CN114914461B - Cadmium-based composite material and preparation method and application thereof - Google Patents

Cadmium-based composite material and preparation method and application thereof Download PDF

Info

Publication number
CN114914461B
CN114914461B CN202210655049.5A CN202210655049A CN114914461B CN 114914461 B CN114914461 B CN 114914461B CN 202210655049 A CN202210655049 A CN 202210655049A CN 114914461 B CN114914461 B CN 114914461B
Authority
CN
China
Prior art keywords
cadmium
composite material
based composite
ppy
catalyst
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
Application number
CN202210655049.5A
Other languages
Chinese (zh)
Other versions
CN114914461A (en
Inventor
杨秀林
邵雪
梁沁睿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangxi Normal University
Original Assignee
Guangxi Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guangxi Normal University filed Critical Guangxi Normal University
Priority to CN202210655049.5A priority Critical patent/CN114914461B/en
Publication of CN114914461A publication Critical patent/CN114914461A/en
Application granted granted Critical
Publication of CN114914461B publication Critical patent/CN114914461B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Hybrid Cells (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a cadmium-based composite material and a preparation method and application thereof, belonging to the technical field of electrocatalytic oxidation reduction, and Cd (NH) 3 ) 2 Cl 2 And carrying out high-temperature phosphating treatment on the/PPy precursor to obtain the cadmium-based composite material. The intrinsic catalytic activity of the catalyst is improved by forming a P-O bond in the carbon material, and the cadmium-based composite material containing the P-O group has high-efficiency oxygen reduction performance in an alkaline solution. As a cathode material of a zinc-air battery, the cadmium-based composite material as a catalyst has good long-term stability, keeps no decline for nearly 300 hours and can reach 208.1mW cm ‑2 The power density of (a). Therefore, the novel cadmium-based composite material containing the P-O group can replace a noble metal Pt/C catalyst to be used for oxygen reduction reaction, thereby reducing the cost.

