CN110040705B - Method for preparing phosphorus-rich phase copper phosphide hollow nanospheres - Google Patents
Method for preparing phosphorus-rich phase copper phosphide hollow nanospheres Download PDFInfo
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- CN110040705B CN110040705B CN201910343200.XA CN201910343200A CN110040705B CN 110040705 B CN110040705 B CN 110040705B CN 201910343200 A CN201910343200 A CN 201910343200A CN 110040705 B CN110040705 B CN 110040705B
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
A method for preparing phosphorus-rich phase copper phosphide hollow nanospheres. Stirring and adding Cu (CH)3COO)2·H2Dissolving O in ethanol solution, adding pyrrole and stirring to form dark blue solution A; placing the solution A in a reaction kettle for solvothermal reaction, washing a product with absolute ethyl alcohol after the reaction is finished, and then drying in a freeze drying oven to obtain a precursor; and (3) placing the precursor in a small porcelain boat, placing red phosphorus in a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, covering and sealing, and then carrying out a phosphating reaction in a vacuum tube furnace, wherein after the reaction is finished, the powder in the small porcelain boat is the phosphorus-rich phase copper phosphide hollow nanosphere. The prepared phosphorus-rich phase copper phosphide hollow nanospheres can be used as a lithium ion battery or sodium ion battery cathode material and an electrocatalytic electrode material. The invention adopts the phosphorization reaction that phosphorus diffuses from the surface to the inside, the oxide precursor also diffuses from the inside to the outside, and the solid sphere is converted into the hollow sphere under the simultaneous action of the two processes.
Description
Technical Field
The invention relates to the field of nano materials and electrochemistry, in particular to a method for preparing phosphorus-rich phase copper phosphide hollow nanospheres.
Background
The transition metal phosphide has wide application in the fields of magnetics, optics, energy storage and the like. The P-P is directly bonded to form multi-phosphide anions, and transition metal phosphide has phases with different phosphorus contents such as metal-rich and phosphorus-rich phases. Among the numerous phosphides, the phosphorus-rich phase copper phosphide (CuP)2) Is a potential material for lithium/sodium ion batteries, and the theoretical specific capacity of the material is as high as 1281mAh g-1Has attractive application prospect. However, as with other electrode materials using a conversion reaction as a mechanism, the material has a huge volume change in the process of storing lithium/sodium, and the hollow structure can effectively relieve the volume change effect of the electrode material and improve the cycle stability of the electrode material.
Due to the higher thermodynamic conditions required for the nucleation and growth of phosphorus-rich phase copper phosphideCurrently, CuP is prepared2The method of (A) is chemical vapor deposition [ Kloc C, Lux-Steiner M C, Keil M, et al growth and catalysis of CuP2single crystals[J].Journal of Crystal Growth,1990,106(4):635-642.]. Ball milling method [ Kim S O, Manthiram A. phosphorous-Rich CuP2Embedded in Carbon Matrix as a High-Performance Anode for Lithium-Ion Batteries[J].ACS Applied Materials&Interfaces,2017,9(19):16221.]And [ Matsumoto K, Kaushik S, Hwang J, et al. high RateCapacity and cycling of CuP2/C Composite Negative Electrode for SodiumSecondary Battery Operating at Room to Intermediate Temperatures Using IonicLiquid[J].ChemElectroChem,2018.]. However, both methods cannot regulate the morphology of the copper phosphide, have high energy consumption and are easy to introduce other heterogeneous substances. Preparing copper phosphide nano-wires [ Li G A, Wang C Y, Chang W C, et al, phosphorus-Rich copper phosphide Nanowires for Field-Effect Transistors and Lithium-Ion Batteries ] by supercritical fluid solid-liquid growth method under high temperature and high pressure conditions].Acs Nano,1936,10(9):8632.]And preparing carbon-coated CuP by thermal decomposition and phosphorization method2Complex [ Shuangqiang C, Feixiang W, Laifa S, et al2Nanocomposites for High Energy Density Sodium Ion Batteries[J].ACS Nano,2018,12(7)7018-7027]And electrochemical deposition [ Chandrasekar M S, Mitra S. Thincopper phosphor films as conversion anode for lithium-ion batteries [ J].Electrochimica Acta,2013,92(1):47–54.]And preparing the copper phosphide film.
