CN116364964A - Preparation method and application of waste wood derived porous carbon integrated dual-function air electrode - Google Patents
Preparation method and application of waste wood derived porous carbon integrated dual-function air electrode Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 15
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- 238000012360 testing method Methods 0.000 description 8
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01M4/96—Carbon-based electrodes
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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
- 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
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
- H01M4/90—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
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- 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
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Abstract
The invention discloses a preparation method and application of a waste wood derived porous carbon integrated dual-function air electrode. The chemical composition of the dual-function air electrode is CoNiLDH@NPC, the invention takes the nitrogen-phosphorus doped self-supporting carbon material derived from waste wood as a substrate for the first time, takes cobalt salt and nickel salt as LDH synthesis sources, synthesizes the LDH catalytic material with a nano-sheet structure on the substrate through in-situ hydrothermal growth, and obtains the integrated nitrogen-phosphorus doped carbon material dual-function air electrode loaded with CoNi-LDH. The dual-function air electrode forms an electrochemical heterogeneous interface formed by the carbon carrier and the nano sheet while retaining the characteristics of a layered porous structure and a larger specific surface area of wood, is favorable for full exposure of active sites, enriches the electron density at the interface, greatly improves the electrocatalytic performance, and has excellent discharge power density and charge-discharge stability.
Description
Technical Field
The invention relates to a preparation method and application of a waste wood derived porous carbon integrated dual-function air electrode, and belongs to the technical field of electrocatalysis.
Background
A rechargeable zinc-air battery (RZAB) has been attracting attention in recent years as a renewable energy conversion and storage device due to its characteristics of environmental protection, non-toxicity, high energy density (1086 Wh/Kg), and the like. However, the energy conversion efficiency of ZABs is severely limited due to the slow kinetics of the four electron transfer pathway during oxygen conversion, where Oxygen Evolution Reactions (OER) and Oxygen Reduction Reactions (ORR) are the core processes of all metal-air cells occurring at the cathode (air electrode) interface. During discharge and charge, although noble metal materials (Pt/C, ruO 2 And IrO 2 ) Is the most advanced ORR and OER electrocatalyst at present, but the lack of scarcity and catalytic stability of these materials has hindered the widespread use of RZAB.
Ion chemical engineering is an effective way to improve catalytic performance, wherein Layered Double Hydroxide (LDH) nanoplatelets are typically represented, consisting of hydroxide-coordinated metal cations as the main layer, and anions or molecular water as the intermediate layer. The structure enables the layer composition of the LDH to be accurately regulated and controlled to obtain good physical and chemical properties, and the lamellar morphology and the lamellar structure can expose a large number of active sites, and the LDH shows excellent activity in the OER catalysis process. For example, cobalt-nickel layered double hydroxide (CoNi-LDH) has a main layer composed of a large amount of divalent cobalt ions and trivalent nickel ions, and the two ions are electronically modulated through valence bands of each other to optimize the free energy of adsorption and desorption of reactants and products and accelerate catalytic kinetics, so that the reaction is facilitated. The CoNi-LDH containing a large amount of nickel ions in a high valence state has extremely high OER activity, but the bifunctional catalytic performance of the CoNi-LDH is not satisfactory due to its low conductivity and lack of ORR active sites. In order to cope with the above problems, LDH nanosheet rivets are usually used on carbon material substrates such as graphene, carbon nanotubes, carbon nano frames and carbon nano cages to achieve good conductivity and catalytic stability. However, the problems of high cost, low catalytic activity and complicated preparation process of the carbon material still exist, and how to conveniently and efficiently prepare the catalyst consisting of LDH and nano carbon material, so that an efficient long-term stable oxygen electrocatalytic process is realized, and the problems and hot spots of the current dual-function catalytic material research are caused.