Description

Cadmium-based composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrocatalytic oxygen reduction, in particular to a cadmium-based composite material and a preparation method and application thereof.
Background
At present, in order to meet the future requirement of green energy, the zinc-air battery is becoming a promising energy storage system due to its advantages of green environmental protection, low cost and high energy conversion efficiency. However, since the kinetics of the air cathode oxygen reduction reaction are hindered, the energy density of the zinc-air battery is only 40-50% of the theoretical density, and therefore a high-activity and high-efficiency ORR catalyst is needed to overcome the slow four-electron transfer kinetics and selectively catalyze the ORR on a low-energy-barrier path, thereby realizing the high energy conversion efficiency of the zinc-air battery.
Noble metal carbon supported platinum catalysts (Pt/C) have been widely used, but their low natural abundance and high production cost have limited the application and commercial development of integrated energy and energy systems. Therefore, there has been much interest in developing highly efficient, inexpensive, and durable oxygen reduction catalysts based on transition metals.
Disclosure of Invention
In order to solve the technical problems, the invention provides a cadmium-based composite material, a preparation method and application thereof, and intrinsic catalytic activity of a catalyst is improved by dispersing P-O groups.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a cadmium-based composite material, which takes PPy as a carbon carrier and is a double-crystal phase composite material and is prepared from Cd 2 P 2 O 7 And Cd 2 P 4 O 12 The composite formed by two substances with different crystal phases has a complex structure.
The invention provides a preparation method of the cadmium-based composite material, which uses Cd (NH) 3 ) 2 Cl 2 the/PPy is a precursor, and the cadmium-based composite material is obtained through high-temperature phosphating treatment.
Further, the Cd (NH) 3 ) 2 Cl 2 The preparation method of the/PPy precursor comprises the following steps:
dissolving PPy carbon carrier, cadmium nitrate and dopamine hydrochloride serving as raw materials in a mixed solution of ammonia water, water and ethanol serving as a solvent, and stirring at normal temperature to react to obtain Cd (NH) 3 ) 2 Cl 2 A PPy precursor.
Further, the preparation method of the PPy carbon carrier comprises the following steps: stirring CTAB (cetyl trimethyl ammonium bromide), ammonium persulfate and pyrrole in HCl to obtain black precipitate, washing and drying.
Further, the mass-to-volume ratio of CTAB, ammonium persulfate and pyrrole is 0.73g:1.73g:1mL.
Further, the mass ratio of the PPy carbon carrier to the cadmium nitrate to the dopamine hydrochloride is 0.1:0.616:0.5;
the volume ratio of ammonia water to ethanol in the mixed solution is 1:20:45.
further, the high-temperature phosphating treatment comprises the following steps: cd (NH) 3 ) 2 Cl 2 Mixing the PPy precursor and red phosphorus, grinding, and mixing the PPy precursor and the red phosphorus in a mass ratio of 1:2, then transferring the mixture into an argon atmosphere, and raising the temperature at the speed of 5 ℃/minThe temperature is raised to 800 ℃ and the mixture is calcined for 2h.
The proper calcination temperature ensures that the prepared product has higher graphitization degree and conductivity, promotes the electron transfer in the electrochemical ORR process, but the catalyst is easy to sinter to destroy the activity; the calcination time can affect the structure of the catalyst, so that the combination effect of the load substance and the carrier is changed, and the catalytic effect is affected; the addition of red phosphorus improves the graphitization degree of the catalyst, adjusts the interaction between a Cd active center and an intermediate, and is beneficial to improving the catalytic activity of the catalyst; the addition of the PPy carbon carrier increases the crystal phase of the catalyst, and is helpful for understanding the catalytic action of different crystal phases in the phosphorus-containing catalyst.
The invention also provides application of the cadmium-based composite material as a catalyst in preparation of an electrode material.
The invention provides a redox electrode, which takes the cadmium-based composite material as a catalyst material, and the preparation method of the redox electrode comprises the following steps: and mixing the cadmium-based composite material with isopropanol and 5wt% of perfluorinated sulfonic acid solution to obtain catalyst ink, dripping the catalyst ink on the surface of the polished working electrode, and drying to obtain the redox electrode.
The invention provides a zinc-air battery cathode electrode, which takes the cadmium-based composite material as a catalyst material, and the preparation method of the zinc-air battery cathode electrode comprises the following steps: mixing the cadmium-based composite material with isopropanol, water and 5wt% of perfluorinated sulfonic acid solution to obtain catalyst ink, dripping the catalyst ink on hydrophilic carbon fiber paper, and drying to obtain the zinc-air battery cathode electrode.
Further, in the preparation process of the redox electrode and the cathode electrode of the zinc-air battery, the mixing mass volume ratio of the cadmium-based composite material to the isopropanol and the 5wt% perfluorosulfonic acid solution is 2mg:495 μ L:5 μ L.