Disclosure of Invention
The invention aims to provide the method for preparing the phosphorus-rich phase copper phosphide hollow nanospheres, which has the advantages of simple process, easiness in control and operation, no need of complex equipment, good safety and stability, green and environment-friendly process and easiness in industrial scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
1) stirring and adding Cu (CH)3COO)2·H2Dissolving O in ethanol solution to obtain Cu (CH)3COO)2·H2Cu (CH) with O concentration of 0.5-3 mol/L3COO)2·H2O ethanol solution, then adding Cu (CH) thereto3COO)2·H20.5-5 per mill of pyrrole in volume of O ethanol solution is stirred to form dark blue solution A;
2) placing the solution A in a reaction kettle for solvothermal reaction at 180-200 ℃, washing a product with absolute ethyl alcohol after the reaction is finished, and drying in a freeze drying oven to obtain a precursor;
3) according to the proportion that the precursor and red phosphorus are 1: and (3) placing the precursor in a small porcelain boat at a molar ratio of 1-5, placing red phosphorus in a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, covering and sealing, and then carrying out a phosphorization reaction at 400-800 ℃ in a vacuum tube furnace, wherein after the reaction is finished, the powder in the small porcelain boat is the phosphorus-phase copper phosphide hollow nanosphere.
The step 1) adopts magnetic stirring.
The filling ratio of the solution A in the step 2) in the reaction kettle is 70-80%.
The reaction kettle in the step 2) is a stainless steel reaction kettle with a polytetrafluoroethylene lining.
The small porcelain boat in the step 3) is 3 × 6cm, and the large porcelain boat is 5 × 12 cm.
The vacuum degree in the step 3) is-0.1 Mpa.
And the phosphating reaction time of the step 3) is 1-4 h.
The prepared phosphorus-rich phase copper phosphide hollow nanospheres can be used as a lithium ion battery or sodium ion battery cathode material and an electrocatalytic electrode material.
Compared with the prior art, the invention has the following beneficial technical effects:
1) the invention adopts a solvothermal method, takes ethanol as a solvent, uses pyrrole as a reducing agent and a morphology control agent, and controls the nucleation growth process of the product to form a spherical morphology formed by nano-particles.
2) After the spherical copper oxide precursor is prepared in a green and efficient manner, the phosphorization is carried out at low temperature for a short time, and in the process, red phosphorus is sublimated to form active gaseous phosphorus. The copper oxide precursor reacts with the solid copper oxide precursor in a dense-seam porcelain boat through a gas phase transport process, and the precursor is converted into copper phosphide while the shape of the precursor is kept from inside to outside.
3) More importantly, in the process, while red phosphorus diffuses from the surface to the inside, the oxide precursor also diffuses from the inside to the outside, and under the simultaneous action of the two processes, the solid sphere is converted into the hollow sphere.
4) The equipment and the instrument of the invention have simpler requirements and can more effectively prepare the phosphorus-rich phase copper phosphide with better crystallinity, smaller particle size, uniform distribution and high purity.
5) The method has the advantages of simple process, easy control and operation, good safety and stability, and easy realization of industrial mass production. The preparation technology is simple, complex equipment is not needed, and the process is green and environment-friendly.
Drawings
FIG. 1 is an XRD pattern of phosphorus-rich phase copper phosphide hollow nanospheres prepared in example 5 of the present invention;
fig. 2 is an SEM image of phosphorus-rich phase copper phosphide hollow nanospheres prepared in example 5 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1:
1) stirring Cu (CH) under magnetic force3COO)2·H2Dissolving O in ethanol solution to obtain Cu (CH)3COO)2·H2Cu (CH) with O concentration of 0.5mol/L3COO)2·H2O ethanol solution, then adding Cu (CH) thereto3COO)2·H20.5 per mill of pyrrole in volume of O ethanol solution is stirred to form dark blue solution A;
2) putting the solution A into a stainless steel reaction kettle with a polytetrafluoroethylene lining according to the filling ratio of 70 percent, carrying out solvothermal reaction at 200 ℃, washing a product with absolute ethyl alcohol after the reaction is finished, and then drying in a freeze drying oven to obtain a precursor;
3) according to the proportion that the precursor and red phosphorus are 1: the precursor is placed in a small porcelain boat of 3 x 6cm at a molar ratio of 1, red phosphorus is placed in a large porcelain boat of 5 x 12cm, the small porcelain boat is sleeved in the large porcelain boat, the small porcelain boat is covered and sealed, then the phosphorization reaction is carried out for 1h at 400 ℃ in a tubular furnace with the vacuum degree of-0.1 Mpa, and after the reaction is finished, the powder in the small porcelain boat is the phosphorized copper hollow nanosphere.