In addition to the development of electrocatalytic materials, the preparation of conventional air electrodes is usually achieved by spraying powdered catalysts onto a conductive substrate, which often results in weak interactions between the catalyst and the substrate, causing the catalyst to fall off during long-term reactions, severely compromising battery performance, and thus direct construction of catalytic materials on conductive substrates has received great attention.
Disclosure of Invention
The purpose of the invention is that: aiming at the technical problems of poor LDH conductivity, insufficient dual-functionality, complicated preparation process, insufficient durability of the traditional spray-type air electrode in long-time reaction and the like in the prior art, the invention provides a preparation method for converting low-cost waste wood into an efficient air electrode in a zinc-air battery.
In order to solve the technical problems, the invention provides a waste wood-derived porous carbon integrated type dual-function air electrode, which has the chemical composition of CoNiLDH@NPC, wherein the dual-function air electrode takes a wood-derived nitrogen-phosphorus doped self-supporting carbon material as a substrate, takes cobalt salt and nickel salt as LDH synthesis sources, synthesizes an LDH catalytic material with a nano-sheet structure on the substrate through in-situ Shui Resheng length, and obtains the integrated nitrogen-phosphorus doped carbon material loaded with CoNi-LDH, namely the dual-function air electrode.
The invention also provides a preparation method of the waste wood-derived porous carbon integrated dual-function air electrode, which comprises the following steps:
step 1): placing wood chips in phosphoric acid deionized water solution for hydrothermal reaction;
step 2): taking out the wood chips after the reaction is finished, mixing the wood chips with urea and monoammonium phosphate after drying, and placing the mixture in a tube furnace for pyrolysis under inert atmosphere to obtain a self-supporting nitrogen-phosphorus doped carbon substrate;
step 3): co (NO) 3 ) 3 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O and CO (NH) 2 ) 2 Adding the mixture into deionized water, and completely dissolving to obtain a mixed solution;
step 4): adding the self-supporting nitrogen-doped carbon substrate obtained in the step 2) into the mixed solution obtained in the step 3), fully soaking, and transferring to a reaction kettle for hydrothermal reaction;
step 5): and after the reaction is finished, taking out the carbon substrate, washing with deionized water, and freeze-drying to obtain the wood-derived porous carbon integrated dual-function air electrode.
Preferably, the wood chip size in the step 1) is 20mm×20mm×3mm, and the concentration of the deionized water solution of phosphoric acid is 25-35 wt%.
Preferably, the temperature of the hydrothermal reaction in the step 1) is 135-145 ℃ and the time is 10-14 h.
Preferably, the drying temperature in the step 2) is 75-85 ℃ and the time is 45-50 h.
Preferably, the mass ratio of urea to monoammonium phosphate in the step 2) is 1:1, and the pyrolysis process conditions are as follows: the temperature is 850-950 ℃, the temperature rising rate is 4-6 ℃/min, and the time is 1-3 h.
Preferably, co (NO) in said step 3) 3 ) 3 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O and CO (NH) 2 ) 2 Is 2:2:20, said Co (NO 3 ) 3 ·6H 2 The molar concentration of O is 0.02-0.03 mol/L.
Preferably, the time of the soaking in the step 4) is 1-3 hours, the temperature of the hydrothermal reaction is 115-125 ℃ and the time is 7-9 hours.
Preferably, the freeze drying time in the step 5) is 20 to 30 hours.
