CN113299492B - MOF-derived porous metal phosphide nanosheet array and application thereof - Google Patents
MOF-derived porous metal phosphide nanosheet array and application thereof Download PDFInfo
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Abstract
An MOF derived porous metal phosphide nanosheet array and application thereof, belonging to the technical field of MOF derivative supercapacitor materials. Using nickel chloride hexahydrate (NiCl)2·6H2O), terephthalic acid (PTA) and foam copper are subjected to reduction phosphorization under relatively mild conditions to prepare the electrode material with excellent supercapacitor performance, namely the in-situ grown carbon-coated Ni on the foam substrate2Porous nanoarrays of P (Ni)2P/C @ substrate). The material has good redox reversible performance.
Description
Technical Field
The invention relates to carbon-coated Ni based on in-situ growth on foam copper2P/Cu3P porous nanoarrays (Ni)2P/C@Cu3P-CF), belonging to the technical field of MOF derivative super capacitor materials.
Background
The economy of China is rapidly increased, and various industries of China gradually make outstanding contributions to the economic development. Under such a large background, China does not forget to be a responsible image of the large country, and continuously makes self contribution to the problems of global energy exhaustion, environmental protection and the like: the research and development of new energy sources are greatly promoted, the development of the technical research of the new energy sources is fully promoted, and the Chinese scheme is continuously provided for solving the energy problems of the country and all countries in the world.
In the field of energy storage, there are advantages and disadvantages in the selection of batteries and capacitors: the battery has the advantages of high energy density, strong persistence and the like, but also has the defects of long charging time and large energy loss; the capacitor has the problems of extremely high charge and discharge rate and strong instantaneous power intensity, but the capacitor is low in capacity and low in durability. To solve these problems, batteries are often used in combination with capacitors, with complementary advantages. Under the background, the appearance of the super capacitor with pseudo-capacitance performance provides a new solution for the problem, the pseudo-capacitance performance has the advantages of high charging rate of the capacitor and high power density of the battery, and a new idea is provided for solving the future energy storage problem of China and even the world.
In the field of pseudocapacitive supercapacitors, the requirements for such supercapacitors are that they should be compatible: the power density is large, the rate capability is good, the cycling stability is excellent, and meanwhile, in order to meet the application requirements under different conditions in the technical field, the material cost is required to be relatively low, and the corresponding technical method can have certain structural functions on different substrates, namely, the preparation method has the characteristic of universality.
The invention researches a method for growing a porous nanosheet array on the foam copper by using nickel phosphide and copper phosphide, and the application of the material in the super capacitor has the characteristics of high energy density, good rate capability, good stability and low cost. Meanwhile, the method has good universality, can grow on different substrates, and can meet the production requirements under different conditions.
Disclosure of Invention
Aiming at the research foundation of the current MOFs super capacitor, the invention provides a method for utilizing nickel chloride hexahydrate (NiCl)2·6H2O), terephthalic acid (PTA) and foamy copper are subjected to reduction phosphorization under relatively mild conditions to prepare electrode material with excellent supercapacitor performance, namely, in-situ grown carbon-coated Ni on foam substrate2Porous nanoarrays of P (Ni)2P/C @ substrate). The material has good redox reversible performance, and the technical scheme of the invention is realized by adopting the following mode.
Ni based on carbon coating2P/Cu3The preparation method of the supercapacitor electrode material with P growing on the foam copper in situ is characterized by comprising the following steps:
(1) foam copper pretreatment: cutting the foam copper into appropriate size (1 × 3 cm)2) By removing oilCleaning the surface with acetone solution as deoiling liquid, ultrasonic cleaning the foamy copper in an ultrasonic cleaning machine at room temperature for 30min, and washing off surface lipid; in order to remove the copper oxide on the surface layer of the copper foam, active sites need to be added, and then the copper foam is transferred into an acid solution (2M HCl) for ultrasonic cleaning for 15min, and then the copper foam is cleaned with a large amount of deionized water for several times and dried in a vacuum drying oven for standby.
