CN113078327A - Preparation method of carbon aerogel containing bimetallic site and application of aluminum-air battery - Google Patents
Preparation method of carbon aerogel containing bimetallic site and application of aluminum-air battery Download PDFInfo
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- CN113078327A CN113078327A CN202110339654.7A CN202110339654A CN113078327A CN 113078327 A CN113078327 A CN 113078327A CN 202110339654 A CN202110339654 A CN 202110339654A CN 113078327 A CN113078327 A CN 113078327A
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- carbon aerogel
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 230000007935 neutral effect Effects 0.000 claims abstract description 32
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 108010010803 Gelatin Proteins 0.000 claims abstract description 14
- 239000008273 gelatin Substances 0.000 claims abstract description 14
- 229920000159 gelatin Polymers 0.000 claims abstract description 14
- 235000019322 gelatine Nutrition 0.000 claims abstract description 14
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
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- BPLKXBNWXRMHRE-UHFFFAOYSA-N copper;1,10-phenanthroline Chemical compound [Cu].C1=CN=C2C3=NC=CC=C3C=CC2=C1 BPLKXBNWXRMHRE-UHFFFAOYSA-N 0.000 claims description 5
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- 238000003786 synthesis reaction Methods 0.000 claims description 5
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 43
- 239000010949 copper Substances 0.000 abstract description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
Abstract
The invention discloses a preparation method of carbon aerogel containing bimetallic sites and application of an aluminum-air battery, the aerogel takes gelatin as a monomer, silicon dioxide as a hard template, an iron/copper-phenanthroline complex as a nitrogen source and a hydrogel precursor synthesized by a metal source, and the hydrogel precursor is subjected to freeze drying, high-temperature pyrolysis and acid washing to obtain carbon aerogel uniformly loaded with iron and copper double-site doping, meanwhile, because the carbon aerogel has abundant three-dimensional folds and porous structures and active bimetallic sites, exhibits excellent oxygen reduction (ORR) electrocatalytic activity under both alkaline and neutral conditions, the performance of a neutral aluminum-air battery assembled by taking the carbon aerogel as the positive electrode is obviously superior to that of a commercial Pt/C electrocatalyst, therefore, the catalyst prepared by the method has potential guiding significance for research and development and production of the non-corrosive flexible wearable metal-air battery.
Description
Technical Field
The invention relates to the technical field of energy storage and conversion, in particular to a preparation method of a nitrogen-doped biomass carbon aerogel-based FeCu loaded bimetallic site porous material and application of the nitrogen-doped biomass carbon aerogel-based FeCu loaded bimetallic site porous material to an aluminum-air battery.
Background
The non-renewability of fossil energy and the increasing environmental pollution have driven the development of sustainable energy technologies, such as metal-air batteries. Among them, aluminum air batteries have high theoretical energy density (2796 Whkg)-1) The battery has the characteristics of low cost, environmental friendliness and the like, has the characteristics of abundant reserves, light weight and low cost, and is considered to be a promising battery. The aluminum-air battery uses metal aluminum as a negative electrode, oxygen in the air as a positive electrode, and generates electric energy through oxidation-reduction reaction, and the performance of the battery depends on the Oxygen Reduction Reaction (ORR) of a catalyst on the negative electrode to a great extent. The traditional aluminum-air battery uses strong alkaline electrolyte to ensure that the battery has larger discharge voltage and power, but the metal aluminum at the negative electrode is seriously self-corroded in an open circuit state and a discharge process, in addition, the alkaline electrolyte has serious corrosivity when being leaked, and once the battery is exposed in the air, the electrolyte is dried and the atmospheric CO is generated2The reaction with potassium hydroxide (KOH) electricity greatly shortens the life of the battery. The use of a neutral salt electrolyte is a good solution to this problem. However, neutral media generally have lower ionic conductivity and very low OH-Concentration, Oxygen Reduction Reaction (ORR) kinetics of a conventional air cathode catalyst in a neutral salt solution is slow. Therefore, there is an urgent need to develop a highly active and durable ORR catalyst capable of efficiently operating in a neutral environment to maximize the performance of a neutral alumina.