The invention also provides application of the waste wood-derived porous carbon integrated dual-function air electrode in a zinc-air battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention takes cheap and easily available waste wood as a raw material for constructing a carbon substrate, and then loads CoNi-LDH on the obtained carbon substrate to prepare the self-supporting air electrode, and aims at the defects of low electronic conductivity, poor catalytic stability, poor dual-function catalytic activity and the like of the CoNi-LDH;
(2) According to the invention, firstly, a nano flake CoNi-LDH is constructed in a wood-derived carbon carrier by adopting an in-situ hydrothermal growth method, a catalytic high-efficiency carbon composite material is constructed, an electrochemical heterogeneous interface formed by the carbon carrier and the nano flake is formed, the porous characteristic of the wood ensures that the carbon carrier has a large specific surface area, gas transmission in the catalytic reaction process is facilitated, and the carbon carrier can be combined with a fully exposed catalytic active site, so that the reaction is promoted, meanwhile, the load of the nano flake regulates the wettability of the surface of an air electrode, a high-efficiency solid-liquid-gas three-phase interface is formed, the heterogeneous catalytic performance of the air electrode is improved, and the stability of the prepared electrode in the charge-discharge process is further improved;
(3) According to the invention, the carbon carrier subjected to nitrogen doping treatment is effectively combined with the CoNi-LDH nanosheets, so that the electron density of an electrochemical heterogeneous interface is further enriched, a widely distributed three-dimensional structure electron transport network is ensured to be formed inside the air electrode, the self impedance of the material is reduced, the electron conductivity of the material is improved, and the dual-functionality of the air electrode prepared by the method is greatly improved;
(4) The waste wood derived difunctional air electrode prepared by the invention has half-wave potential of up to 0.85V in the ORR catalytic process, shows over-potential of only 320mV in the OER process, and directly uses the self-supporting electrode in a zinc-air battery, and shows up to 263mW/cm 2 The peak discharge power density and the charge-discharge cycle performance of up to 500h show great potential commercial prospect.
Drawings
FIG. 1 is an SEM image of the waste wood prepared in comparative example 1 derived from a supporting nitrogen-doped carbon substrate (a), the CoNi-LDH catalytic material (b) prepared in comparative example 2, and the waste wood-derived integrated bifunctional air electrode (c) prepared in example 1;
FIG. 2a is a graph comparing ORR polarization curves of the materials prepared in examples and comparative examples with Pt/C;
FIG. 2b shows the materials prepared in the examples and comparative examples together with RuO 2 OER polarization curve contrast plot of (b);
FIG. 3a is a self-supporting morphology and powder morphology of a waste wood-derived integrated dual function air electrode prepared in example 1 with Pt/C-RuO 2 Is a graph of the discharge power;
FIG. 3b is a self-supporting morphology and powder morphology of 10mA/cm for the waste wood-derived integrated dual function air electrode prepared in example 1 2 Charge-discharge comparison plot at constant current.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
The microscopic morphology of the product of the present invention was tested by scanning transmission electron microscopy (SEM, hitachi S-4800). Half cell performance and cell discharge performance were tested using a cinnabar CHI760 series electrochemical workstation. The charge and discharge performance was performed on a CT2001A blue cell test system.
Example 1
The embodiment provides a preparation method of a waste wood derived integrated dual-function air electrode (CoNiLDH@NPC), which comprises the following specific preparation steps:
step 1): placing wood chips with the size of 20mm multiplied by 3mm in a 30wt% solution of phosphoric acid deionized water;
step 2): transferring the phosphoric acid aqueous solution containing the wood chips in the step 1) into an oven to carry out hydrothermal reaction at 140 ℃ for 12 hours, and then taking out the wood chips to dry at 80 ℃ for 48 hours;
step 3): mixing the completely dried wood chips with urea (2 g) and monoammonium phosphate (2 g), placing the mixture in a tube furnace, protecting the mixture by using nitrogen, maintaining the mixture at 900 ℃ for 2 hours at a heating rate of 5 ℃/min, and cooling the mixture to room temperature to obtain a self-supporting nitrogen-phosphorus doped carbon substrate;
step 4): 2mmol Co (NO) 3 ) 3 ·6H 2 O、2mmol Ni(NO 3 ) 2 ·6H 2 O and 20mmol CO (NH) 2 ) 2 Adding the mixture into 80mL of deionized water, and completely dissolving to obtain a mixed solution;
step 5): adding the self-supporting nitrogen-doped carbon substrate obtained in the step 3) into the mixed solution obtained in the step 4), fully soaking for 2 hours, and transferring the mixture into a reaction kettle to carry out hydrothermal treatment at 120 ℃ for 8 hours;
step 6): and after the reaction is finished, taking out the carbon substrate, washing with deionized water, freeze-drying for 24 hours to obtain the waste wood-derived integrated dual-function air electrode, wherein the microscopic morphology of the waste wood-derived integrated dual-function air electrode is shown in a figure 1c, and grinding the waste wood-derived integrated dual-function air electrode to obtain the dual-function air electrode in a powder form.
