electrode material which has high specific capacity and excellent cycling stability and is simple and easy to prepare is still a difficult challenge.
The conventional Al doping method is to directly mix and dissolve an Al source, a Ni source and a Co source and then carry out homogeneous coprecipitation, wherein Al (OH)3Ksp of (A) is much smaller than that of Ni (OH)2And Co (OH)2Ksp of (1), so Al is in the alkaline system3+In preference to Ni2+And Co2+Precipitation, which makes the phase inhomogeneous. Therefore, the phase uniformity can be achieved by a method of first forming a simple complex at room temperature, dispersing the complex uniformly, and then performing hydrothermal treatment. Al in this case3+While not acting as an active site, its greater polarity distorts the nickel-cobalt lattice symmetry, thereby exposing more active sites, while at the same time Al3+The material can stably maintain the alpha phase under the positive action of the (C), so that the material has excellent cycling stability while maintaining high specific capacity.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-stability aluminum-doped alpha-phase NiCo-LDHs electrode material. Compared with the conventional NiCoAl ternary electrode material, the material is directly used in homogeneous phasePrecipitation method in the presence of Al3+The invention adopts complex as a precursor, and the aluminum-doped alpha-phase NiCo-LDHs which stably exists is synthesized by a two-step method, so that the uniformity of the phase can be realized, and the high specific capacity is maintained and the excellent cycling stability is realized.
The preparation method of the high-stability aluminum-doped alpha-phase NiCo-LDHs electrode material comprises the following steps:
step 1: dissolving a nickel source, a cobalt source and an aluminum source in a mixed solution of deionized water and ethanol according to a certain proportion to obtain a metal ion solution; simultaneously preparing a part of ammonium chloride solution and adding ammonia water to enable the ammonium chloride solution to have a pH buffering effect, and obtaining ammonia water/ammonium chloride solution; the two solutions are mixed thoroughly at room temperature for complexation.
Step 2: and (3) centrifugally collecting the complex obtained in the step (1), adding the complex into a prepared thiourea solution, performing ultrasonic dispersion, and then filling the solution into a hydrothermal kettle for hydrothermal reaction.
And step 3: and collecting a product obtained by the reaction, centrifuging, washing to remove redundant impurities, and drying to obtain a target product.
In the step 1, the nickel source, the cobalt source and the aluminum source are all soluble salts, and can be any one of nitrate and hydrate thereof, sulfate and hydrate thereof, chloride and hydrate thereof, but the anion radicals of the three metal sources are required to be consistent.
In the step 1, the total concentration of metal ions is 20-40 mmol.L-1，Al3+The concentration accounts for 0.1-15% of the total metal ion concentration, and the molar ratio of the nickel source to the cobalt source is (0.1-10): 1.
in the step 1, the concentration of the ammonium chloride solution is 20-50 mmol.L-1(ii) a And adding 5-10 wt% of ammonia water into the ammonium chloride solution until the pH value of the solution is adjusted to 10-11.
In the step 1, during complexation, the mixture is stirred vigorously (stirring speed is 800-1200 r.min)-1) And quickly adding the metal ion solution into the ammonia water/ammonium chloride solution, and then continuously stirring for 5-30 minutes.
In the step 1 and the step 2, the solvent used for preparing the solution is formed by mixing deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is (1-5): 1.
in the step 2, the concentration of thiourea is 20-40 mmol.L-1The total molar amount of thiourea remains the same as the total molar amount of metal ions in step 1; the time of ultrasonic dispersion is 5-60 minutes.
In the step 2, the temperature of the hydrothermal reaction is 90-140 ℃, and the reaction time is 8-15 h.
In the step 3, deionized water is adopted for alternate washing for multiple times; the drying process can be carried out in a vacuum drier at normal temperature.
The Al-doped alpha-phase NiCo-LDHs electrode material prepared by the invention can be used as a super capacitor anode material and has excellent electrochemical performance.
The invention has the beneficial effects that:
(1) the used raw materials are rich, and the cost is low; low requirement on equipment, simple operation, safety and no pollution.
(2) The obtained nickel-cobalt-based electrode material has high stability, can keep 92% of capacity after 10000 times of charge-discharge cycles, can basically play the advantage of maintenance-free performance when being used for a super capacitor, and paves roads for practicality.
(3) The material is in an alpha-phase LDH structure, is beneficial to the rapid ion transmission, and shows 1 A.g when being used as a super capacitor electrode material-1727C g at current density-1High specific capacitance and excellent rate performance.