Transition metal/nitrogen doped carbon aerogels with 3D interpenetrating network structures are considered to be a promising ORR catalyst. The hierarchical porous carbon aerogel has high-activity single metal atom sites and rich electron/mass transfer channels; in addition, the microporous defects in the carbon aerogel can trap and stabilize metal atom sites. Both experimental and theoretical analyses prove that the iron monatomic catalyst has the highest activity for oxygen reduction in an alkaline medium, and the electronic structure of the iron atom can be influenced by doping another transition metal on the carbon substrate, so that the Oxygen Reduction Reaction (ORR) kinetic activity of the iron atom is further improved. Therefore, the improvement of the ORR activity of the Fe monatomic catalyst in a neutral salt solution has great practical application value in a neutral aluminum air battery.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide a preparation method for synthesizing a high-performance bimetallic site carbon aerogel catalyst by using biomass gelatin hydrogel as a precursor and application of the catalyst to an aluminum air battery. The preparation method is green and environment-friendly, and has low cost and excellent electrochemical performance. The aerogel is formed by carbonizing freeze-dried renewable biomass hydrogel, has an ordered three-dimensional network and a unique fold structure, and can be used as a novel carbon substrate anchoring metal site to synthesize some electrocatalytic materials.
In order to achieve the aim, the invention designs a preparation method of carbon aerogel containing bimetal sites, which comprises the following specific steps:
s100, synthesis of gelatin hydrogel: mixing a proper amount of gelatin, silicon dioxide nanoparticles and deionized water, stirring in a water bath at 60 ℃, recovering to room temperature after completely dissolving, sequentially adding an iron-phenanthroline complex, a copper-phenanthroline complex and a zinc acetate solution, uniformly mixing, and freezing the obtained solution at-4 ℃ to form hydrogel;
s200, preparing iron-copper double-site carbon aerogel: freezing and drying the hydrogel synthesized in the step S100 overnight, and heating in a hydrogen-argon mixed atmosphere; and then grinding the material subjected to high-temperature carbonization into powder, adding deionized water and analytically pure hydrofluoric acid, carrying out magnetic stirring to remove silicon dioxide particles and unstable metal nanoparticles, and sequentially carrying out vacuum filtration and oven drying to finally obtain the iron-copper double-site loaded nitrogen-doped carbon aerogel.
Further, the gelatin is gelatin having a freezing force of 250bloom in step S100.
Further, in step S100, the silica nanoparticles are silica nanoparticles having a particle size of 15 nm.
Further, in step S100, the concentrations of the iron-phenanthroline complex and the copper-phenanthroline complex are both 0.2mol/L, and the concentration of the zinc acetate solution is 1 mol/L.
Further, the hydrogen content in the hydrogen-argon mixed atmosphere described in step S200 was 3%, and the temperature increase rate was 5 ℃/min.
Further, the temperature for heating and carbonizing the hydrogel in step S200 is 850-.
The application of the aluminum-air battery prepared by the method in the preparation method of the double-metal-site-containing carbon aerogel comprises the following steps:
s1, taking a 10% sodium chloride solution as an electrolyte of the liquid neutral aluminum-air battery;
s2, taking 20% polyacrylamide hydrogel as an electrolyte of the solid neutral aluminum-air battery;
s3, taking the aluminum sheet and the prepared carbon aerogel catalyst as an anode and a cathode of the aluminum-air battery respectively, wherein the cathode is formed by laminating a gas diffusion layer, a foam Ni layer and a catalyst layer, and mixing 60% of NCAG/Fe-Cu, 10% of acetylene black and 30% of polytetrafluoroethylene to prepare a catalyst layer;
s4, tabletting the prepared catalytic layer to 0.3-0.4mm, and vacuum drying at 60 ℃ for 2-4 h.