The invention discloses the following technical effects:
1. the composite material of the present invention contains P-O groups. The transition metal phosphate has a mixed polyanion skeleton and a rich crystal structure, and has excellent physicochemical properties. In addition, phosphates can help the catalyst to produce more active sites and protect the active sites from corrosion and dissolution in a strongly alkaline environment, thereby increasing catalytic activity. The red phosphorus regulates the interaction between the Cd active center and the intermediate, and rich oxygen elements in the PPy carbon carrier and phosphorus elements easily form P-O bonds to closely influence the polymerization mode of anions, so that the performance of the material is better.
2. Cadmium phosphate is a typical oxysalt and is less applicable to the field of electrocatalysis. Cadmium phosphate has abundant lattice oxygen and more oxygen than other cadmium-based materials, which provides greater potential for forming P-O bonds. The cadmium-based composite material catalyst with high activity is prepared by a reasonable strategy, and the cadmium-based composite material catalytic material with the P-O group obtained by high-temperature phosphorization not only has good oxygen reduction (ORR) catalytic performance, but also has long-term stability and high power density when being applied to a zinc-air battery, so that the cadmium-based composite material with the P-O group is prepared by a controllable method, and the excellent performance is attributed to the P-O group, large specific surface area and active sites.
3. The novel cadmium-based composite material prepared by the invention has high-efficiency oxygen reduction performance in alkaline solution; as a cathode material of a zinc-air battery, the cadmium-based composite catalyst has good long-term stability, does not fade after 230 hours, has high power density, and can reach 208.1 mW.cm -2 。
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an X-ray powder diffraction pattern of a cadmium-based composite material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a cadmium-based composite material prepared in example 1 of the present invention; wherein, the picture a is PPy carbon carrier scanning electron microscope picture, and the picture b is Cd (NH) 3 ) 2 Cl 2 a/PPy precursor scanning electron microscope picture, a c picture is a cadmium-based composite material scanning electron microscope picture, a d picture is a transmission electron microscope picture, an e picture is a high-power transmission electron microscope picture, an f picture is an element dispersion energy spectrogram, and g is a high-angle annular dark field and a corresponding element distribution picture;
FIG. 3 is a diagram of an X-ray photoelectron spectrum Cd 3d of a composite material prepared in examples 1 to 3 of the present invention;
FIG. 4 is a graph of X-ray photoelectron spectroscopy (O1 s) of a composite material prepared in example 1 of the present invention;
fig. 5 is a CV curve of the redox electrode prepared in effect verification 1 of the present invention;
FIG. 6 is an RRDE curve of the redox electrode prepared in validation of the effects 1 of the present invention at 1600 rpm;
FIG. 7 shows RRDE curves (left) and K-L diagrams (right) of electrodes prepared from cadmium-based composite material in the effect verification 1 of the invention at different rotating speeds;
FIG. 8 is H of the redox electrode prepared in the verification of the Effect 1 of the present invention 2 O 2 Yield and corresponding electron transfer number;
fig. 9 is a tafel slope of the redox electrode prepared in effect verification 1 of the present invention;
fig. 10 is a schematic view of a zinc-air battery according to the effect verification 2 of the present invention;
fig. 11 is a graph showing the power density of the catalyst in the zinc-air battery in effect verification 2 according to the present invention;
fig. 12 is a graph of open circuit voltage of a zinc-air cell of the catalyst in the zinc-air cell of the effect verification 2 of the present invention;
FIG. 13 is a diagram of a zinc-air cell series lighting red LED lamp in effect verification 2 of the present invention;
fig. 14 is a discharge curve of a zinc-air battery assembled by cadmium-based composite materials in effect verification 2 of the present invention at different current densities;
fig. 15 is a graph of specific capacity of a zinc-air battery assembled with a cadmium-based composite material according to the effect verification 2 of the present invention;
fig. 16 is a constant current discharge and charge voltage curve of a zinc-air battery in effect verification 2 of the present invention;
fig. 17 is a comparison of voltage differences between the first turn (left) and the last turn (right) of the effect verification 2 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated or intervening value in a stated range, and every other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
The normal temperature in the embodiment of the invention refers to 25 +/-2 ℃.
The process of collecting the precipitate by centrifugation in the embodiments of the present invention is a conventional technical means in the art, and is not the focus of the present invention, and is not described herein again.
