CN110517896B - Nitrogen-doped nickel-cobalt bimetallic phosphide material and preparation method thereof - Google Patents
Nitrogen-doped nickel-cobalt bimetallic phosphide material and preparation method thereof Download PDFInfo
- Publication number
- CN110517896B CN110517896B CN201910712412.0A CN201910712412A CN110517896B CN 110517896 B CN110517896 B CN 110517896B CN 201910712412 A CN201910712412 A CN 201910712412A CN 110517896 B CN110517896 B CN 110517896B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nickel
- nitrogen
- solution
- doped nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 15
- 150000004692 metal hydroxides Chemical class 0.000 claims description 15
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 12
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 230000001965 increasing effect Effects 0.000 claims description 7
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 6
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 6
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 nickel phosphide compound Chemical class 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
- C01B25/088—Other phosphides containing plural metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a nitrogen-doped nickel-cobalt bimetallic phosphide material and a preparation method thereof. The nitrogen-doped nickel-cobalt bimetal phosphide is used for etching Cu by a template method by utilizing a soft-hard acid-base theory2The material has the characteristics of large specific surface area, good conductivity and stable structure, can be used as a super capacitor electrode material, shows extremely high specific capacity and has good rate capability.
Description
Technical Field
The invention relates to a nitrogen-doped nickel-cobalt bimetallic phosphide material and a preparation method thereof, belonging to the field of nano material preparation.
Background
With the increasing activity and global consumption of humans, humans have been facing increasingly severe energy crisis. Meanwhile, the continuous burning of fossil fuels by human activities has caused serious environmental pollution and destruction of the ecological environment of the earth, and thus scientists are actively striving to find and develop unconventional energy sources such as nuclear energy, solar energy, wind energy, hydrogen energy, hydraulic energy, and the like. To make good use of these new sources of energy, it is often necessary to use some form of energy that is stored and then released when needed. As a novel economic and efficient energy storage device, the super capacitor has the advantages of high power density, long cycle life, high charging and discharging speed, low maintenance cost and the like, and has wide application prospect.
At present, the main factor restricting the development of the super capacitor is the electrode material, and the specific capacitance of the electrode material can be improved by a doping atom modification method. Zhang, X et al synthesized two-dimensional Ni-Co bimetallic phosphide nanosheets by three-step method [ Zhang, Xiaoming, et al. "Porous NiCoP nanosheets as effective and stable Porous electronic for advanced asymmetric composites superparameters." Journal of Materials Chemistry A6.37 (2018):17905 and 17914 ]. Jin, Yuhong et al synthesized Mesoporous nickel cobalt bimetallic phosphide microspororice [ Jin, Yuhong, et al, "meso pore NiCoP microflowers as a super electrode material for supercapacitors," Applied Surface Science 450(2018): 170-. The electrode material of the super capacitor prepared by the method is too large in size and too small in specific surface area, so that the specific capacitance is lower. Therefore, an electrode material with simple operation and good performance needs to be researched.
Disclosure of Invention
The invention aims to provide a nitrogen-doped nickel-cobalt double-metal phosphide material and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
nitrogen-doped nickel-cobalt bimetallic phosphide material in Cu2After the nickel-cobalt double hydroxide is obtained by taking O as a template, simultaneously carrying out phosphorization and nitrogen doping in one step to obtain nitrogen-doped nickel-cobalt double metal phosphide; the material is in a nano hollow cubic structure.
A preparation method of nitrogen-doped nickel-cobalt bimetallic phosphide comprises the following steps:
in the first step, at 0.01mol L-1Adding dropwise copper chloride dihydrate solution into sodium hydroxide solution, stirring in a constant temperature water bath at 55 deg.C for 30min, adding dropwise ascorbic acid solution, and stirring in a constant temperature water bath at 55 deg.C for 3 hr.
Step two, the precipitate obtained in the step one is dried after being centrifugally washed to prepare Cu2O powder;
third step, Cu obtained in the second step2Ultrasonically dispersing O powder into a mixed solution of deionized water and ethanol, adding polyvinylpyrrolidone K30, nickel chloride hexahydrate and cobalt chloride hexahydrate, and magnetically stirring at room temperature for 30 min;
fourthly, dripping a sodium thiosulfate solution into the mixed solution obtained in the third step, stirring for 10min at room temperature, centrifugally washing, and drying to obtain nickel-cobalt double hydroxide;
and fifthly, after cleaning and drying the nickel-cobalt double metal hydroxide obtained in the fourth step, calcining the nickel-cobalt double metal hydroxide for 2 hours at 300 ℃ in an argon atmosphere to obtain the nitrogen-doped nickel-cobalt double metal phosphide.