Further, a specific method for using 20% polyacrylamide hydrogel as the electrolyte of the solid-state neutral aluminum-air battery comprises the following steps: and (2) magnetically stirring an acrylamide monomer and deionized water with a screw bottle, adding a crosslinking agent MBAA and an initiator after the acrylamide monomer and the deionized water are completely dissolved, putting the solution into an oven after uniform stirring, and soaking the formed gel in a 10% sodium chloride solution for 48 hours.
Further, the initiator is potassium persulfate.
The invention has the beneficial effects that: the invention uses green cheap gelatin to synthesize hydrogel, and the chemical network with good tissue not only can be easily processed into carbon aerogel with three-dimensional porosity and abundant folds, but also can generate micropore defects in the pyrolysis process, thereby stably anchoring transition metal in a carbon skeleton to form the bimetallic site catalyst. The preparation method is simple in process, low in cost, green, safe and renewable, and the obtained composite material has a positive guiding effect on the research and development and large-scale production of the next-generation neutral aluminum-air battery.
Drawings
FIG. 1 shows G/Fe (PM) in example 1 of the present invention3-Cu(PM)3Scanning electron microscope images (containing physical images) of hydrogels;
FIG. 2 is a transmission electron microscope image (including object image) of the nitrogen-doped carbon aerogel porous material in example 1 of the present invention;
FIG. 3 is a high-power transmission electron microscope image of the nitrogen-doped carbon aerogel porous material in example 1 of the present invention;
FIG. 4 is an X-ray photoelectron spectroscopy (XPS) graph of the nitrogen-doped carbon aerogel porous material according to example 1 of the present invention;
FIG. 5 is an X-ray diffraction (XRD) pattern of the nitrogen-doped carbon aerogel porous material according to example 1 of the present invention;
FIG. 6 is a Raman view of the nitrogen-doped carbon aerogel porous material according to example 1 of the present invention;
FIG. 7 shows N of the nitrogen-doped carbon aerogel porous material in example 1 of the present invention2Adsorption-desorption isotherms;
FIG. 8(a) is a diffusion polarization curve (scan rate 10mV/S) of nitrogen-doped carbon aerogel porous material and commercial 20% Pt/C in oxygen-saturated 0.1MKOH solution, respectively, according to example 1 of the present invention; (b) half-wave potential and kinetic current density (at 0.85V) for each catalyst;
FIG. 9(a) shows the hydrogen peroxide yield and electron transfer number of the nitrogen-doped carbon aerogel porous material and the commercial 20% Pt/C in 0.1MKOH solution saturated with oxygen in example 1 according to the present invention; (b) is the tafel slope of each catalyst;
FIG. 10(a) is a diffusion polarization curve (scan rate 10mV/S) of nitrogen-doped carbon aerogel porous material and commercial 20% Pt/C catalyzed ORR in 10% NaCl solution saturated with oxygen, respectively, in example 1 of the present invention; (b) half-wave potential and kinetic current density (at 0.75V) for each catalyst;
FIG. 11(a) shows the hydrogen peroxide yield and the electron transfer number of the nitrogen-doped carbon aerogel porous material and the commercial 20% Pt/C in 10% NaCl solution saturated with oxygen, respectively, in example 1 of the present invention; (b) is the tafel slope of each catalyst;
FIG. 12 is a cyclic voltammogram of the nitrogen-doped carbon aerogel porous material scanned in 10% NaCl solution for 1 cycle and 8000 cycles (scan rate is 100mV/S) in example 1;
fig. 13(a) is a discharge polarization curve and a power density curve of a neutral liquid aluminum-air battery using the nitrogen-doped carbon aerogel porous material as the positive electrode material in example 1 of the present invention; (b) is a corresponding open circuit voltage curve;