(2) In-situ growth of Ni-MOF @ CF precursors: 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) are added into a conical flask, 40ml of N, N-Dimethylformamide (DMF) is added into magnetons, and the mixture is stirred for 30min on a magnetic stirrer; slowly adding 2ml deionized water dropwise while stirring with burette, transferring to 1 × 3cm after the above treatment2And (3) adding the foamy copper in the vacuum drying oven into a 100ml hydrothermal kettle, then adding the foamy copper into the hydrothermal kettle, transferring the hydrothermal kettle into an electric air drying oven after soaking, gradually heating to 120 ℃, keeping the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, then adding into methanol, ultrasonically cleaning for 30s, taking out the material, and storing in a vacuum 80 ℃ drying oven for later use. And preparing light green uniform flaky Ni-MOF @ CF.
(3) Reduction phosphating
And putting the Ni-MOF @ CF into a tubular furnace, setting a temperature rise program of 5 ℃/min to be heated to 400 ℃, keeping the temperature for 120min in a hydrogen argon atmosphere, naturally cooling to room temperature, and taking out a sample. Subjecting the sample to CVD (chemical vapor deposition) to remove NaH2PO3150mg is placed at the upstream of a porcelain ark, the porcelain ark is placed in a tube furnace and is heated and insulated under the condition that nitrogen is used as protective gas and the gas flow rate is 50ml/min, the heating procedure is 2 ℃/min to 300 ℃, the insulation is carried out for 60min, the porcelain ark is naturally cooled to the room temperature and then taken out, and then Ni is obtained2P/C@Cu3The P-CF preparation is complete.
The foam copper can be replaced by foam nickel and carbon cloth, and finally the MOF derived porous single metal nickel phosphide nanosheet array is obtained, namely the final product is Ni2P/C @ foamed nickel, Ni2P/C @ carbon cloth.
The invention relates to an MOF (Metal organic framework) derived porous metal phosphide nanosheet array junctionForm Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2The application of the P/C @ carbon cloth as an electrode material of a super capacitor.
The material obtained by the invention has excellent redox reversible performance and hydrophilicity, especially Ni2P/C@Cu3The P-CF also has the advantages of large capacity, good rate capability and good cycle stability as a capacitive material.
Drawings
FIG. 1 Ni-loaded material prepared in example 1 of the present invention2P/C@Cu3XRD pattern of P-CF nanoarrays.
FIG. 2 Ni prepared according to example 1 of the present invention2P/C@Cu3SEM images at different magnifications of P-CF nanoarrays.
FIG. 3 Ni prepared according to example 1 of the present invention2P/C@Cu3CV plots for P-CF nanoarrays at different sweep rates.
FIG. 4 Ni prepared according to example 1 of the present invention2P/C@Cu3GCD plots of P-CF nanoarrays at different sweep rates.
FIG. 5 Ni prepared according to example 1 of the present invention2P/C@Cu320mAcm of P-CF nano array2Capacity fade graph at rate of charge and discharge.
FIG. 6 Ni prepared according to example 2 of the present invention2P/C@Cu3Contact angle test pattern of P-CF nano array.
FIG. 7 is a magnified experimental image of a Ni-MOF @ CF nanoarray prepared in example 3 of the present invention.
FIG. 8 is an SEM micrograph of Ni-MOF @ NiF nanosheet arrays and Ni-MOF @ CC nanosheet arrays prepared in example 4 of the present invention.
Detailed Description
The essential features and the significant advantages of the invention will be further elucidated below, without being limited thereto, with reference to the accompanying drawings and the specific embodiments.
Example 1
(1) Cutting the foam copper into appropriate size (1 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min to remove surface fatAnd (4) quality. In order to wash away impurities such as copper foam surface oxide after deoiling, it is necessary to transfer it into an acid solution (2)MHCl), simultaneously adding active sites of the foamy copper, then ultrasonically cleaning for 15min at room temperature to remove copper oxide on the surface layer, taking out, cleaning with a large amount of deionized water for several times, and drying in a vacuum drying oven for later use.