FIG. 1c shows that under the condition of example 1, the integrated dual-function air electrode maintains the porous characteristic of wood, ensures that the electrode has a larger specific surface area, is favorable for gas diffusion in the catalytic reaction process, can be combined with the fully exposed catalytic active sites to promote the reaction, and simultaneously, the load of the nano sheet adjusts the wettability of the surface of the air electrode to form a solid-liquid-gas three-phase interface which operates efficiently, thereby improving the heterogeneous catalytic performance of the air electrode and further improving the stability of the prepared electrode in the charge and discharge process.
Comparative example 1
The comparative example provides a preparation method of a waste wood-derived self-supporting nitrogen-doped carbon substrate, which comprises the following specific preparation steps:
step 1): placing wood chips with the size of 20mm multiplied by 3mm in a 30wt% solution of phosphoric acid deionized water;
step 2): transferring the phosphoric acid aqueous solution containing the wood chips in the step 1) into an oven to carry out hydrothermal reaction at 140 ℃ for 12 hours, and then taking out the wood chips to dry at 80 ℃ for 48 hours;
step 3): the fully dried wood chips were mixed with urea (2 g) and monoammonium phosphate (2 g), placed in a tube furnace, protected with nitrogen, maintained at 900 ℃ for 2h at a heating rate of 5 ℃/min, and cooled to room temperature to give a self-supporting nitrogen-phosphorus doped carbon substrate with a microstructure as shown in fig. 1 a.
Comparative example 2
The comparative example provides a preparation method of a CoNi-LDH catalytic material, which comprises the following specific preparation steps:
step 1): 2mmol Co (NO) 3 ) 3 ·6H 2 O、2mmol Ni(NO 3 ) 2 ·6H 2 O and 20mmol CO (NH) 2 ) 2 Adding the mixture into 80mL of deionized water, and obtaining a mixed solution after complete dissolution;
step 2): transferring the solution prepared in the step 1) into a reaction kettle, and carrying out hydrothermal treatment at 120 ℃ for 8 hours;
step 3): and (3) centrifugally collecting the precipitate obtained in the step (2), washing with deionized water, and freeze-drying for 24 hours to obtain the CoNi-LDH catalytic material, wherein the microstructure of the CoNi-LDH catalytic material is shown in figure 1 b.
Examining the microscopic morphologies of the self-supporting nitrogen-doped carbon substrate prepared in example 1 and the self-supporting nitrogen-doped carbon substrate prepared in comparative examples 1 and 2 and the CoNi-LDH catalytic material by using SEM, namely SEM images shown in figures 1a-c, it can be known that the wood-derived nitrogen-phosphorus-doped carbon substrate has a characteristic of layering and porosity, the CoNi-LDH is a lamellar nano structure, and a catalytic efficient carbon composite material can be constructed by effectively combining the two materials, so as to form an electrochemical heterogeneous interface formed by a carbon carrier and a nano sheet; the porous characteristic of the wood ensures that the wood has a larger specific surface area, is favorable for gas diffusion in the catalytic reaction process, and can realize effective combination with fully exposed catalytic active sites so as to promote the reaction. Moreover, the load of the nano-sheet adjusts the wettability of the surface of the air electrode to form a solid-liquid-gas three-phase interface which operates efficiently, so that the heterogeneous catalysis performance of the air electrode is improved, and the stability of the prepared electrode in the charge and discharge processes is further improved.