fig. 14 shows discharge polarization curves and power density curves of the positive electrode cell of the neutral solid-state aluminum-air cell device using nitrogen-doped carbon aerogel porous material and commercial Pt/C in example 1 of the present invention in different compression states;
FIG. 15 is a graph showing open circuit voltage curves of the positive electrode cell of the neutral solid state aluminum air cell device using the nitrogen-doped carbon aerogel porous material and commercial Pt/C according to example 1 of the present invention;
fig. 16 is a constant current discharge curve of the positive electrode cell using the nitrogen-doped carbon aerogel porous material and commercial Pt/C as the neutral solid-state aluminum air cell device in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the first embodiment, the first step is,
the embodiment of the invention designs a preparation method of carbon aerogel containing bimetal sites, which has the following specific technical scheme:
synthesis of S100 gelatin hydrogel: placing 60mg of gelatin with freezing force of 250bloom, 30mg of silica nanoparticles with particle size of 15nm and 2.51mL of deionized water in a 20mL glass bottle, stirring at room temperature for 40-60min, and heating at 60 deg.CStirring in water bath for 10-20min, recovering to room temperature after completely dissolving, sequentially adding 150 μ L of 0.2mol/L iron-o-diazaphenanthrene complex, 100 μ L of 0.2mol/L copper-o-diazaphenanthrene complex, 80 μ L of 1mol/L zinc acetate solution, mixing, freezing at-4 deg.C for 20min to obtain hydrogel named as G/Fe (PM)3-Cu(PM)3；
S200, preparation of iron-copper double-site carbon aerogel: G/Fe (PM) synthesized in step S1003-Cu(PM)3After the hydrogel is frozen and dried overnight, the hydrogel is heated for 2 to 4 hours in a hydrogen-argon mixed atmosphere (the content of hydrogen is 3 percent) with the gas speed of 100mL/min, and the temperature rising speed is 5 ℃/min; and then grinding the material subjected to high-temperature carbonization into powder, wherein the carbonization temperature is 900 ℃, adding 3.75mL of deionized water and analytically pure HF, magnetically stirring for 2 hours to remove silicon dioxide particles and unstable metal nanoparticles, sequentially performing vacuum filtration and drying in an oven at 60 ℃, and finally obtaining the iron-copper double-site loaded nitrogen-doped carbon aerogel which is named as NCAG/Fe-Cu.
The invention also discloses an application of the bimetallic site carbon aerogel prepared by the method in an aluminum air battery, in particular to a catalytic application of a neutral aluminum air battery, which comprises the following specific application steps:
s1, taking a 10% sodium chloride solution as an electrolyte of the liquid neutral aluminum-air battery;
s2, taking 20% polyacrylamide hydrogel as an electrolyte of the solid neutral aluminum-air battery, and the specific method comprises the following steps: taking 4g of acrylamide monomer and 16ml of deionized water, magnetically stirring the acrylamide monomer and the deionized water in a screw bottle, adding a crosslinking agent MBAA after the acrylamide monomer and the deionized water are completely dissolved, then adding potassium persulfate serving as an initiator, uniformly stirring, injecting the solution into a 2mm glass mold, putting the glass mold into a 60 ℃ oven overnight, and then soaking the formed gel in 10% sodium chloride solution or 10% NaCl + 40% betaine solution for 48 hours.
S3, respectively taking the aluminum sheet and the prepared carbon aerogel catalyst as an anode and a cathode of the aluminum-air battery, wherein the cathode is formed by laminating a gas diffusion layer, a foam Ni layer and a catalyst layer, and mixing 60% of NCAG/Fe-Cu, 10% of acetylene black and 30% of polytetrafluoroethylene to prepare the catalyst layer.
S4, pressing the prepared catalytic layer to 0.3-0.4mm, and then carrying out vacuum drying for 3h at the temperature of 60 ℃.