(2) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to an Erlenmeyer flask, after which 40ml of N, N-Dimethylformamide (DMF) was added to the magnetons and stirred on a magnetic stirrer for 30 min. Slowly dropwise adding 2ml deionized water into a burette while stirring, transferring the deionized water into a 100ml hydrothermal kettle, then adding the foamy copper into the vacuum drying oven into the hydrothermal kettle, and transferring the hydrothermal kettle into an electric air blowing drying oven after soaking. And (3) gradually heating the sample to 120 ℃ in an electric air drying box, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, performing ultrasonic treatment for 30s, taking out the material to obtain the light green uniform flaky Ni-MOF @ CF, and storing the Ni-MOF @ CF in a vacuum drying box at 80 ℃ for later use.
(3) Putting the Ni-MOF @ CF into a tube furnace in a hydrogen argon atmosphere, heating to 400 ℃ at a temperature of 5 ℃/min, keeping the temperature for 120min, naturally cooling to room temperature, taking out a sample, and carrying out NaH (chemical vapor deposition) by using CVD (chemical vapor deposition)2PO3150mg was placed upstream of the porcelain ark in a tube furnace. Heating at nitrogen flow rate of 50ml/min, setting the temperature at 2 deg.C/min to 300 deg.C, and maintaining for 60 min. Naturally cooling to room temperature, and taking out the sample, namely Ni2P/C@Cu3The P-CF preparation is complete.
(4) To Ni2P/C@Cu3XRD measurement of P-CF nanosheet array referring specifically to FIG. 1, the above-mentioned Ni is2P/C@Cu3P-CF nano sheet array used as working electrode in three-electrode system (counter electrode: graphite electrode, reference electrode: mercury oxide electrode) (1)MPotassium hydroxide)). In the voltage range of 0-0.6V, the material is tested to have the advantages of large capacity, good multiplying power performance and good cycling stability through cyclic sweep voltammetry (CV) at different sweep rates, constant current charge-discharge curve (GCD) curves at different current densities and 5000 times of constant current charge-discharge curves, and has the advantages of high capacity, good multiplying power performance and good cycling stabilitySee fig. 2, fig. 3, fig. 4 and fig. 5. Thus, Ni having excellent electrochemical properties was obtained2P/C@Cu3An array of P-CF nanosheets.
Example 2
(1) Cutting the foam copper into proper size (1 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min, and washing off surface lipid. In order to wash away impurities such as copper foam surface oxide after deoiling, it is necessary to transfer it into an acid solution (2)MHCl), simultaneously adding active sites of the foamy copper, then ultrasonically cleaning for 15min at room temperature to remove copper oxide on the surface layer, taking out, cleaning with a large amount of deionized water for several times, and drying in a vacuum drying oven for later use.
(2) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to a flask, 40ml of N, N-Dimethylformamide (DMF) was added to the flask and stirred on a magnetic stirrer for 30 min. Slowly dropwise adding 2ml deionized water into a burette while stirring, transferring the deionized water into a 100ml hydrothermal kettle, then adding the foamy copper into the vacuum drying oven into the hydrothermal kettle, and transferring the hydrothermal kettle into an electric air blowing drying oven after soaking. And (3) gradually heating the sample to 120 ℃ in an electric air drying box, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, ultrasonically cleaning for 30s, taking out the material to obtain the light green uniform flaky Ni-MOF @ CF, and storing the Ni-MOF @ CF in a vacuum drying box at 80 ℃ for later use.
(3) Putting the Ni-MOF @ CF into a tube furnace, heating to 400 ℃ at a temperature of 5 ℃/min, keeping the temperature for 120min, naturally cooling to room temperature, taking out a sample, and using a Chemical Vapor Deposition (CVD) method to carry out NaH2PO3150mg was placed upstream of the porcelain ark in a tube furnace. Heating at nitrogen flow rate of 50ml/min, setting the temperature at 2 deg.C/min to 300 deg.C, and maintaining for 60 min. Naturally cooling to room temperature, and taking out the sample, namely Ni2P/C@Cu3The P-CF preparation is complete.
(4) Mixing Ni2P/C@Cu3Placing the P-CF nanosheet on a glass slide of a contact angle measuring instrument, sucking deionized water by using a superfine needle tube and dropping liquid drops at the momentThe process of dropping and disappearing the droplets was performed using a continuous recording camera. After shooting, the liquid drops are contacted with the thin sheet, and a picture of an absorption process is taken out, so that the ultrathin nanosheet is found to have extremely strong water absorption, and the liquid drops are absorbed within three thousandth of a second. While the contact angle is shown in figure 6.