Further, in the first step, a sodium hydroxide solution and a copper chloride dihydrate solution are added dropwise at a volume ratio of 1:10 and a concentration of 2mol L-1The dropping rate was 1 drop per second.
Further, in the first step, ascorbic acid solution and copper chloride dihydrate solution are added dropwise at a volume ratio of 1:10 and a concentration of 0.6mol L-1The dropping rate was 1 drop per second.
Further, in the second step and the fourth step, the rotating speed of the centrifuge is 9000r min-1The centrifugation time was 3min and the oven temperature was 60 ℃.
Further, in the third step, Cu2O powder is ultrasonically dispersed in a mixed solution of deionized water and ethanol with the volume ratio of 1:1, and the concentration is 1g L-1。
Further, in the fourth step, a sodium thiosulfate solution and ethanol are added dropwise, wherein the volume ratio of the sodium thiosulfate solution to the ethanol is 4:5, and the concentration of the sodium thiosulfate solution to the ethanol is 1mol L-1The dropping rate was 1 drop per second.
Further, in the fifth step, sodium hypophosphite monohydrate and ammonium bicarbonate with the mass ratio of 12:4:1 and the nickel-cobalt double metal hydroxide prepared in the fourth step are respectively placed at the upper part, the middle part and the lower part of the tubular furnace in the argon atmosphere for 1 min-1The temperature rising rate of (2) is increased to 300 ℃ for calcining for 2 h.
Compared with the prior art, the invention has the advantages that: (1) the prepared nitrogen-doped nickel-cobalt bimetallic phosphide has mild reaction conditions and simple operation; (2) the nitrogen-doped nickel-cobalt bimetallic phosphide prepared by the method has uniform size of about 700nm, and the thickness of a hollow shell layer is about 100 nm; (3) more active sites can be obtained by nitrogen-doped nickel-cobalt double-metal phosphide, the specific capacitance of the electrode material is improved, and the current density is 1A g-1Its specific capacitance is up to 1726.02F g-1At a current density of 30A g-1When the specific capacitance reaches 1483.73F g-1The capacity retention rate is 86.95%, and the high-performance lithium ion battery has good rate performance.
Drawings
FIG. 1 is a diagram of the synthetic mechanism of the present invention.
Fig. 2 is a transmission electron microscope image of a nickel cobalt double hydroxide and a nitrogen-doped nickel cobalt double phosphide prepared in comparative example and example 1 of the present invention (wherein a to B are transmission electron microscope images of a nickel cobalt double hydroxide, and C to D are transmission electron microscope images of a nitrogen-doped nickel cobalt double phosphide).
FIG. 3 is an XRD diffraction pattern of the materials prepared in examples 1-3 of the present invention.
FIG. 4 is a graph comparing the charge and discharge curves of the nitrogen-doped nickel cobalt bimetallic phosphide, nickel cobalt bimetallic hydroxide, nickel phosphide compound and cobalt phosphide compound prepared in examples 1 to 3 of the present invention and comparative example 1 with those of the graph A and the graph comparing the capacity characteristics with those of the graph B.
Detailed Description
With reference to fig. 1, the nitrogen-doped nickel-cobalt bimetallic phosphide of the present invention is prepared by the following steps:
in the first step, at 0.01mol L-12mol L of copper chloride dihydrate solution is dropped-1Stirring sodium hydroxide solution in constant temperature water bath at 55 deg.C for 30min, and adding 0.6mol L-1The ascorbic acid solution is continuously stirred for 3 hours in a constant-temperature water bath at 55 ℃.
Step two, the precipitate obtained in the step one is dried after being centrifugally washed;
third step, Cu obtained in the second step2Ultrasonically dispersing O powder into a mixed solution of deionized water and ethanol, adding polyvinylpyrrolidone K30 and nickel chloride hexahydrate and cobalt chloride hexahydrate (0: 1; 1: 1; 1:0) in different proportions, and magnetically stirring at room temperature for 30 min;
the fourth step, 1mol L of the mixed solution obtained in the third step is dropped into it-1Stirring the sodium thiosulfate solution at room temperature for 10min, centrifuging, washing and drying to obtain nickel-cobalt double hydroxide;
fifthly, after the nickel-cobalt double metal hydroxide obtained in the fourth step is cleaned and dried, 600mg of sodium hypophosphite monohydrate, 200mg of ammonium bicarbonate and 55mg of the nickel-cobalt double metal hydroxide obtained in the fourth step are respectively placed at the upper, middle and lower streams of the tube furnace in argon atmosphere for 1 min-1The temperature rise rate is increased to 300 ℃ and the mixture is calcined for 2 hours to prepare the nitrogen-doped nickel-cobalt double-metal phosphide.