In the second embodiment, the first embodiment of the method,
the preparation method of the bimetal site carbon aerogel catalyst provided by the embodiment of the invention comprises the following specific steps:
s100, synthesizing a biomass hydrogel: weighing 60mg of 250bloom gelatin and 30mg of silicon dioxide nanoparticles (15nm) in a small glass bottle, adding 2.51M L deionized water, stirring at normal temperature for 40min to completely absorb the swelling, heating in a water bath at 60 ℃ for 10min, recovering the room temperature after completely dissolving, sequentially adding 150 mu L of 0.2M iron-phenanthroline complex, 100 mu L0.2M copper-phenanthroline complex and 80 mu L of 1M zinc acetate solution, uniformly mixing, and freezing the obtained solution in a refrigerator at-4 ℃ for 20min to form hydrogel named as G/Fe (PM)3-Cu(PM)3。
S200, preparation of iron-copper double-site carbon aerogel: G/Fe (PM) synthesized in step S1003-Cu(PM)3The hydrogel was freeze-dried overnight under a hydrogen-argon atmosphere (3% H) at a gas flow rate of 100mL/min2) Heating at medium 900 deg.C for 3h at a temperature rise rate of 5 deg.C/min; and then grinding the material subjected to high-temperature carbonization into powder, adding 3.75mL of deionized water and analytically pure HF, magnetically stirring for 2h to remove silicon dioxide particles and unstable metal nanoparticles, sequentially performing vacuum filtration and drying in an oven at 60 ℃ for 60min to finally obtain the nitrogen-doped carbon aerogel loaded with the iron-copper double sites, and naming the nitrogen-doped carbon aerogel as NCAG/Fe-Cu.
Preparation of comparative samples: respectively with G/Fe (PM)3，G/Cu(PM)3The biomass sol is used as a precursor, and three groups of comparison samples are prepared by adopting the same synthesis steps. The corresponding products were named NCAG/Fe, NCAG/Cu.
Electrochemical testing: the electrochemical test was carried out in a three-electrode system, in which a platinum sheet electrode was used as the counter electrode, a saturated Ag/Ag Cl electrode as the reference electrode, and a glassy carbon electrode as the working electrode, and in order to prepare the catalyst ink, 3mg of the catalyst was dissolved in 475. mu.L of a mixed solution (1: 1) of water and ethanol, 25. mu.L of an LNafion solution (5%) was added, and the catalyst ink was dispersed ultrasonically for 1 hour to obtain a uniformly dispersed catalyst ink. The catalyst loadings for the cyclic voltammetry test and the rotating disk test were 250. mu.g cm-2 and 400. mu.g cm-2, respectively.
Synthesis of all-solid-state gel electrolyte: taking 4g of acrylamide monomer and 16ml of deionized water, magnetically stirring the acrylamide monomer and the deionized water in a screw bottle, adding 4mg of cross-linking agent MBAA after the acrylamide monomer and the deionized water are completely dissolved, then adding 10mg of potassium persulfate serving as an initiator, uniformly stirring, injecting the solution into a 2mm glass mold, putting the glass mold into a 60 ℃ oven for overnight, and then soaking the formed gel in 10% sodium chloride solution or 10% NaCl + 40% betaine solution for 48 hours to obtain the product named PAM-10% NaCl.
Assembling the neutral aluminum-air battery: respectively taking an aluminum sheet and the prepared carbon aerogel catalyst as an anode and a cathode of an aluminum-air battery, taking 10% sodium chloride solution or PAM-10% NaCl as an electrolyte, wherein the cathode is formed by combining a gas diffusion layer, a foam Ni layer and a catalyst layer, the catalyst layer is prepared by mixing 60% of NCAG/Fe-Cu, 10% of acetylene black and 30% of polytetrafluoroethylene, and the prepared catalyst layer is pressed to 0.3mm and then is subjected to vacuum drying at the temperature of 60 ℃ for 3 hours.