Example 2:
1) stirring Cu (CH) under magnetic force3COO)2·H2Dissolving O in ethanol solution to obtain Cu (CH)3COO)2·H2Cu (CH) with O concentration of 1mol/L3COO)2·H2O ethanol solution, then adding Cu (CH) thereto3COO)2·H 22 per mill of pyrrole in volume of O ethanol solution is stirred to form a dark blue solution A;
2) placing the solution A in a stainless steel reaction kettle with a polytetrafluoroethylene lining according to a filling ratio of 75% for solvothermal reaction at 190 ℃, washing a product with absolute ethyl alcohol after the reaction is finished, and drying in a freeze drying oven to obtain a precursor;
3) according to the proportion that the precursor and red phosphorus are 1: 2, placing the precursor in a small porcelain boat of 3 x 6cm, placing red phosphorus in a large porcelain boat of 5 x 12cm, sleeving the small porcelain boat into the large porcelain boat, covering and sealing, and carrying out a phosphorization reaction for 2 hours at 500 ℃ in a tubular furnace with the vacuum degree of-0.1 Mpa, wherein after the reaction is finished, the powder in the small porcelain boat is the phosphorized copper hollow nanosphere.
Example 3:
1) stirring Cu (CH) under magnetic force3COO)2·H2Dissolving O in ethanol solution to obtain Cu (CH)3COO)2·H2Cu (CH) with O concentration of 2mol/L3COO)2·H2O ethanol solution, then adding Cu (CH) thereto3COO)2·H2O, pyrrole with the volume of 3 per mill of the ethanol solution is stirred to form a dark blue solution A;
2) placing the solution A in a stainless steel reaction kettle with a polytetrafluoroethylene lining according to the filling ratio of 80% for solvothermal reaction at 180 ℃, washing a product with absolute ethyl alcohol after the reaction is finished, and drying in a freeze drying oven to obtain a precursor;
3) according to the proportion that the precursor and red phosphorus are 1: and (3) placing the precursor in a small porcelain boat of 3 x 6cm in a molar ratio of 4, placing red phosphorus in a large porcelain boat of 5 x 12cm, sleeving the small porcelain boat into the large porcelain boat, covering and sealing, carrying out phosphating reaction for 4 hours at 800 ℃ in a tubular furnace with the vacuum degree of-0.1 Mpa, and obtaining the powder in the small porcelain boat, namely the phosphorus-phase copper phosphide hollow nanospheres after the reaction is finished.
Example 4:
1) stirring Cu (CH) under magnetic force3COO)2·H2Dissolving O in ethanol solution to obtain Cu (CH)3COO)2·H2Cu (CH) with O concentration of 3mol/L3COO)2·H2O ethanol solution, then adding Cu (CH) thereto3COO)2·H2Pyrrole with the volume of 5 per mill of the ethanol solution O is stirred to form a dark blue solution A;
2) putting the solution A into a stainless steel reaction kettle with a polytetrafluoroethylene lining according to the filling ratio of 78 percent, carrying out solvothermal reaction at 180 ℃, washing a product with absolute ethyl alcohol after the reaction is finished, and drying in a freeze drying oven to obtain a precursor;
3) according to the proportion that the precursor and red phosphorus are 1: and 3, placing the precursor in a small porcelain boat of 3 x 6cm in a molar ratio, placing red phosphorus in a large porcelain boat of 5 x 12cm, sleeving the small porcelain boat into the large porcelain boat, covering and sealing, carrying out a phosphorization reaction for 3 hours at 600 ℃ in a tubular furnace with the vacuum degree of-0.1 Mpa, and obtaining the powder in the small porcelain boat, namely the phosphorized copper hollow nanospheres after the reaction is finished.
Example 5:
1) stirring Cu (CH) under magnetic force3COO)2·H2Dissolving O in ethanol solution to obtain Cu (CH)3COO)2·H2Cu (CH) with O concentration of 1mol/L3COO)2·H2O ethanol solution, then adding Cu (CH) thereto3COO)2·H2Pyrrole with the volume of 5 per mill of the ethanol solution O is stirred to form a dark blue solution A;
2) putting the solution A into a stainless steel reaction kettle with a polytetrafluoroethylene lining according to the filling ratio of 70 percent, carrying out solvothermal reaction at 180 ℃, washing a product with absolute ethyl alcohol after the reaction is finished, and then drying in a freeze drying oven to obtain a precursor;
3) according to the proportion that the precursor and red phosphorus are 1: and (2) placing the precursor in a small porcelain boat of 3 x 6cm in a molar ratio of 5, placing red phosphorus in a large porcelain boat of 5 x 12cm, sleeving the small porcelain boat into the large porcelain boat, covering and sealing, carrying out phosphating reaction for 3 hours at 500 ℃ in a tubular furnace with the vacuum degree of-0.1 Mpa, and obtaining the powder in the small porcelain boat, namely the phosphorus-phase copper phosphide hollow nanospheres after the reaction is finished.