Example 3
(1) Cutting the foam copper into 4 times (4 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min, and washing off surface lipid. In order to wash away impurities such as copper foam surface oxide after deoiling, it is necessary to transfer it into an acid solution (2)MHCl), and then ultrasonic cleaning is carried out for 15min at room temperature to remove copper oxide on the surface layer, and after being taken out, the copper oxide is cleaned by a large amount of deionized water for a plurality of times and dried in a vacuum drying oven for standby.
(2) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to a flask, 40ml of N, N-Dimethylformamide (DMF) was added to the flask and stirred on a magnetic stirrer for 30 min. Slowly dropwise adding 2ml deionized water into a burette while stirring, transferring the deionized water into a 100ml hydrothermal kettle, then adding the foamy copper into the vacuum drying oven into the hydrothermal kettle, and transferring the hydrothermal kettle into an electric air blowing drying oven after soaking. And (3) gradually heating the sample to 120 ℃ in an electric air drying box, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, ultrasonically cleaning for 30s, taking out the material to obtain the uniform light green flaky Ni-MOF @ CF, and storing the uniform light green flaky Ni-MOF @ CF in a vacuum drying box at 80 ℃ for later use.
(3) The appearance of a nanosheet array of Ni-MOF @ CF is observed, and the growth condition and the 1-fold size (1 x 3 cm) of the nanosheet array are found2) The flaky growth conditions are the same, and the presented light green color is basically consistent, so that the amplified experiment can be performed. As shown in fig. 7.
Example 4
(1) Cutting foamed nickel into proper size (1 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min, and washing off the surface layerA lipid. In order to wash off impurities such as deoiled foam nickel surface oxide, the impurities need to be transferred into an acid solution (2M HCl), active sites of the foam nickel are added at the same time, ultrasonic cleaning is carried out at room temperature for 15min to remove nickel oxide on the surface layer, and after the impurities are taken out, a large amount of deionized water is used for cleaning for several times and drying is carried out in a vacuum drying oven for standby.
(2) Cutting the carbon cloth into appropriate size (1 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min, and washing off surface lipid. In order to wash off impurities such as deoiled foamy copper surface oxides, the impurities need to be transferred into an acid solution (2M HCl), active sites of foamy copper are added at the same time, ultrasonic cleaning is carried out at room temperature for 15min to remove copper oxide on the surface layer, and after the impurities are taken out, a large amount of deionized water is used for cleaning for several times and drying is carried out in a vacuum drying oven for later use.
(3) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to a flask, 40ml of N, N-Dimethylformamide (DMF) was added to the flask and stirred on a magnetic stirrer for 30 min. Slowly dripping 2ml deionized water by using a burette while stirring, transferring the deionized water into a 100ml hydrothermal kettle, and then adding the foamed nickel in the vacuum drying oven into the hydrothermal kettle for soaking. After soaking, the hydrothermal kettle is transferred to an electric air blowing drying box. And (3) gradually heating the sample to 120 ℃ in an electric air drying box, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, ultrasonically cleaning for 30s, taking out the material to obtain light green flaky Ni-MOF @ NiF, and storing the Ni-MOF @ NiF in a vacuum drying box at 80 ℃ for later use.
(4) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to a flask, 40ml of N, N-Dimethylformamide (DMF) was added to the flask and stirred on a magnetic stirrer for 30 min. Slowly dripping 2ml deionized water into the hydrothermal kettle of 100ml by using a burette while stirring, and then adding the carbon cloth in the vacuum drying oven into the hydrothermal kettle for soaking. After soaking, the hydrothermal kettle is transferred to an electric air blowing drying box. Gradually heating the sample to 120 ℃ in an electric air blowing drying box, preserving the temperature for 180min, and naturally cooling to room temperatureAnd taking out the prepared material, slowly washing the material with DMF, adding the material into methanol, ultrasonically washing the material for 30s, taking out the material as light green flaky Ni-MOF @ CC, and storing the material in a vacuum drying oven at 80 ℃ for later use.