The dropping rate of all the solutions is 1 drop per second.
Example 1
In the first step, at 0.01mol L-12mol L of copper chloride dihydrate solution is dropped-1Stirring sodium hydroxide solution in constant temperature water bath at 55 deg.C for 30min, and adding 0.6mol L-1The ascorbic acid solution is continuously stirred for 3 hours in a constant-temperature water bath at 55 ℃.
Step two, the precipitate obtained in the step one is dried after being centrifugally washed;
thirdly, ultrasonically dispersing the sample obtained in the second step into a mixed solution of deionized water and ethanol, adding 26mg of nickel chloride hexahydrate, 26mg of cobalt chloride hexahydrate and 5g of polyvinylpyrrolidone K30 into the mixed solution, and magnetically stirring the mixture at room temperature for 30 min;
the fourth step, 1mol L of the mixed solution obtained in the third step is dropped into it-1Stirring the sodium thiosulfate solution at room temperature for 10min, centrifuging, washing and drying to obtain nickel-cobalt double metal hydroxide;
fifthly, after the nickel-cobalt double metal hydroxide obtained in the fourth step is cleaned and dried, 600mg of sodium hypophosphite monohydrate, 200mg of ammonium bicarbonate and 50mg of the nickel-cobalt double metal hydroxide obtained in the fourth step are respectively placed at the upper, middle and lower reaches of the tube furnace in argon atmosphere for 1 min-1The temperature rise rate is increased to 300 ℃ and the mixture is calcined for 2 hours to prepare the nitrogen-doped nickel-cobalt bimetallic phosphide N-NiCoP.
Example 2:
in the first step, at 0.01mol L-12mol L of copper chloride dihydrate solution is dropped-1Stirring sodium hydroxide solution in constant temperature water bath at 55 deg.C for 30min, and adding 0.6mol L-1The ascorbic acid solution is continuously stirred for 3 hours in a constant-temperature water bath at 55 ℃.
Step two, the precipitate obtained in the step one is dried after being centrifugally washed;
thirdly, ultrasonically dispersing the sample obtained in the second step into a mixed solution of deionized water and ethanol, adding 52mg of nickel chloride hexahydrate and 5g of polyvinylpyrrolidone K30 into the mixed solution, and magnetically stirring the mixture at room temperature for 30 min;
the fourth step, 1mol L of the mixed solution obtained in the third step is dropped into it-1Stirring the sodium thiosulfate solution at room temperature for 10min, centrifuging, washing and drying to obtain nickel hydroxide;
fifthly, after the nickel-cobalt double metal hydroxide obtained in the fourth step is cleaned and dried, 600mg of sodium hypophosphite monohydrate, 200mg of ammonium bicarbonate and 50mg of the nickel-cobalt double metal hydroxide obtained in the fourth step are respectively placed at the upper, middle and lower reaches of the tube furnace in argon atmosphere for 1 min-1Temperature rise ofThe speed is increased to 300 ℃ to calcine for 2h, and the nickel phosphide compound NiP is obtained.
Example 3:
in the first step, at 0.01mol L-12mol L of copper chloride dihydrate solution is dropped-1Stirring sodium hydroxide solution in constant temperature water bath at 55 deg.C for 30min, and adding 0.6mol L-1The ascorbic acid solution is continuously stirred for 3 hours in a constant-temperature water bath at 55 ℃.
Step two, the precipitate obtained in the step one is dried after being centrifugally washed;
thirdly, ultrasonically dispersing the sample obtained in the second step into a mixed solution of deionized water and ethanol, adding 52mg of cobalt chloride hexahydrate and 5g of polyvinylpyrrolidone K30 into the mixed solution, and magnetically stirring the mixture at room temperature for 30 min;
the fourth step, 1mol L of the mixed solution obtained in the third step is dropped into it-1Stirring the sodium thiosulfate solution at room temperature for 10min, centrifuging, washing and drying to obtain cobalt hydroxide;
fifthly, after the nickel-cobalt double metal hydroxide obtained in the fourth step is cleaned and dried, 600mg of sodium hypophosphite monohydrate, 200mg of ammonium bicarbonate and 50mg of the nickel-cobalt double metal hydroxide obtained in the fourth step are respectively placed at the upper, middle and lower reaches of the tube furnace in argon atmosphere for 1 min-1The temperature rising rate of the catalyst is increased to 300 ℃ to calcine for 2 hours, and the cobalt phosphide compound CoP is obtained.