Example 2
10mg of the bifunctional air electrode prepared in the form of powder in example 1, the nitrogen-phosphorus doped carbon substrate prepared in comparative example 1, the CoNi-LDH catalytic material prepared in comparative example 2, and commercialized Pt/C, ruO were each prepared 2 The powder was dissolved in 2mL of a solution consisting of ethanol and 5% Nafion, sonicated for 30 minutes to form a uniform slurry, and the resulting slurry was then drop-coated onto a rotating disk electrode having a glass carbon surface loading of 0.1mg/cm 2 And after being fully dried, the electrode is used as a working electrode, a three-electrode system is formed by the electrode, a platinum wire counter electrode and a silver/silver chloride reference electrode, a potassium hydroxide solution is used as an alkaline electrolyte, a Chen Hua company CHI760 series electrochemical workstation is used for testing, and a linear voltammetry scanning method (the scanning speed is 5 mV/s) is adopted for examining the ORR and OER performances.
The test results are shown in FIGS. 2a and b, and FIG. 2a shows the ORR catalytic performance of the catalytic materials prepared in the examples and comparative examples compared with that of commercial noble metal catalysts, and it can be found that the limiting current density of CoNiLDH@NPC during ORR catalysis is 5.58mA/cm 2 The half-wave potential was 0.85V, compared to a commercial Pt/C catalyst (5.66 mA/cm 2 0.89V) is very close to, and is superior to, the ORR catalytic performance of the nitrogen-phosphorus doped carbon substrate and the CoNi-LDH prepared in the comparative example. FIG. 2b is a comparison of OER catalytic performance of catalytic materials prepared in examples and comparative examples with commercial noble metal catalysts, showing that CoNiLDH@NPC has a maximum limiting current density during OER catalysis and a current density of 10mA/cm 2 The overpotential (320 mV) at this point is much less than all of the comparative materials; the carbon carrier doped with nitrogen element and CoNi-LDH are effectively compounded to form a heterogeneous interface with rich electron density, a widely distributed three-dimensional structure electron transmission network is formed in the air electrode, the self impedance of the material is reduced, the electron conductivity of the material is improved, the electrocatalytic double-function is greatly improved, and the air electrode CoNiLDH@NPC prepared by the embodiment has optimal half-cell performance.
Example 3
10mg of the integrated bifunctional air electrode prepared in example 1 and in powder form and Pt/C-RuO were each prepared 2 The powder was dissolved in ethanol and 5% Nafion solution and sonicated for 30 minutes to form a uniform catalyst slurry which was sprayed onto hydrophobic carbon paper (loading 2mg/cm 2 ) And drying to obtain an air electrode, taking the air electrode as a positive electrode, directly taking the integrated double-function air electrode in a self-supporting form as a positive electrode material without spraying operation, taking a zinc sheet as a negative electrode, taking a 6M potassium hydroxide solution as an electrolyte, and respectively placing the parts in a battery device to assemble the zinc-air battery. Discharge power density test (5 mV/s sweep rate) using electrochemical workstation equipped with current amplifier, charge and discharge test (10 mA/cm current density) using battery test system 2 ) One cycle (10 minutes discharge, 10 minutes charge) was performed for 20 minutes.
Test results as shown in fig. 3a, b, fig. 3a shows a comparison of the discharge power density for the different forms of examples, and it was found that zinc air cells assembled using self-supporting conildh@npc exhibited extremely high peak discharge power density (263 mW/cm during the test 2 ) The electric power output power of the battery assembled by the powder-form material is superior to that of the battery assembled by the powder-form material, and the integrated double-function air electrode has excellent discharge performance. FIG. 3b is a graph showing comparison of charge and discharge stability at a current density of 10mA/cm for the example 2 When the zinc-air battery assembled by the self-supporting CoNiLDH@NPC can stably run for 500 hours, namely 1500 charge-discharge cycles, the voltage difference is 0.79V without obvious increasing trend, and the voltage difference is superior to the charge-discharge cycle time and the charge-discharge pressure difference of the battery assembled by using the powder-form material.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to be limiting in any way and in nature, and it should be noted that several modifications and additions may be made to those skilled in the art without departing from the invention, which modifications and additions are also intended to be construed as within the scope of the invention.