The following analysis was then performed:
first, morphology and Structure analysis of catalyst
As shown in fig. 1(SEM), the hydrogel formed in step S100 of example 1 maintains a honeycomb-shaped three-dimensional skeleton, except for surface roughness, after being lyophilized. As shown in fig. 2(TEM), the carbon aerogel composite material finally obtained in example 1 has a three-dimensional layered porous carbon structure, and the porosity thereof is about 10 nm.
The black dots shown in fig. 3(HRTEM) reveal the formation of individual metal atoms anchored in the final carbon aerogel composite obtained in example 1.
As shown in fig. 4(XPS spectrum), the electron binding energy of Fe is negatively shifted due to the introduction of Cu in the bimetallic site catalyst, i.e. electrons on Cu are transferred to Fe, so that the electron cloud density on the iron site is increased, which is beneficial to improving the binding energy of ORR intermediate product on the iron site.
As shown in fig. 5(XRD pattern), both the bimetallic Fe/Cu site porous composite material and the Fe or Cu single metal porous composite material have a diffraction peak generated by the (002) plane of graphitic carbon within a range of 20-30 degrees, but the diffraction peak corresponding to the (002) plane of graphitic carbon of the iron-doped sample is shifted forward compared with that of the copper-doped sample, which indicates that the doping of iron is more beneficial to improving the graphitization degree of carbon, thereby improving the conductivity of the material.
As shown in FIG. 6 (Raman spectrum), I of the bimetallic Fe/Cu site porous composite and Fe or Cu monometallic porous compositeD/IGThe values are respectively 0.85, 0.84 and 0.93, and combined with an XRD (X-ray diffraction) spectrum, the bimetal Fe/Cu site porous composite material has the characteristics of multiple defects and high crystallinity, and respectively shows that the bimetal Fe/Cu site porous composite material has rich active sites and high-efficiency electron transfer.
As shown in FIG. 7 (N)2Adsorption and desorption curve), the test shows that the prepared bimetallic Fe/Cu site porous composite carbon aerogel material shows IV-type isotherm H2(b) The hysteresis loop, which implies a composite pore network structure consisting essentially of mesopores with a size of about 10nm, was tested to give a specific surface area of 1008m2g-1The porous material has rich pore structure, can provide more active sites and is favorable for mass transfer.
Second, analysis of electrochemical Properties of the catalyst
As shown in fig. 8a, when the ORR performance test under alkaline condition (0.1M KOH) is performed on the material by using the rotating disc technology RDE, the half-wave potential of the Fe/Cu bimetallic site carbon aerogel catalyst reaches 0.94V by analyzing the diffusion polarization curve diagram of the Fe/Cu bimetallic site carbon aerogel catalyst, and the half-wave potential of the commercial Pt/C catalyst with the same loading amount is 0.87V; as shown in FIG. 8b, the kinetic current density (Jk) of the aerogel, calculated from the Koutecky-Levich curve, was 25.5mAcm-2About 2.3 times (11.2mA cm) that of commercial Pt/C-2)。
As shown in FIG. 9a, the Fe/Cu bimetallic site carbon aerogel catalyst exhibits the lowest H over a wide potential range (+0.2V to 0.9V)2O2Yield, indicating high efficiency4 electron transfer paths. As shown in FIG. 9b, the Fe/Cu bimetallic site carbon aerogel catalyst exhibits a lower Tafel slope (55 mVdec) in the high potential range-1) Significantly lower than the equivalent loading of commercial Pt/C catalyst (79 mVdec)-1) The catalyst has high-efficiency ORR kinetic process.