The embodiment of the invention provides a cadmium-based composite material, which takes PPy as a carbon carrier and Cd 2 P 2 O 7 And Cd 2 P 4 O 12 The composite material prepared by the invention is a double-crystal phase composite material and is prepared by Cd 2 P 2 O 7 And Cd 2 P 4 O 12 The two different crystal phases are composed, and the structure is complex.
The embodiment of the invention provides a preparation method of a cadmium-based composite material, which uses Cd (NH) 3 ) 2 Cl 2 the/PPy is a precursor, and the cadmium-based composite material is obtained through high-temperature phosphating treatment.
The method for preparing the cadmium-based composite material after high-temperature phosphating is simple to operate and high in yield.
Example of the invention Cd (NH) 3 ) 2 Cl 2 The preparation method of the/PPy precursor comprises the following steps:
dissolving PPy carbon carrier, cadmium nitrate and dopamine hydrochloride serving as raw materials in a mixed solution of ammonia water, water and ethanol serving as a solvent, and stirring at normal temperature to react to obtain Cd (NH) 3 ) 2 Cl 2 @ PPy precursor.
The preparation method of the PPy carbon carrier comprises the following steps: stirring CTAB (cetyl trimethyl ammonium bromide), ammonium persulfate and pyrrole in HCl to obtain black precipitate, washing and drying.
In the embodiment of the invention, the mass-volume ratio of CTAB, ammonium persulfate and pyrrole is 0.73g:1.73g:1mL.
According to the embodiment of the invention, the mass ratio of the PPy carbon carrier to the cadmium nitrate to the dopamine hydrochloride is 0.1:0.616:0.5;
the volume ratio of ammonia water to ethanol in the mixed solution is 1:20:45.
for example, the present inventionExample PPy carbon support was prepared by dissolving 1mL pyrrole, 0.73g CTAB and 1.73g ammonium persulfate in 60mL 1M HCl solution and stirring for 24 h. Cd (NH) in the invention 3 ) 2 Cl 2 the/PPy precursor can be obtained by adding 0.616g of cadmium nitrate and 0.5g of dopamine hydrochloride into 20mL of deionized water and 1mL of ammonia water solution (the mass concentration of ammonia water is 25-28%), and stirring at normal temperature for 15 h.
Further, the high-temperature phosphating treatment comprises the following steps: cd (NH) 3 ) 2 Cl 2 Mixing the PPy precursor and red phosphorus, grinding, and mixing the PPy precursor and the red phosphorus in a mass ratio of 1:2, then transferring the mixture into an argon atmosphere, and heating to 800 ℃ at a heating rate of 5 ℃/min to calcine the mixture for 2h.
The proper calcination temperature ensures that the prepared product has higher graphitization degree and conductivity, promotes the electron transfer in the electrochemical ORR process, but the catalyst is easy to sinter to destroy the activity; the calcination time can affect the structure of the catalyst, so that the combination effect of the load substance and the carrier is changed, and the catalytic effect is affected; the addition of red phosphorus improves the graphitization degree of the catalyst, adjusts the interaction between a Cd active center and an intermediate, and is beneficial to improving the catalytic activity of the catalyst; the addition of the PPy carbon carrier increases the crystal phase of the catalyst, and is helpful for understanding the catalytic action of different crystal phases in the phosphorus-containing catalyst.
The embodiment of the invention also provides application of the cadmium-based composite material as a catalyst in preparation of an electrode material.
The invention relates to a redox electrode, which takes a cadmium-based composite material as a catalyst material, and a preparation method of the redox electrode comprises the following steps: and mixing the cadmium-based composite material with isopropanol and 5wt% of perfluorinated sulfonic acid solution to obtain catalyst ink, dripping the catalyst ink on the surface of the polished working electrode, and drying to obtain the redox electrode.
The invention relates to a zinc-air battery cathode electrode, which takes a cadmium-based composite material as a catalyst material, and the preparation method of the zinc-air battery cathode electrode comprises the following steps: mixing the cadmium-based composite material with isopropanol, water and 5wt% of perfluorinated sulfonic acid solution to obtain catalyst ink, dripping the catalyst ink on hydrophilic carbon fiber paper, and drying to obtain the zinc-air battery cathode electrode.
In the preparation process of the redox electrode and the cathode electrode of the zinc-air battery, the mixing mass volume ratio of the cadmium-based composite material to the isopropanol and the 5wt% perfluorinated sulfonic acid solution is 2mg:495 mu L of: 5 μ L.
Example 1
(1) 0.73g CTAB and 1.73g ammonium persulfate were weighed into 60mL 1M HCl solution and stirred for 10min. 1mL of pyrrole is measured and added into the solution dropwise to prepare a uniform mixed solution, the mixture is stirred continuously for 24 hours, and the precipitate is collected by a centrifugal method to obtain the PPy carbon carrier.
(2) Dispersing the washed and dried PPy carbon carrier into a mixed solution consisting of 1mL of ammonia water (mass concentration of 25%), 20mL of deionized water and 45mL of ethanol, adding 0.616g of cadmium nitrate and 0.5g of dopamine hydrochloride, stirring for 15h, and collecting precipitate by a centrifugal method to obtain Cd (NH) 3 ) 2 Cl 2 A PPy precursor.
(3) 0.1g of Cd (NH) was weighed 3 ) 2 Cl 2 The PPy precursor and 0.2g of red phosphorus are ground uniformly, the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min, and the mixture is calcined for 2 hours in the argon atmosphere at 800 ℃. And cooling to room temperature, and collecting powder to finish the preparation of the cadmium-based composite material.