(5) The SEM images of the Ni-MOF @ NiF nanosheet array and the Ni-MOF @ CC nanosheet array are determined, and particularly, as shown in FIG. 8, the growth condition is good, and the method can be used for growth of other types of substrates, namely has universality. Then further carbonizing and phosphorizing.
Claims (4)
1. Ni based on carbon coating2P/Cu3The preparation method of the supercapacitor electrode material with P growing on the foam copper in situ is characterized by comprising the following steps:
(1) foam copper pretreatment: cutting the foamy copper into a proper size, cleaning the surface by using degreasing liquid, wherein the degreasing liquid is an acetone solution, ultrasonically cleaning the foamy copper in an ultrasonic cleaning machine for 30min at room temperature, and washing away surface lipid; in order to remove copper oxide on the surface layer of the foamy copper and increase active sites, the foamy copper needs to be transferred into an acid solution for ultrasonic cleaning for 15min, then is cleaned with ionized water for several times and is dried in a vacuum drying oven for standby;
(2) in-situ growth of Ni-MOF @ CF precursors: 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) are added into a conical flask, 40ml of N, N-Dimethylformamide (DMF) is added into magnetons, and the mixture is stirred for 30min on a magnetic stirrer; slowly adding 2ml of deionized water while stirring by using a burette, transferring the mixed solution in the conical flask to a position 1 × 3cm away from the conical flask after the treatment2Soaking a 100ml hydrothermal kettle of the foamy copper, transferring the hydrothermal kettle into an electric air drying box, gradually heating to 120 ℃, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, ultrasonically cleaning for 30s, taking out the material, and storing in a vacuum drying box at 80 ℃ for later use; preparing light green uniform flaky Ni-MOF @ CF;
(3) reduction phosphating
Putting the Ni-MOF @ CF into a tube furnace, setting a temperature rise program of 5 ℃/min to 400 ℃, and heating in hydrogenKeeping the temperature for 120min under argon atmosphere, naturally cooling to room temperature, and taking out a sample; using a CVD process, reacting NaH with a hydrogen peroxide2PO3150mg is placed at the upstream of a porcelain ark, the porcelain ark is placed in a tube furnace and is heated and insulated under the condition that nitrogen is used as protective gas and the gas flow rate is 50ml/min, the heating procedure is 2 ℃/min to 300 ℃, the insulation is carried out for 60min, the porcelain ark is naturally cooled to the room temperature and then taken out, and then Ni is obtained2P/C@Cu3The P-CF preparation is complete.
2. A preparation method of an MOF-derived porous metal phosphide nanosheet array structure material is characterized in that the foamed copper in claim 1 is replaced by foamed nickel and carbon cloth, and an MOF-derived porous single-metal nickel phosphide nanosheet array is finally obtained, namely the final product is Ni2P/C @ foamed nickel, Ni2P/C @ carbon cloth.
3. MOF-derived porous metal phosphide nanosheet array structure Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2P/C @ carbon cloth, said Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2The P/C @ carbon cloth is prepared according to the process of claim 1 or 2.
4. MOF-derived porous metal phosphide nanosheet array structure Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2Application of P/C @ carbon cloth as super capacitor electrode material, and Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2The P/C @ carbon cloth is prepared according to the process of claim 1 or 2.
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| CN104979556A (en) * | 2015-05-15 | 2015-10-14 | 三峡大学 | Nitrogen-doped Cu3P/C-Cu lithium-ion battery negative electrode material and preparation method thereof |
| CN107317008A (en) * | 2017-06-20 | 2017-11-03 | 大连理工常州研究院有限公司 | The preparation method and application of core-shell type carbon-clad metal phosphide nano-complex particle |
| CN108823598A (en) * | 2018-06-05 | 2018-11-16 | 青岛科技大学 | A kind of Ag modification porous structure Cu3P/ foam copper combination electrode and preparation method thereof |
| CN112791736A (en) * | 2019-11-14 | 2021-05-14 | 天津理工大学 | WP2/Cu3Application of P composite nano-structure catalyst in aspect of hydrogen production by electrolyzing water |
| CN110980673A (en) * | 2019-12-25 | 2020-04-10 | 湖北大学 | Metal phosphide, preparation method thereof and application thereof in super capacitor |
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