Claims (10)
1. The integrated double-function air electrode is characterized in that the chemical composition of the double-function air electrode is CoNiLDH@NPC, the double-function air electrode takes a nitrogen-phosphorus doped self-supporting carbon material derived from wood as a substrate, cobalt salt and nickel salt as LDH synthesis sources, and LDH catalytic materials with nano-sheet structures are synthesized on the substrate through in-situ Shui Resheng length, so that the integrated nitrogen-phosphorus doped carbon material loaded with CoNi-LDH is obtained, namely the double-function air electrode.
2. The method for preparing the waste wood-derived porous carbon integrated dual-function air electrode as claimed in claim 1, comprising the steps of:
step 1): placing wood chips in phosphoric acid deionized water solution for hydrothermal reaction;
step 2): taking out the wood chips after the reaction is finished, mixing the wood chips with urea and monoammonium phosphate after drying, and placing the mixture in a tube furnace for pyrolysis under inert atmosphere to obtain a self-supporting nitrogen-phosphorus doped carbon substrate;
step 3): co (NO) 3 ) 3 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O and CO (NH) 2 ) 2 Adding the mixture into deionized water, and completely dissolving to obtain a mixed solution;
step 4): adding the self-supporting nitrogen-doped carbon substrate obtained in the step 2) into the mixed solution obtained in the step 3), fully soaking, and transferring to a reaction kettle for hydrothermal reaction;
step 5): and after the reaction is finished, taking out the carbon substrate, washing with deionized water, and freeze-drying to obtain the wood-derived porous carbon integrated dual-function air electrode.
3. The method for preparing a waste wood-derived porous carbon integrated dual-function air electrode according to claim 2, wherein the wood chip size in the step 1) is 20mm x 3mm, and the concentration of the deionized water solution of phosphoric acid is 25-35 wt%.
4. The method for preparing the integrated dual-functional air electrode of the porous carbon derived from the waste wood according to claim 2, wherein the hydrothermal reaction in the step 1) is carried out at the temperature of 135-145 ℃ for 10-14 h.
5. The method for preparing the integrated porous carbon dual-function air electrode derived from waste wood according to claim 2, wherein the drying temperature in the step 2) is 75-85 ℃ and the drying time is 45-50 h.
6. The method for preparing the integrated porous carbon dual-functional air electrode derived from waste wood, as set forth in claim 2, wherein the mass ratio of urea to monoammonium phosphate in the step 2) is 1:1, and the pyrolysis process conditions are as follows: the temperature is 850-950 ℃, the temperature rising rate is 4-6 ℃/min, and the time is 1-3 h.
7. The method for preparing a waste wood-derived porous carbon integrated dual-function air electrode according to claim 2, wherein Co (NO 3 ) 3 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O and CO (NH) 2 ) 2 Is 2:2:20, said Co (NO 3 ) 3 ·6H 2 The molar concentration of O is 0.02-0.03 mol/L.
8. The method for preparing the integrated porous carbon dual-functional air electrode derived from the waste wood according to claim 2, wherein the time of soaking in the step 4) is 1-3 hours, the temperature of the hydrothermal reaction is 115-125 ℃ and the time is 7-9 hours.
9. The method for preparing the waste wood-derived porous carbon integrated dual-function air electrode according to claim 2, wherein the time of freeze-drying in the step 5) is 20-30 hours.
10. Use of the waste wood-derived porous carbon integrated bifunctional air electrode of claim 1 in zinc-air batteries.
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