FIG. 1 is an X-ray powder diffraction pattern of a cadmium-based composite material prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of a cadmium-based composite material prepared according to example 1 of the present invention; wherein a-c is a scanning electron microscope image, d is a transmission electron microscope image, e is a high-power transmission electron microscope image, f is an element energy spectrogram, and g is a high-angle annular dark field and a corresponding element distribution image.
By analyzing fig. 1 and 2: FIG. 1 shows that the composite material is formed by Cd 2 P 2 O 7 And Cd 2 P 4 O 12 Two crystalline phases. All well-defined peaks were associated with Cd 2 P 2 O 7 (JCPDS: 31-0233) and Cd 2 P 4 O 12 (JCPDS: 26-0267) the crystal signals were highly uniform, exhibiting excellent crystallinity and high purity. Furthermore, in 2a, PPy carbon supports exhibit a typical spherical morphology. FIG. 2b is Cd (NH) 3 ) 2 Cl 2 The precursor showed a hollow sphere morphology with a rough surface. Fig. 2c shows that the cadmium-based composite material modified with red phosphorus still maintains good hollow sphere morphology. Figure 2d records a transmission electron micrograph of the hollow structure of the catalyst. FIG. 2e high resolution TEM image with 0.326nm spacing attributed to Cd 2 P 2 O 7 The (210) plane of (1), the 0.331nm lattice fringe being attributed to Cd 2 P 4 O 12 The (310) crystal plane of (c). Fig. 2f is an energy dispersive spectrum, signals of Cd, P, O, N, and C are significant, indicating that doping of elements was successful. Fig. 2g is a large angle annular dark field scan and corresponding element mapping showing good distribution of Cd, P, O, N, C elements throughout the catalyst structure of the cadmium-based composite.
Example 2
Step (1) same as example 1;
(2) Weighing a PPy carbon carrier, uniformly grinding, heating to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours at 800 ℃ in an argon atmosphere, cooling to room temperature, and collecting powder to finish the preparation of NC.
Example 3
Steps (1) and (2) are the same as steps (2) and (3) in example 1 to complete Cd 2 P 2 O 7 Preparation of/C.
Example 4
The procedures (1) and (2) are the same as those in example 1.
(3) 0.1g of Cd (NH) was weighed 3 ) 2 Cl 2 Grinding the/PPy precursor uniformly, heating to 800 ℃ at the heating rate of 5 ℃/min, and calcining for 2h in the argon atmosphere at 800 ℃. After cooling to room temperature, the powder was collected to complete the preparation of NC.
The X-ray photoelectron spectrum Cd 3d of the composite materials prepared in examples 1 to 3 is shown in FIG. 3; according to the XPS diagram of FIG. 3. In the Cd 3d high resolution region, two peaks at 405.08 and 411.88eV were fitted to reveal Cd 3+ The deconvolution peaks for states 406.13 and 412.93eV belong to Cd 2+ Configuration. In addition, cd 2+ /Cd 3+ (83.2) the ratio is higher than that of the cadmium-based composite (78.7) sample, indicating that the valence portion of the sample is reduced and oxygen-rich vacancies are created.
FIG. 4 is an X-ray photoelectron spectrum O1s chart of the composite material produced in example 1 of the present invention in which deconvolution peaks at 529.8, 531 and 532.6eV are assigned to the crystal lattice O, vo and chemisorbed oxygen, respectively. In the cadmium-based composite material, 30.0% of oxygen vacancies were exhibited. These oxygen vacancies are to oxygen intermediates such as O 2 Molecule, OH － And O 2 The ions play the role of an electrochemical active center, the intrinsic conductivity of the catalyst is improved, and the electrocatalytic reaction is promoted. In the deconvolved P2P spectrum, the peak at 133.8eV is attributable to the oxidized phosphate species. According to previous reports, doping of P-O bonds can change charge density distribution and electronic structure of metal active centers, and improve catalytic activity of ORR.
Effect verification 1
The preparation of the redox electrode using the Pt/C catalyst, the composite material of examples 1-4 as the catalyst, and the rotating ring disk electrode as the working electrode, respectively, was as follows:
the working electrode was polished with 0.05 μm alumina on a felt polishing pad, followed by water, 0.5 mol. L -1 Washing with sulfuric acid and ethanol for three times;
2mg of the synthesized catalyst powder was weighed, mixed with 495. Mu.L of isopropyl alcohol and 5. Mu.L of 5wt% Nafion solution, and sonicated for 30min. 19.610. Mu.L of catalyst ink was added dropwise to the polished RRDE surface using a pipette gun and dried in the natural environment. The catalyst loading on the working electrode was 0.318mg cm -2 The Pt/C catalyst load is 0.081 mg-cm -2 。
Oxygen reduction testing was performed on a CHI 760E electrochemical workstation (CH Instruments, chenhua Co, china) using a three electrode system. A typical three-electrode system is adopted, a carbon rod is used as a counter electrode, and KCl saturated Ag/AgCl is used as a reference electrode. Before testing, N is 2 (or O) 2 ) Bubbling for 30min from the electrolyte, and maintaining the bubbling state during the measurement to maintain N in the solution 2 (or O) 2 ) The saturated state of (c). Cyclic Voltammetry (CV) test at 50 mV. S in 0.1M KOH solution -1 At a scanning rate of N 2 (or O) 2 ) In a saturated solution. In N 2 (or O) 2 ) Saturated 0.1MIn KOH solution, at different rotation rates (400-2025 rpm) and 10 mV. Multidot.s -1 Scan rate a linear scan test (LSV) was performed. At 1600rpm, RRDE measures the number of electron transfers (n) and H in the ORR 2 O 2 Yield.
Figure GDA0004035348980000111
Figure GDA0004035348980000112
Wherein i D And i R Respectively the disk current and the ring current. N is the collection efficiency of the platinum loop (N = 0.37).
Fig. 5 is a CV curve of the redox electrode prepared in effect verification 1 of the present invention; FIG. 6 is a RRDE curve of the redox electrode prepared in the verification of the effect 1 of the present invention at a rotation speed of 1600 rpm; FIG. 7 is RRDE curve (left) and K-L diagram (right) of the electrode prepared from cadmium-based composite material in the effect verification 1 of the invention at different rotating speeds; FIG. 8 is H of the redox electrode prepared in effect verification 1 of the present invention 2 O 2 Yield and corresponding electron transfer number; fig. 9 is a tafel slope of the redox electrode prepared in effect verification 1 of the present invention. From fig. 4-9 it can be derived that: in FIG. 5, for the cadmium-based composite, a significant characteristic oxygen reduction peak was readily observed at 0.82V, comparable to the 20wt% Pt/C catalyst. In FIG. 6, the ORR polarization curve of the cadmium-based composite material shows an initial potential of 0.99V and a half-wave potential of 0.84V, which are equivalent to the reference Pt/C (0.82, 0.86), and are significantly better than NC and Cd 2 P 2 O 7 The components of/C, cd/NC and other reported cadmium-based composite based ORR electrocatalysts optimized the samples. In fig. 7, to further investigate the ORR mechanism of cadmium-based composites, LSVs were recorded at various rotational speeds of 625 to 2500rpm in oxygen saturated 0.1M KOH solutions. The results show that the limiting diffusion current density (J) increases with increasing rotation speed L ) This means that the higher the rotation speed, the faster the diffusion rate. The corresponding Koutecky-Levich curve is shown in FIG. 7, whereAlmost the same slope is observed between 0.30 and 0.70V, indicating that ORR on the cadmium-based composite follows first order kinetics (intercalation) with respect to the oxygen concentration in the electrolyte. FIG. 8 shows the electron transfer number (n) and hydrogen peroxide (H) 2 O 2 ) The yield was between 0.1 and 0.6V. The n value of the cadmium-based composite material is close to 4,H in the whole potential range 2 O 2 The yield was less than 10%, indicating that the catalyst is cadmium-based composite pair 4e - The oxygen reduction has high selectivity. The cadmium-based composite material in FIG. 9 shows 74.8mV dec -1 Smaller Tafel slope. For Pt/C, the values are 64mV dec -1 This indicates that the cadmium-based composite material has excellent kinetic properties during ORR.
Effect verification 2
Zinc-air cell testing:
fig. 10 is a schematic view of a zinc-air battery. Fig. 11 shows the power density when the cadmium-based composite material and Pt/C were used as the air cathode. It can be seen that the power density of the cadmium-based composite material-based zinc-air battery is 208mA cm -2 Is far higher than that of a noble metal Pt/C-based zinc-air battery (128 mA.m) -2 ) Thus, the cadmium-based composite material has better discharge performance. The open circuit voltage measurement in fig. 12 provides a stable voltage of 1.51V for the cadmium-based composite air cathode, comparable to the noble metal-based Pt/C (1.49V), which lasts 10h without loss. In addition, two batteries connected in series in fig. 13 may be used as a power source for driving the 3.0V red diode. Subsequently, in FIG. 14, the amount of the compound is in the range of 2 to 20mA cm -2 When the current density is reduced to 20mA cm -2 In the process, reversible recovery occurs, and the platform voltage only loses 0.02V, so that the result shows that the cadmium-based composite material has strong long-term discharge capacity. In FIG. 15, the specific capacities, when normalized to the weight of the zinc electrode consumed, were 739.6 and 689.3mAh g -1 . As shown in fig. 16, the cadmium-based composite-based zinc-air battery showed significant charge and discharge cycle stability compared to the noble metal Pt/C catalyst having a discharge time exceeding 200 h. FIG. 17 shows that after 230h of constant current charging and discharging, the voltage gap of the cadmium-based composite catalyst is increased from 0.96V to 1.02V, even exceedingThe long-term stability of the recently reported electrocatalyst-assembled zinc-air cells, these results indicate that the cadmium-based composite is a highly efficient, robust and attractive oxygen electrocatalyst.
In conclusion, it can be concluded that: the intrinsic catalytic activity of the catalyst is improved by the novel cadmium-based composite material. The novel cadmium-based composite material has high-efficiency oxygen reduction performance in alkaline solution and is prepared by adopting cyclic voltammetry and linear scanning method in O 2 Testing in saturated 0.1M KOH solution showed: a distinct redox peak at 0.82V (vs. rhe); half-wave potential 0.87V (vs. rhe); at 0.2V, the diffusion limiting current density was 5.48mA cm -2 (ii) a As a cathode material of a zinc-air battery, the cadmium-based composite catalyst has good long-term stability, keeps 155h without fading, has high power density and can reach 208.1 mW.m -2 。
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (9)

1. The cadmium-base composite material is characterized by that it uses PPy as carbon carrier and uses Cd as double-crystal phase composite material 2 P 2 O 7 And Cd 2 P 4 O 12 A composite of two different crystalline phases of matter;
the cadmium-based composite material is used as an ORR catalyst for preparing an electrode material.
2. A method for preparing the cadmium-based composite material as defined in claim 1, wherein Cd (NH) 3 ) 2 Cl 2 the/PPy is a precursor and is obtained by high-temperature phosphating treatment.
3. The method of claim 2, wherein the Cd (NH) is 3 ) 2 Cl 2 Perpy precursorThe preparation method of the body comprises the following steps:
dissolving PPy carbon carrier, cadmium nitrate and dopamine hydrochloride serving as raw materials in a mixed solution of ammonia water, water and ethanol serving as a solvent, and stirring at normal temperature to react to obtain Cd (NH) 3 ) 2 Cl 2 A PPy precursor.
4. The method according to claim 3, wherein the step of preparing the PPy carbon support comprises: stirring CTAB, ammonium persulfate and pyrrole in HCl to obtain black precipitate, washing and drying.
5. The preparation method according to claim 4, wherein the mass volume ratio of CTAB, ammonium persulfate and pyrrole is 0.73g:1.73g:1mL.
6. The preparation method according to claim 3, wherein the mass ratio of the PPy carbon carrier to the cadmium nitrate to the dopamine hydrochloride is 0.1:0.616:0.5;
the volume ratio of ammonia water to ethanol in the mixed solution is 1:20:45.
7. the method according to claim 2, wherein the high-temperature phosphating treatment comprises: cd (NH) 3 ) 2 Cl 2 Mixing the PPy precursor and red phosphorus, grinding, and mixing the PPy precursor and the red phosphorus in a mass ratio of 1:2, then transferring the mixture into an argon atmosphere, and heating to 800 ℃ at the heating rate of 5 ℃/min to calcine for 2h.
8. A redox electrode comprising the cadmium-based composite material according to claim 1 as a catalyst material, wherein the redox electrode is prepared by a method comprising the steps of: and mixing the cadmium-based composite material with isopropanol and 5wt% of perfluorinated sulfonic acid solution to obtain catalyst ink, dripping the catalyst ink on the surface of the polished working electrode, and drying to obtain the redox electrode.
9. A cathode electrode for a zinc-air battery, characterized in that the cadmium-based composite material according to claim 1 is used as a catalyst material, and the preparation method of the cathode electrode for the zinc-air battery comprises the following steps: mixing the cadmium-based composite material with isopropanol, water and 5wt% of perfluorosulfonic acid solution to obtain catalyst ink, dripping the catalyst ink on hydrophilic carbon fiber paper, and drying to obtain the zinc-air battery cathode electrode.
CN202210655049.5A 2022-06-10 2022-06-10 Cadmium-based composite material and preparation method and application thereof Active CN114914461B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210655049.5A CN114914461B (en) 2022-06-10 2022-06-10 Cadmium-based composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210655049.5A CN114914461B (en) 2022-06-10 2022-06-10 Cadmium-based composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114914461A CN114914461A (en) 2022-08-16
CN114914461B true CN114914461B (en) 2023-02-28

Family

ID=82770289

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210655049.5A Active CN114914461B (en) 2022-06-10 2022-06-10 Cadmium-based composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114914461B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107651656A (en) * 2017-09-15 2018-02-02 电子科技大学 A kind of Ni2P4O12Nano-particle material and its preparation method and application
CN113287215A (en) * 2018-12-19 2021-08-20 舍弗勒技术股份两合公司 Fuel cell or electrolyser
WO2022095492A1 (en) * 2020-11-04 2022-05-12 江苏科技大学 High-performance metal-air cell positive electrode catalyst and preparation method therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107651656A (en) * 2017-09-15 2018-02-02 电子科技大学 A kind of Ni2P4O12Nano-particle material and its preparation method and application
CN113287215A (en) * 2018-12-19 2021-08-20 舍弗勒技术股份两合公司 Fuel cell or electrolyser
WO2022095492A1 (en) * 2020-11-04 2022-05-12 江苏科技大学 High-performance metal-air cell positive electrode catalyst and preparation method therefor

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Highly active M2P2O7@NC (M = Co and Zn) for bifunctional electrocatalysts for ORR and HER;Lian-Hua Xu等;《Journal of Catalysis》;20190725;第377卷;第20-27页 *
Hydrogen Production Improvement on Water Decomposition Through Internal Interfacial Charge Transfer in M3(PO4)2-M2P2O7 Mixed-Phase Catalyst (M = Co, Ni, and Cu);Junyeong Kim等;《Catalysts》;20190713;第9卷;第1-14页 *

Also Published As

Publication number Publication date
CN114914461A (en) 2022-08-16

Similar Documents

Publication Publication Date Title
CN109678153A (en) The preparation method and its catalytic applications in fuel battery negative pole of a kind of N doping porous carbon
EP3062372A1 (en) Tungsten-based material super battery and supercapacitor
CN111001428A (en) Metal-free carbon-based electrocatalyst, preparation method and application
CN114628696B (en) Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst
CN115172741A (en) Preparation method and application of ternary metal Prussian blue positive electrode material
CN113506884A (en) Preparation method of transition metal-nitrogen-carbon electrocatalyst, electrode and battery
CN112002909B (en) Preparation method of Zn-Cu-N-based co-doped carbon composite material
CN113224325A (en) High-efficiency bifunctional oxygen electrocatalyst with heterogeneous structure and heterogeneous metals, and preparation and application thereof
CN114914461B (en) Cadmium-based composite material and preparation method and application thereof
CN115347200B (en) Conjugated microporous polymer catalyst and preparation method and application thereof
CN114944495B (en) Difunctional oxygen electrocatalyst with CoN/MnO double active sites and preparation and application thereof
CN116895770A (en) Nickel-nickel oxide heterostructure catalyst, electrode, preparation method and application thereof
CN114843529B (en) Porous carbon sphere derived based on water system ZIF, and preparation method and application thereof
CN114709428B (en) Defect tungsten oxide/ruthenium nanoparticle composite catalyst and preparation method and application thereof
CN101901916B (en) Carbon-carried manganese tetraoxide composite catalytic material and preparation method thereof
CN115513470A (en) Bimetallic monatomic nitrogen-doped porous carbon electrocatalyst and preparation method thereof
CN113394415A (en) Oxygen-enriched vacancy NC @ BiOCl-CNTs composite material as well as preparation method and application thereof
CN114220971A (en) Three-dimensional ordered cobalt-nitrogen microporous carbon material with strong catalytic action and preparation method and application thereof
CN113201746A (en) Fluorine modified nickel cobaltate modified carbon nanotube electrode catalyst
CN113201750A (en) Fluorine modified copper cobaltate modified carbon nanotube electrode catalyst
CN116130683B (en) Ternary nano nitride material for solid metal fuel cell and preparation method thereof
CN115566207B (en) Transition metal pyrophosphate ORR catalyst anchored on MOFs derived carbon skeleton, and preparation method and application thereof
CN115434041B (en) Tin-doped porous carbon fiber material with in-situ reaction in MOF pores, and preparation method and application thereof
CN114914460B (en) Dual-function catalytic material and preparation method and application thereof
CN110156078B (en) Preparation method and application of potassium-vanadium-oxygen ternary compound

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