Drawings
FIG. 1 is an SEM photograph of Al-doped alpha-phase NiCo-LDHs obtained in example 1.
FIG. 2 shows the electrochemical properties of Al-doped α -phase NiCo-LDHs obtained in example 1 in a three-electrode system: (a) a CV curve; (b) a CD curve; (c) specific capacities at different current densities; (d) and (4) cycle performance.
FIG. 3 is an SEM photograph of Al-doped alpha-phase NiCo-LDHs obtained in example 2.
FIG. 4 shows the electrochemical properties of Al-doped α -phase NiCo-LDHs obtained in example 2 in a three-electrode system: (a) a CV curve; (b) a CD curve; (c) specific capacities at different current densities; (d) and (4) cycle performance.
Fig. 5 shows the electrochemical performance of the assembled asymmetric supercapacitor of example 1: (a) a CV curve; (b) a CD curve; (c) specific capacitance at different current densities.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, which are provided to more clearly illustrate the performance of the present invention, but are not limited to the following examples.
Example 1:
2.7mmol of Ni (NO)3)2·6H2O、0.9mmol Co(NO3)2·6H2O and 0.4mmol Al (NO)3)3·9H2Dissolving O in a mixed solution of 45mL of deionized water and 15mL of ethanol, and stirring until the O is dissolved; then 4.5mmol of NH4Cl and 20mL of 5% aqueous ammonia were added to a mixed solution of 52.5mL of deionized water and 17.5mL of ethanol. After stirring evenly, pouring the metal ion solution into a vigorously stirred ammonia water/ammonium chloride solution, reacting for 5 minutes, and then centrifuging and collecting the generated complex. Preparation of 30 mmol. L-1150mL of the thiourea solution, the collected complex was added, ultrasonic dispersion was carried out for 10 minutes, and then the mixture was put into a 200mL hydrothermal reactor and kept at 110 ℃ for 10 hours. And centrifugally washing the obtained product for 4 times by using deionized water, and drying the product for 24 hours at normal temperature in a vacuum drier to obtain Al-doped NiCo-LDHs.
In the embodiment, the complex precursor is ultrasonically dispersed and then assembled through hydrothermal reaction, and the thiourea solution used in hydrothermal process can vulcanize the surface of the material under the premise of not changing the LDH structure of the material, thereby further increasing the electrochemical activity of the material. The final appearance is a plate structure (figure 1) assembled by fine flakes, which not only has a large number of active sites and a large specific surface area, and can enable ions to be rapidly transmitted, but also has the condensation capability, and the structure is not easy to collapse.
The application of the Al-doped NiCo-LDHs obtained in the embodiment as the electrode material of the super capacitor is as follows: assembling a three-electrode system, preparing electrode slurry by using Al-doped NiCo-LDHs as an active substance, conductive carbon black (SP) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder (the mass ratio is 80: 15: 5) and Dimethylacetamide (DMAC) as a solvent, and coating the electrode slurry on current collector graphite paper(1 cm. times.2 cm) with a coating area of 1cm2And drying the left and right parts to be used as working electrodes. The electrochemical performance of the electrode material in a three-electrode system was tested by using 1M KOH as the electrolyte, Ag/AgCl as the reference electrode, Pt as the counter electrode, and Al-doped NiCo-LDHs as the working electrode, as shown in FIG. 2. The Cyclic Voltammetry (CV) curves and constant current Charge and Discharge (CD) curves in FIG. 2 show the behavior of typical cell-type materials of Al-doped NiCo-LDHs at current densities of 1, 2, 5, 10 and 20 A.g-1The specific capacities of the electrodes were 727, 703, 660, 679, 616 and 556C g, respectively-1. At a current density of 20A g-1, the capacity retention was 76%, indicating good rate capability. The Al-doped NiCo-LDHs electrode material obtained by this example was at 10A g-1The capacity retention rate is 92% after 10000 cycles under constant current charge and discharge, which shows that the electrode material has excellent cycle stability.