Comparative example 1
Firstly, adding copper chloride dihydrate into deionized water and dripping 2mol L of the copper chloride dihydrate-1Stirring sodium hydroxide solution in constant temperature water bath at 55 deg.C for 30min, and adding 0.6mol L-1The ascorbic acid solution is continuously stirred for 3 hours in a constant-temperature water bath at 55 ℃.
Step two, the precipitate obtained in the step one is dried after being centrifugally washed;
thirdly, ultrasonically dispersing the sample obtained in the second step into a mixed solution of deionized water and ethanol, adding 26mg of nickel chloride hexahydrate, 26mg of cobalt chloride hexahydrate and 5g of polyvinylpyrrolidone K30 into the mixed solution, and magnetically stirring the mixture at room temperature for 30 min;
the fourth step, 1mol L of the mixed solution obtained in the third step is dropped into it-1Sodium thiosulfate solution, stirring at room temperatureAnd stirring for 10min, centrifugally washing and drying to obtain the nickel-cobalt double metal hydroxide NiCo-LDH.
Claims (7)
1. The nitrogen-doped nickel-cobalt double-metal phosphide material is characterized in that Cu is used2After the nickel-cobalt double hydroxide is obtained by taking O as a template, simultaneously carrying out phosphorization and nitrogen doping in one step to obtain nitrogen-doped nickel-cobalt double metal phosphide; the material is in a nano hollow cubic structure; the method comprises the following steps:
in the first step, at 0.01mol L-1Dripping a copper chloride dihydrate solution into a sodium hydroxide solution, stirring for 30min in a constant-temperature water bath at 55 ℃, dripping an ascorbic acid solution, and continuously stirring for 3h in the constant-temperature water bath at 55 ℃;
step two, the precipitate obtained in the step one is dried after being centrifugally washed to prepare Cu2O powder;
third step, Cu obtained in the second step2Ultrasonically dispersing O powder into a mixed solution of deionized water and ethanol, adding polyvinylpyrrolidone K30, nickel chloride hexahydrate and cobalt chloride hexahydrate, and magnetically stirring at room temperature for 30 min;
fourthly, dripping a sodium thiosulfate solution into the mixed solution obtained in the third step, stirring for 10min at room temperature, centrifugally washing, and drying to obtain nickel-cobalt double hydroxide;
and fifthly, after cleaning and drying the nickel-cobalt double metal hydroxide obtained in the fourth step, calcining the nickel-cobalt double metal hydroxide for 2 hours at 300 ℃ in an argon atmosphere to obtain the nitrogen-doped nickel-cobalt double metal phosphide.
2. The nitrogen-doped nickel-cobalt bimetallic phosphide material of claim 1, wherein in the first step, a sodium hydroxide solution and a copper chloride dihydrate solution are added dropwise at a volume ratio of 1:10 and a concentration of 2mol L-1The dropping rate was 1 drop per second.
3. The nitrogen-doped nickel-cobalt bimetallic phosphide material of claim 1, wherein in the first step, the ascorbic acid solution and the copper chloride dihydrate solution are added dropwise in a volume ratio of 1:10 and at a concentration of 0.6mol L-1At a dropping rate of1 drop per second.
4. The nitrogen-doped nickel-cobalt bimetallic phosphide material of claim 1, wherein in the second step and the fourth step, the centrifuge speed is 9000 rpm-1The centrifugation time was 3min and the oven temperature was 60 ℃.
5. The nitrogen-doped nickel-cobalt bimetallic phosphide material of claim 1, wherein in the third step, the Cu2O powder is ultrasonically dispersed in a mixed solution of deionized water and ethanol at a volume ratio of 1:1, and the concentration is 1g L-1。
6. The nitrogen-doped nickel-cobalt bimetallic phosphide material of claim 1, wherein in the fourth step, a sodium thiosulfate solution and ethanol are added dropwise at a volume ratio of 4:5 and a concentration of 1mol L-1The dropping rate was 1 drop per second.