As can be seen from FIG. 1, the diffraction peak of the prepared material well conforms to the standard card 76-1190, and the corresponding phase is CuP2The diffraction peak has sharp peak shape and good crystallinity.
As can be seen from FIG. 2, the prepared CuP2The material is in a nanometer spherical shape, the diameter of the nanometer sphere is about 150-180nm, and the inside of the material is hollow as seen from the cracked nanometer sphere. In addition, a small amount of nanowires is present.
Example 6:
1) stirring Cu (CH) under magnetic force3COO)2·H2Dissolving O in ethanol solution to obtain Cu (CH)3COO)2·H2Cu (CH) with O concentration of 1mol/L3COO)2·H2O ethanol solution, then adding Cu (CH) thereto3COO)2·H2Pyrrole with the volume of 1 per mill of the ethanol solution O is stirred to form a dark blue solution A;
2) putting the solution A into a stainless steel reaction kettle with a polytetrafluoroethylene lining according to the filling ratio of 70 percent, carrying out solvothermal reaction at 200 ℃, washing a product with absolute ethyl alcohol after the reaction is finished, and then drying in a freeze drying oven to obtain a precursor;
3) according to the proportion that the precursor and red phosphorus are 1: and (3) placing the precursor in a small porcelain boat of 3 x 6cm in a molar ratio of 5, placing red phosphorus in a large porcelain boat of 5 x 12cm, sleeving the small porcelain boat into the large porcelain boat, covering and sealing, carrying out a phosphorization reaction for 4 hours at 400 ℃ in a tubular furnace with a vacuum degree of-0.1 Mpa, and obtaining the powder in the small porcelain boat, namely the phosphorized copper hollow nanospheres after the reaction is finished.
Claims (7)
1. A method for preparing phosphorus-rich phase copper phosphide hollow nanospheres is characterized by comprising the following steps:
1) stirring and adding Cu (CH)3COO)2·H2Dissolving O in ethanol solution to obtainCu(CH3COO)2·H2Cu (CH) with O concentration of 0.5-3 mol/L3COO)2·H2O ethanol solution, then adding Cu (CH) thereto3COO)2·H20.5-5 per mill of pyrrole in volume of O ethanol solution is stirred to form dark blue solution A;
2) placing the solution A in a reaction kettle for solvothermal reaction at 180-200 ℃, washing a product with absolute ethyl alcohol after the reaction is finished, and drying in a freeze drying oven to obtain a precursor;
3) according to the proportion that the precursor and red phosphorus are 1: and (3) placing the precursor in a small porcelain boat at a molar ratio of 1-5, placing red phosphorus in a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, covering and sealing, and then carrying out a phosphorization reaction at 400-800 ℃ in a vacuum tube furnace, wherein after the reaction is finished, the powder in the small porcelain boat is the phosphorus-rich phase copper phosphide hollow nanosphere.
2. The method for preparing phosphorus-rich phase copper phosphide hollow nanospheres according to claim 1, wherein: the step 1) adopts magnetic stirring.
3. The method for preparing phosphorus-rich phase copper phosphide hollow nanospheres according to claim 1, wherein: the filling ratio of the solution A in the step 2) in the reaction kettle is 70-80%.
4. The method for preparing phosphorus-rich phase copper phosphide hollow nanospheres according to claim 1, wherein: the reaction kettle in the step 2) is a stainless steel reaction kettle with a polytetrafluoroethylene lining.
5. The method for preparing phosphorus-rich phase copper phosphide hollow nanospheres according to claim 1, wherein: the small porcelain boat in the step 3) is 3 multiplied by 6cm, and the large porcelain boat is 5 multiplied by 12 cm.
6. The method for preparing phosphorus-rich phase copper phosphide hollow nanospheres according to claim 1, wherein: the vacuum degree in the step 3) is-0.1 MPa.
7. The method for preparing phosphorus-rich phase copper phosphide hollow nanospheres according to claim 1, wherein: and the phosphating reaction time of the step 3) is 1-4 h.
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| CN106861729A (en) * | 2017-01-13 | 2017-06-20 | 天津大学 | A kind of hollow sea urchin shape phosphide material and preparation method |
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