Example 2:
2.55mmol of Ni (NO)3)2·6H2O、0.85mmol Co(NO3)2·6H2O and 0.6mmol Al (NO)3)3·9H2Dissolving O in a mixed solution of 45mL of deionized water and 15mL of ethanol, and stirring until the O is dissolved; then 4.5mmol of NH4Cl and 20mL of 5% aqueous ammonia were added to a mixed solution of 52.5mL of deionized water and 17.5mL of ethanol. After stirring evenly, pouring the metal ion solution into a vigorously stirred ammonia water/ammonium chloride solution, reacting for 5 minutes, and then centrifuging and collecting the generated complex. Preparation of 30 mmol. L-1150mL of the thiourea solution, the collected complex was added, ultrasonic dispersion was carried out for 10 minutes, and then the mixture was put into a 200mL hydrothermal reactor and kept at 110 ℃ for 10 hours. And centrifugally washing the obtained product for 4 times by using deionized water, and drying the product for 24 hours at normal temperature in a vacuum drier to obtain Al-doped NiCo-LDHs.
The obtained Al-doped NiCo-LDHs was used to prepare electrodes according to the procedure of example 1, and the performance was tested in a three-electrode system. At current densities of 1, 2, 5, 10 and 20 A.g-1The specific capacities of the electrodes were 666, 632, 575, 521 and 456C g, respectively-1. At 10 A.g-1The capacity retention rate is 92.3 percent after 10000 cycles under current density. Watch (A)The Al content is obviously continuously increased, the electrode material can still maintain high cycle stability, but Al3+Not available as active site, excessive Al3+The specific capacity of the electrode material is reduced.
To further increase the utility of the invention, we assembled an asymmetric supercapacitor with the electrode prepared in example 1 as the positive electrode, activated carbon as the negative electrode, potassium hydroxide doped Polybenzimidazole (PBI) as the electrolyte and separator, and tested its electrochemical performance (fig. 5), the supercapacitor having a large specific capacitance at 0.5A · g-1The specific capacitance is 132F g at current density-1I.e. at 450 W.Kg-1The energy density was 59.45 Wh.Kg at the power density of (1)-1The energy storage device has good application potential.
Claims (6)
1. A preparation method of a high-stability aluminum-doped alpha-phase NiCo-LDHs electrode material is characterized by comprising the following steps:
step 1: dissolving a nickel source, a cobalt source and an aluminum source in a mixed solution of deionized water and ethanol according to a certain proportion to obtain a metal ion solution; simultaneously preparing a part of ammonium chloride solution and adding ammonia water to enable the ammonium chloride solution to have a pH buffering effect, and obtaining ammonia water/ammonium chloride solution; fully mixing the two solutions at normal temperature for complexing;
step 2: centrifugally collecting the complex obtained in the step 1, adding the complex into a prepared thiourea solution, performing ultrasonic dispersion, and then filling the solution into a hydrothermal kettle for hydrothermal reaction;
and step 3: collecting a product obtained by the reaction, centrifugally washing to remove redundant impurities, and drying to obtain a target product;
in the step 1, the nickel source, the cobalt source and the aluminum source are soluble salts; the nickel source is any one of nitrate and hydrate thereof, sulfate and hydrate thereof, chloride and hydrate thereof, the cobalt source is any one of nitrate and hydrate thereof, sulfate and hydrate thereof, chloride and hydrate thereof, and the aluminum source is any one of nitrate and hydrate thereof, sulfate and hydrate thereof, chloride and hydrate thereof; and the anions of the nickel source, the cobalt source and the aluminum source are the same;
in the step 1, the concentration of the ammonium chloride solution is 20-50 mmol.L-1(ii) a Adding 5-10 wt% of ammonia water into the ammonium chloride solution until the pH value of the solution is adjusted to 10-11;
in the step 2, the concentration of thiourea is 20-40 mmol.L-1The total molar amount of thiourea remains the same as the total molar amount of metal ions in step 1; the time of ultrasonic dispersion is 5-60 minutes.
2. The method of claim 1, wherein:
in the step 1, the total concentration of metal ions is 20-40 mmol.L-1，Al3+The concentration accounts for 0.1-15% of the total metal ion concentration, and the molar ratio of the nickel source to the cobalt source is (0.1-10): 1.
3. the method of claim 1, wherein:
in the step 1 and the step 2, the solvent used for preparing the solution is formed by mixing deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is (1-5): 1.
4. the method of claim 1, wherein:
in the step 2, the temperature of the hydrothermal reaction is 90-140 ℃, and the reaction time is 8-15 h.
5. The method of claim 1, wherein:
in the step 3, deionized water is adopted for alternate washing for multiple times; the drying process is carried out in a vacuum drier at normal temperature.
6. The use of the aluminum-doped α -phase NiCo-LDHs electrode material prepared by any one of the preparation methods of claims 1-5, wherein: the aluminum-doped alpha-phase NiCo-LDHs electrode material is used as a positive electrode material of a super capacitor.
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