7. The nitrogen-doped nickel-cobalt bimetallic phosphide material of claim 1, wherein in the fifth step, sodium hypophosphite monohydrate and ammonium bicarbonate in a mass ratio of 12:4:1 and the nickel-cobalt bimetallic hydroxide prepared in the fourth step are respectively placed at the upper, middle and lower streams of a tube furnace in an argon atmosphere at 1 ℃ for min-1The temperature rising rate of (2) is increased to 300 ℃ for calcining for 2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910712412.0A CN110517896B (en) | 2019-08-02 | 2019-08-02 | Nitrogen-doped nickel-cobalt bimetallic phosphide material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910712412.0A CN110517896B (en) | 2019-08-02 | 2019-08-02 | Nitrogen-doped nickel-cobalt bimetallic phosphide material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110517896A CN110517896A (en) | 2019-11-29 |
| CN110517896B true CN110517896B (en) | 2021-12-10 |
Family
ID=68624226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910712412.0A Active CN110517896B (en) | 2019-08-02 | 2019-08-02 | Nitrogen-doped nickel-cobalt bimetallic phosphide material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110517896B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112456557A (en) * | 2020-11-26 | 2021-03-09 | 北京化工大学 | Method for preparing copper-based delafossite-type oxide material |
| CN112908714B (en) * | 2021-02-03 | 2022-09-06 | 湘潭大学 | Micro-nano spherical zinc-doped nickel-cobalt bimetallic phosphide and preparation method and application thereof |
| CN114045500B (en) * | 2021-11-19 | 2023-04-07 | 北京科技大学 | Preparation method of self-supporting multi-level structure electrode |
| CN116023201B (en) * | 2022-12-27 | 2024-03-15 | 浙江新化化工股份有限公司 | Preparation method of aromatic alcohol |
-
2019
- 2019-08-02 CN CN201910712412.0A patent/CN110517896B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110517896A (en) | 2019-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110517896B (en) | Nitrogen-doped nickel-cobalt bimetallic phosphide material and preparation method thereof | |
| Ameri et al. | Engineering of hierarchical NiCoSe 2@ NiMn-LDH core-shell nanostructures as a high-performance positive electrode material for hybrid supercapacitors | |
| Hussain et al. | Controlled synthesis and growth mechanism of zinc cobalt sulfide rods on Ni-foam for high-performance supercapacitors | |
| CN110853937A (en) | Preparation method of nickel-cobalt bimetallic selenide/carbon composite for supercapacitor | |
| Wang et al. | Controllable synthesis of hollow multishell structured Co3O4 with improved rate performance and cyclic stability for supercapacitors | |
| Zhang et al. | Metal–organic framework derived porous CuO/Cu 2 O composite hollow octahedrons as high performance anode materials for sodium ion batteries | |
| Zhang et al. | Crystallization design of MnO 2 towards better supercapacitance | |
| CN108390014A (en) | The preparation method of foamed nickel supported different-shape cobalt black nano material | |
| Cheng et al. | Etching strategy synthesis of hierarchical Ni-Mn hydroxide hollow spheres for supercapacitors | |
| CN102163711B (en) | Method for preparing lithium ion battery negative material by utilizing mesoporous carbon supported nano particles | |
| CN103268929A (en) | Carbon/copper/metal oxide composite porous material and preparation method and application thereof | |
| Liu et al. | Synthesis of self-templated urchin-like Ni2Co (CO3) 2 (OH) 2 hollow microspheres for high-performance hybrid supercapacitor electrodes | |
| Zhao et al. | Design of trimetallic sulfide hollow nanocages from metal–organic frameworks as electrode materials for supercapacitors | |
| CN111525119B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN108461729B (en) | Tellurium-sulfur composite carbon material and preparation method and application thereof | |
| CN107316987A (en) | A kind of oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites and preparation method thereof | |
| Li et al. | Facile preparation of MnO2 with large surface area in a rotor–stator reactor for supercapacitors | |
| CN105185606A (en) | Preparation method of novel cobaltous dihydroxycarbonate-nitrogen-doped graphene combined electrode material | |
| Omar et al. | Facile synthesis of a binary composite from watermelon rind using response surface methodology for supercapacitor electrode material | |
| CN109336196A (en) | Three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene and preparation method thereof, application | |
| CN111899988A (en) | Macro preparation method and application of nickel-cobalt double-metal hydroxide electrode material | |
| CN110233248B (en) | High-area specific volume battery negative electrode material and preparation method and application thereof | |
| CN110759389B (en) | Cu (Ni, Co)2S4Electrode material and preparation method thereof | |
| Li et al. | Mo-doped ZIF-67 derived Ni, Co, Mo trimetallic sulfide/carbon nanotubes for supercapacitors | |
| Wang et al. | A novel three-dimensional hierarchical porous lead-carbon composite prepared from corn stover for high-performance lead-carbon batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |