CN114188549B - Preparation and application of nitrogen-sulfur-doped cellulose as flexible zinc-air battery electrode - Google Patents

Preparation and application of nitrogen-sulfur-doped cellulose as flexible zinc-air battery electrode Download PDF

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CN114188549B
CN114188549B CN202111521069.5A CN202111521069A CN114188549B CN 114188549 B CN114188549 B CN 114188549B CN 202111521069 A CN202111521069 A CN 202111521069A CN 114188549 B CN114188549 B CN 114188549B
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cellulose
air battery
battery electrode
dispersion liquid
nitrogen
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CN114188549A (en
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王猛
庞怀鹏
孙佩佩
邓建林
高萌
李勇
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New Material Institute of Shandong Academy of Sciences
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    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/88—Processes of manufacture
    • 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
    • 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
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses preparation and application of nitrogen-sulfur doped cellulose as a flexible zinc-air battery electrode, and belongs to the technical field of batteries. The flexible zinc-air battery electrode material is cellulose-based carbon foam, and raw materials comprise nanocellulose and first dispersion liquid. The preparation method comprises the following steps: placing a cellulose raw material in an oxidant for oxidation modification, and homogenizing to obtain nano cellulose; dispersing a heteroatom compound and/or a carbon material in a solvent to obtain a first dispersion liquid; and mixing the nanocellulose and the first dispersion liquid, freezing, drying and pyrolyzing to obtain the flexible zinc-air battery electrode material. The cellulose-based carbon foam has a directional pore channel structure and high flexibility, can effectively promote electron transfer and mass transfer, and can improve the specific surface area of the material, thereby exposing more catalytic active sites and endowing the cellulose-based carbon foam with excellent electrocatalytic performance.

Description

Preparation and application of nitrogen-sulfur-doped cellulose as flexible zinc-air battery electrode
Technical Field
The invention relates to the technical field of batteries, in particular to preparation and application of nitrogen-sulfur-doped cellulose as a flexible zinc-air battery electrode.
Background
With the vigorous development of wearable electronic technology, people have a great demand for flexible portable devices, and rechargeable Zinc Air Batteries (ZABs) have attracted much attention as energy storage devices for portable devices due to their advantages of high theoretical specific energy density, low cost, high safety, and the like. The development of cheap electrode materials with high-efficiency electro-catalytic performance of the flexible zinc-air battery is the key of research, and currently, electrode catalyst materials mainly comprise noble metal (Pt) and ruthenium/iridium-based oxide, so that the price is high and the resources are scarce. Conventional metal-air batteries generally use a powdered catalyst as an electrode material, requiring the introduction of an organic binder, which reduces the quality, energy density, and cycle life of the battery. In addition, rigid electrode materials are difficult to meet the requirements of flexible energy storage equipment, and higher requirements are put forward on the mechanical properties of the electrode materials. Therefore, the development and design of flexible electrodes with high-activity catalytic sites and self-supporting structures are great challenges for the development of flexible zinc-air batteries.
Cellulose is one of the most abundant natural high molecular polymers on the earth, is an inexhaustible natural renewable resource, has the properties of high carbon content, high flexibility, high mechanical strength and the like, and has very high application value in the field of energy storage materials. However, cellulose itself is difficult to conduct electricity and has poor electrochemical performance, and how to realize high stability, high electrocatalysis and high flexibility of the cellulose electrocatalysis material, so that the substitution of the traditional commercial Pt/C electrocatalysis material is still a great challenge.
Disclosure of Invention
The invention provides a preparation method and application of nitrogen-sulfur-doped cellulose as a flexible zinc-air battery electrode, which aims to solve the technical problem that the application of the existing metal-air battery is limited.
In order to achieve the purpose, the invention provides the following scheme:
one purpose of the invention is to provide a flexible zinc-air battery electrode material, which is cellulose-based carbon foam and comprises raw materials of nanocellulose and first dispersion liquid;
the raw material of the nano-cellulose comprises a cellulose raw material and an oxidant; nanocrystallization of cellulose can increase the specific surface area of cellulose and impart a uniform pore structure to the cellulose aerogel.
The raw material of the first dispersion liquid includes a heteroatom compound and/or a carbon material.
Further, the cellulose raw material is one or more of softwood kraft pulp board, cotton pulp and filter paper; the oxidant includes 2,2,6,6-tetramethylpiperidine-nitrogen-oxide (TEMPO), naBr, and NaClO.
Further, the heteroatom compound is a nitrogen-containing compound and a sulfur-containing compound; the carbon material is one or two of graphene, carbon nanotubes and carbon black.
Further, the nitrogen-containing compound is one or more of urea, melamine, dicyandiamide and dicyandiamide; the sulfur-containing compound is one or more of thiourea, carbon disulfide, dimethyl sulfoxide and trithiocyanuric acid.
The invention also provides a preparation method of the flexible zinc-air battery electrode material, which comprises the following steps:
(1) Preparing nano-cellulose: washing a cellulose raw material with deionized water, placing the cellulose raw material in an oxidant solution for oxidation modification, washing the cellulose raw material with deionized water after the reaction is finished (removing unreacted substances and impurities on the surface of fibers), and homogenizing the cellulose raw material with a high-pressure homogenizer to obtain semitransparent nanocellulose;
(2) Preparation of the first dispersion: dispersing a heteroatom compound and/or a carbon material in a solvent to obtain a first dispersion liquid;
(3) And uniformly mixing the nanocellulose and the first dispersion liquid to obtain a second dispersion liquid, placing the second dispersion liquid in a mold for freezing, solidifying the second dispersion liquid, and drying and pyrolyzing the second dispersion liquid to obtain the flexible zinc-air battery electrode material, namely the cellulose-based carbon foam.
Mixing the nano-cellulose with the first dispersion liquid, uniformly dispersing the carbon material in the first dispersion liquid in the nano-cellulose to form a nano-cellulose foam skeleton, and simultaneously, uniformly loading the heteroatom compound in the first dispersion liquid in the nano-cellulose to form a precursor.
Further, in the step (1), the solute of the oxidant solution is 2,2,6,6-tetramethylpiperidine-nitrogen-oxide, naBr and NaClO, and the solvent is water and/or NaOH; the mass volume ratio of the cellulose raw material, 2,2,6,6-tetramethyl piperidine-nitrogen-oxide and the solvent is 1g (0.014-0.018) g:100mL; the mass ratio of 2,2,6,6-tetramethylpiperidine-nitrogen-oxide to NaBr is (1-8): 25, and the molar weight of NaClO in the oxidant solution is 30-80 mmol/L.
Further, in the step (1), the pH value of the oxidant solution is 9-11; the homogenizing pressure is 80-110 MPa, and the homogenizing times are 3-5 times.
Further, in the step (2), the solvent is ethanol and/or water; the concentration of the heteroatom compound is 0.1-0.5 wt%; the content of the carbon material is 0.3-0.5 wt%.
Further, the freezing is liquid nitrogen freezing, preferably directional freezing, using bottom liquid nitrogen to quickly freeze, and the upper part is exposed to air, so that ice crystals grow from the bottom to the top of the cellulose foam.
The second dispersion is directionally frozen to control its microstructure to have a pore structure that tends to be uniform, thereby improving its mechanical flexibility.
Further, in the step (3), the mass ratio of the nano-cellulose to the first dispersion liquid is 1 (200-1000); the drying is freeze drying, the temperature is-50 to-20 ℃, and the time is 24 to 48 hours;
the pyrolysis is carried out in inert atmosphere, the inert atmosphere is argon and/or nitrogen, the pyrolysis temperature is 800-1000 ℃, the time is 2-4 h, and the heating rate is 1-10 ℃/min.
High temperature pyrolysis (high temperature carbonization) can achieve graphitization of the cellulose foam, enrich the pore structure of the foam, and effectively embed heteroatoms into carbon lattices. The addition of the heteroatom compound can increase the alkaline sites on the surface of the material, enhance the hydrophilicity of the material and change the lattice structure of the carbon foam, so that the cellulose-based carbon foam has excellent electrocatalytic performance.
The invention also aims to provide application of the flexible zinc-air battery electrode material in preparation of a flexible metal-air battery.
Further, the metal-air battery is a zinc-air battery.
The invention also provides a cathode electrocatalyst which is prepared from the flexible zinc-air battery electrode material (cellulose-based carbon foam).
The invention also provides a flexible cathode, which comprises the cathode electrocatalyst.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides cellulose-based carbon foam, which is prepared by modifying the surface of cellulose and mechanically treating to obtain nano-cellulose, mixing the nano-cellulose with a first dispersion solution, directionally freezing, drying, and pyrolyzing to obtain the cellulose-based carbon foam.
Cellulose raw materials (needle wood sulfate pulp boards, cotton pulp, filter paper and the like) and an oxidant solution are subjected to oxidation modification reaction, and the oxidant can react with hydroxyl at the C6 position of the cellulose to oxidize the hydroxyl into carboxyl, so that negative charges are given to the surface of the cellulose, and the stability of the cellulose in water is improved. The modified cellulose is subjected to high-pressure homogenization, so that the cellulose can be decomposed to a nanometer level, the specific surface area of the cellulose is increased, the porosity of cellulose foam and carbon foam is increased, more reactive sites are provided, and the loading of heteroatoms is facilitated.
Mixing the nanocellulose with the first dispersion liquid is beneficial to dispersing the carbon material in the first dispersion liquid and forming a uniform carbon foam structure; and the addition of the heteroatom compound effectively changes the structure of the cellulose-based carbon foam, improves the graphitization degree of the cellulose-based carbon foam, increases the alkaline sites on the surface of the cellulose-based carbon foam, and enhances the hydrophilicity of the cellulose-based carbon foam. The cellulose-based carbon foam has a directional pore channel structure and high flexibility, can effectively promote electron transfer and mass transfer, can improve the specific surface area of a material, thereby exposing more catalytic active sites, and can endow the cellulose-based carbon foam with excellent electrocatalytic performance.
(2) The cellulose-based carbon foam is used for preparing a cathode electrocatalyst, a cathode and a flexible metal-air battery, so that the material has excellent electrocatalytic performance, and simultaneously, cellulose with rich sources and low price is used as a carbon source, so that the use of expensive noble metal materials is avoided, the preparation cost is greatly reduced, and a new idea is provided for high-value utilization of the cellulose.
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 electron microscope image of different stages of a material in example 1 of the present invention, wherein a is a transmission electron microscope image of nanocellulose, b is a 3D model image of cellulose-based carbon foam, and c and D are scanning electron microscope images of cellulose-based carbon foam in different directions;
FIG. 2 is a graph comparing adsorption volumes of cellulose-based carbon foams in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 3 is a graph comparing OER of cellulose-based carbon foam with platinum on carbon in example 1, comparative example 1, and comparative example 2 of the present invention;
FIG. 4 is a charge-discharge cycle diagram of flexible zinc-air cells prepared with the cathode electrocatalyst according to example 11 and comparative example 11 of the present invention;
FIG. 5 is a graph showing the discharge stability at different bending angles of a flexible zinc-air cell prepared by using the cathode electrocatalyst according to example 11.
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 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. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a 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 herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. 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.
In the present invention, those whose specific conditions are not specified in the examples are conducted under the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the present invention, the concentration of the heteroatom compound is 0.1 to 0.5wt%, and typical but non-limiting concentrations are 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, or 0.5wt%; the carbon material is present in an amount of 0.3 to 0.5wt%, with typical but non-limiting concentrations being 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, or 0.5wt%.
In the invention, the mould during freezing is a cubic groove with an opening on the surface, the bottom of the cube is made of copper material, and the periphery of the cube is made of polytetrafluoroethylene; the freezing step is to pour the second dispersion into a mold, and the bottom of the mold is immersed in liquid nitrogen, so that the ice crystals in the dispersion grow upwards along the bottom of the mold.
In the invention, the temperature of freeze drying is-50 to-20 ℃ and the time is 24 to 48 hours, the typical but not limiting temperature is-50 ℃, 40 ℃, 30 ℃, 35 ℃ or-20 ℃, and the typical but not limiting time is 24 hours, 30 hours, 35 hours, 40 hours, 45 hours or 48 hours;
in the invention, the pyrolysis temperature is 800-1000 ℃, the time is 2-4 h, the heating rate is 1-10 ℃/min, the typical but non-limiting pyrolysis temperature is 800 ℃, 850 ℃, 900 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃ or 1000 ℃, the typical but non-limiting pyrolysis time is 2h, 2.5h, 3h, 3.5h or 4h, and the typical but non-limiting heating rate is 1 ℃/min, 2 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min.
Example 1
(1) Preparing nano-cellulose: putting 1g of softwood kraft pulp board (solar paper industry) into 100mL of deionized water, adding 0.016g of TEMPO and 0.1g of NaBr, stirring until the TEMPO and the NaBr are dissolved, then adding 5.0mmol of NaClO solution, starting reaction, dropwise adding NaOH into the solution to maintain the pH of the solution at about 10, filtering and washing to be neutral after the reaction is finished, and then carrying out 5-time circular homogenization in a high-pressure homogenizer (100 MPa) to obtain the nano-cellulose;
(2) Preparation of the first dispersion: dispersing a heteroatom compound (the mass ratio of dicyandiamide to thiourea is 1:1) and a carbon material (carbon nano tube) in a solvent to enable the content of the heteroatom compound in the solution to be 0.4wt% and the content of the carbon material to be 0.5wt% to obtain a first dispersion liquid;
(3) Uniformly mixing the nanocellulose and the first dispersion liquid to obtain a second dispersion liquid, wherein the mass ratio of the nanocellulose to the first dispersion liquid is 1.
Example 2
The preparation method of the cellulose-based carbon foam provided in this example is the same as that of example 1, except that the carbon material is replaced with graphene, and the remaining process steps and process parameters are the same.
Example 3
The preparation method of the cellulose-based carbon foam provided in this example is the same as that of example 1, except that the heteroatom compound is replaced by dicyandiamide and trithiocyanuric acid (the mass ratio is 1:1).
Example 4
The method for preparing a cellulose-based carbon foam provided in this example was the same as in example 1 except that no heteroatom compound was added.
Example 5
The preparation method of the cellulose-based carbon foam provided in this example was the same as that of example 1 except that no carbon material was added.
Example 6
The method for preparing the cellulose-based carbon foam provided in this example was the same as example 1 except that the dispersion was directly placed in a low temperature (-25 ℃) refrigerator without using a mold freezing method, and the remaining process steps and process parameters were the same as those of example 1.
Example 7
The preparation method of the cellulose-based carbon foam provided in this example is the same as that of example 1 except that the pyrolysis temperature is 800 ℃, the heating rate is 10 ℃/min, and the rest of the process steps and process parameters are the same.
Example 8
The method for preparing the cellulose-based carbon foam according to this example was the same as example 1, except that the kind of the cellulose raw material was replaced with cotton pulp, and the remaining process steps and process parameters were the same.
Example 9
The method for preparing the cellulose-based carbon foam according to this example was the same as example 1, except that the type of the cellulose raw material was replaced with filter paper, and the remaining process steps and process parameters were the same.
Example 10
The method for preparing a cellulose-based carbon foam provided in this example was the same as in example 1 except that the heteroatom compound was replaced with urea and thiourea (mass ratio 1:1).
Examples 11 to 20
Examples 11-20 provide an assembled flexible solid zinc-air battery cathode electrocatalyst made using the cellulose-based carbon foams provided in examples 1-10, respectively;
the preparation method of the flexible solid zinc-air battery comprises the following steps:
adding 1.0g of polyvinyl alcohol (Mw = 30000-70000) powder into 10mL of deionized water, carrying out magnetic stirring at 90 ℃ for 2h to fully dissolve the polyvinyl alcohol, then adding 1.0mL of mixed solution of KOH (18 mol/L) and ZnOAc (0.02 mol/L), wherein the molar ratio of KOH to ZnOAc is 900. And finally, placing cellulose-based carbon foam (1cm x 0.5 cm) and zinc foil (with the thickness of 0.05 mm) on two sides of the PVA gel respectively, using the pressed Ni foam as a current collector of an air electrolyte, and packaging the two layers together to form the flexible solid-state battery.
Comparative example 1
This comparative example provides a method for preparing cellulose-based carbon foam, in which nanocellulose was directly freeze-dried and pyrolyzed at high temperature without adding the first dispersion, and the remaining steps and process parameters were the same as in example 1, compared to example 1.
Comparative example 2
This comparative example provides a method for preparing a cellulose-based carbon foam by directly mixing commercially available microcrystalline cellulose with the first dispersion and adding 0.5mol of FeCl 3 And placing the mixture into a mold for directional freezing, freezing and drying the frozen mixture for 24h at the temperature of minus 50 ℃ in a freeze dryer, finally pyrolyzing the frozen mixture in a tubular furnace at the heating rate of 5 ℃/min for 2h at the temperature of 900 ℃ in the nitrogen atmosphere to obtain the flexible zinc-air battery electrode material.
Comparative example 3
The comparative example provides a method for preparing a cellulose-based carbon foam, which includes the same process steps and process parameters as example 1, except that the heteroatom compound is replaced with melamine.
Comparative example 4
The preparation method of the cellulose-based carbon foam provided in the present comparative example was the same as example 1 except that the heteroatom compound was replaced with trithiocyanuric acid, and the remaining process steps and process parameters were the same.
Comparative example 5
The comparative example provides a method for preparing a cellulose-based carbon foam, which includes the same process steps and process parameters as example 1, except that the heteroatom compound is replaced with dicyanodiamide.
Comparative example 6
The method for preparing the cellulose-based carbon foam according to the present comparative example was the same as example 1 except that the nanocrystallization was not performed in step (1) but the cellulose raw material was directly mixed with the first dispersion solution, and the remaining process steps and process parameters were the same as those of example 1.
Comparative examples 7 to 12
Comparative examples 7 to 12 provide a cathode electrocatalyst prepared using the cellulose-based carbon foams provided in comparative examples 1 to 6, respectively, and the preparation method of the cathode electrocatalyst was the same as in examples 11 to 20.
To verify the technical effects of the respective examples and comparative examples, the following experiments were conducted.
Experimental example 1
Observing the microscopic morphology of the material in example 1, as shown in a diagram of fig. 1, the diameter of the obtained nanocellulose is 5-10 nm and the length is up to tens of microns after the cellulose raw material is modified and mechanically treated. As shown in b of fig. 1, after directional freezing and freeze-drying in a mold, a vertical pore structure with a uniform trend is obtained, and after pyrolysis carbonization under inert gas, the volume is reduced by 70%, and the pore structure is still substantially consistent with the cellulose-based aerogel, so that the structure not only has very high mechanical flexibility, but also is beneficial to providing more active sites.
Experimental example 2
The adsorption volumes of the cellulose-based carbon foams were measured and analyzed using a specific surface analyzer (SSA 6000) as represented by example 1, comparative example 1, and comparative example 2, as shown in fig. 2. Example 1 celluloseThe adsorption volume of the base carbon foam is up to 160m 2 The adsorption curve has a typical IV-type isotherm, which indicates that a large number of mesopores exist in example 1, and the higher adsorption volume and the multi-scale pore structure are favorable for exposing more surface active sites and are favorable for rapidly carrying out electrochemical reaction. The cellulose carbon aerogel of comparative example 1 does not contain the heteroatom compound in the first dispersion, and the adsorption capacity is lower than that of example 1. In comparative example 2, the adsorption volume was slightly higher than that of example 1 due to the addition of carbon black having a higher adsorption volume.
Experimental example 3
The Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) of the cathode electrocatalysts provided in examples 11 to 20 were examined and supported with commercial platinum on carbon (Pt/C) and ruthenium oxide (RuO) 2 ) For comparison, the specific results are shown in table 1.
The specific detection method comprises the following steps: a2 mg sample of the cathode electrocatalyst was weighed, dispersed in 200. Mu.L of a 5wt% mixture of perfluorosulfonic acid and 800. Mu.L of ethanol, and the mixture was sonicated to give a homogeneous test solution. The prepared cathode electrocatalyst test solution is coated on a rotating disc working electrode, and a three-electrode system is used during testing, wherein a counter electrode is a carbon rod, and an Ag/AgCl (saturated KCI) electrode is a reference electrode. Cyclic voltammetry testing: the scanning range is 0.05-1.1V, and the scanning speed is 10mV/s; linear sweep voltammetry: the scanning range is 0.2-1.1V, the scanning speed is respectively 10mV/s, and the rotating speed is 1600rpm. The test was carried out in 0.1mol/LKOH electrolyte solution at room temperature. Tafel curve: the scanning rate was 10mV/s, and the rotation speed was 1600rpm. Test voltage according to formula (E) RHE ＝E Ag/AgCl +0.059pH + 0.197) to the relative standard hydrogen electrode (VS) RHE ) A voltage.
TABLE 1
Figure BDA0003407608740000131
As can be seen from the data in table 1, the electrocatalytic performance of the cellulose-based carbon foam provided by example 1 of the present invention is generally superior to that of the other examples. Meanwhile, fig. 3 is a graph of oxygen reduction electrocatalytic performance of the carbon-supported platinum, the cellulose-based carbon foams of example 1, comparative example 1, and comparative example 2. As can be seen from fig. 3, the oxygen reduction electrocatalytic performance of the cellulose-based carbon foam provided in example 1 is significantly better than that of comparative examples 1 and 2, and the initial potential, half-wave potential and limiting current density are almost similar to those of commercial platinum on carbon, mainly due to the interaction between the nitrogen-sulfur element doping and the cellulose carbon foam support.
Experimental example 4
Comparing the cathode electrocatalyst provided in example 11 and comparative example 11 to prepare a flexible zinc-air cell, as shown in fig. 4, the charge-discharge cycle performance of the flexible zinc-air cell prepared using the cathode electrocatalyst of example 11 was significantly better than that of comparative example 11, and the flexible zinc-air cell of example 11 also showed good cycle stability with almost no significant voltage decay after 300 minutes.
In addition, in order to verify the mechanical flexibility and the operation stability of the flexible zinc-air battery prepared by using the cathode electrocatalyst of the invention, as shown in fig. 5, the flexible zinc-air battery based on the cathode electrocatalyst of example 11 was bent at different bending angles, and the change of the voltage gap of the discharge curve was small, which indicates that the flexible zinc-air battery has good mechanical flexibility and discharge stability.
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 (7)

1. The flexible zinc-air battery electrode material is characterized by being cellulose-based carbon foam, and the raw materials comprise nanocellulose and first dispersion liquid;
the raw material of the nano-cellulose comprises a cellulose raw material and an oxidant;
the raw material of the first dispersion liquid comprises a heteroatom compound and/or a carbon material;
the cellulose raw material is one or more of softwood kraft pulp board, cotton pulp and filter paper; the oxidant comprises 2,2,6,6-tetramethylpiperidine-nitrogen-oxide, naBr and NaClO;
the preparation method of the flexible zinc-air battery electrode material comprises the following steps:
(1) Preparing nano cellulose: placing a cellulose raw material in an oxidant solution for oxidation modification, and performing homogenization treatment to obtain nano cellulose;
(2) Preparation of the first dispersion: dispersing a heteroatom compound and/or a carbon material in a solvent to obtain a first dispersion liquid;
(3) Uniformly mixing the nanocellulose and the first dispersion liquid to obtain a second dispersion liquid, and freezing, drying and pyrolyzing the second dispersion liquid to obtain a flexible zinc-air battery electrode material, namely cellulose-based carbon foam;
in the step (3), the mass ratio of the nano-cellulose to the first dispersion liquid is 1 (200-1000); the freezing is liquid nitrogen freezing; the drying is freeze drying, the temperature is-50 to-20 ℃, and the time is 24 to 48 hours; the pyrolysis temperature is 800-1000 ℃, the time is 2-4 h, and the heating rate is 1-10 ℃/min.
2. The flexible zinc-air battery electrode material of claim 1, wherein the heteroatom compound is a nitrogen-containing compound and a sulfur-containing compound; the carbon material is one or two of graphene, carbon nanotubes and carbon black.
3. The flexible zinc-air battery electrode material according to claim 2, wherein the nitrogen-containing compound is one or more of urea, melamine, dicyandiamide and dicyanodiamine; the sulfur-containing compound is one or more of thiourea, carbon disulfide, dimethyl sulfoxide and trithiocyanuric acid.
4. The flexible zinc-air battery electrode material as claimed in claim 1, wherein in step (1), the oxidant solution has solutes of 2,2,6,6-tetramethylpiperidine-nitrogen-oxide, naBr and NaClO, and the solvent is water and/or NaOH; the mass volume ratio of the cellulose raw material, 2,2,6,6-tetramethyl piperidine-nitrogen-oxide and the solvent is 1g (0.014-0.018) g:100mL; the mass ratio of 2,2,6,6-tetramethylpiperidine-nitrogen-oxide to NaBr is (1-8) to 25, and the molar weight of NaClO in the oxidant solution is 30-80 mmol/L; the pH value of the oxidant solution is 9-11; the homogenizing pressure is 80-110 MPa, and the homogenizing times are 3-5 times.
5. The flexible zinc-air battery electrode material according to claim 1, wherein in the step (2), the solvent is ethanol and/or water; the concentration of the heteroatom compound is 0.1-0.5 wt%; the content of the carbon material is 0.3-0.5 wt%.
6. Use of a flexible zinc-air battery electrode material according to any one of claims 1 to 3 in the preparation of a flexible metal-air battery.
7. Use according to claim 6, wherein the metal-air battery is a zinc-air battery.
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