As shown in fig. 10a, when the ORR performance test under neutral condition (10% NaCl) is performed on the material by using the rotating disc technology RDE, the half-wave potential of the Fe/Cu bimetallic site carbon aerogel catalyst reaches 0.84V by analyzing the diffusion polarization curve diagram, and the half-wave potential of the commercial Pt/C catalyst with the same loading amount is 0.78V; as shown in FIG. 10b, the kinetic current density (Jk) of the aerogel, calculated from the Koutecky-Levich curve, was 10.6mAcm-2While that of commercial Pt/C is 3.0mA cm-2。
As shown in FIG. 11a, the Fe/Cu bimetallic site carbon aerogel catalyst exhibits the lowest H over a wide potential range (+0.2V to 0.9V) even under neutral conditions2O2Yield, indicating a highly efficient 4 electron transfer pathway. As shown in FIG. 11b, the Fe/Cu bimetallic site carbon aerogel catalyst exhibits a lower Tafel slope (76 mVdec) in the high potential range-1) Significantly lower than the equivalent loading of commercial Pt/C catalyst (176 mVdec)-1) The catalyst also has efficient ORR kinetic process under neutral condition.
FIG. 12 is a comparison graph of the Fe/Cu bimetallic site carbon aerogel catalyst after 8000 cycles in 10% NaCl solution at a scanning rate of 100mV/S within a potential range of 0.223V to 1.023V and before cycles, and it is obvious that compared with a single Fe metal sample, the peak potential of the composite material after 8000 cycles is only shifted negatively by 13mV, and the current density is not obviously declined, which indicates that Cu doping is beneficial to improving the stability of an independent iron-based material.
Third, analysis of electrochemical properties of neutral aluminum-air cell
As shown in fig. 13, the bimetallic Fe/Cu site porous composite carbon aerogel of the present invention is used as a positive electrode material of a neutral liquid aluminum-air battery, has excellent ORR catalytic performance, and shows a high open-circuit voltage and a high power density in the neutral liquid aluminum-air battery.
Fig. 14 is an open circuit voltage of the neutral solid state aluminum air cell test, which is significantly higher than the commercial Pt/C catalyst under the same conditions, and which can still maintain more than 96% when the solid state cell is placed in a-20 ℃ refrigerator.
As shown in FIG. 15, in the neutral solid-state aluminum air cell using polyacrylamide with 10% NaCl as electrolyte, even if the gel is in different compression states, the discharge performance of the cell is basically unchanged from the corresponding power density, and the performance of the catalyst used in the aluminum air cell is outstanding and exceeds the performance of the similar cell reported in most documents at present.
Fig. 16 is a constant current discharge test chart of the solid-state aluminum air battery, and it is obvious that the voltage plateau at each current density is higher and more stable than that of the aluminum-air battery using the carbon aerogel as the cathode, further proving the uniqueness and superiority of the catalyst material, and possibly creating a positive guiding role for the development and production of the non-corrosive flexible wearable metal-air battery.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. A preparation method of carbon aerogel containing bimetallic site is characterized by comprising the following steps: the method comprises the following specific steps:
s100, synthesis of gelatin hydrogel: mixing a proper amount of gelatin, silicon dioxide and deionized water, stirring in a water bath at 60 ℃, recovering to room temperature after completely dissolving, sequentially adding an iron-phenanthroline complex, a copper-phenanthroline complex and a zinc acetate solution, uniformly mixing, and freezing the obtained solution at-4 ℃ to form hydrogel;
s200, preparing iron-copper double-site carbon aerogel: freezing and drying the hydrogel synthesized in the step S100 overnight, and heating in a hydrogen-argon mixed atmosphere; and then grinding the material subjected to high-temperature carbonization into powder, adding deionized water and analytically pure hydrofluoric acid, carrying out magnetic stirring to remove silicon dioxide and unstable metal nanoparticles, and sequentially carrying out vacuum filtration and oven drying to finally obtain the iron-copper double-site loaded nitrogen-doped carbon aerogel.
2. The method of claim 1, wherein the method comprises the steps of: the gelatin is gelatin having a freezing force of 250bloom in step S100.
3. The method of claim 1, wherein the method comprises the steps of: the silica is silica nanoparticles having a particle size of 15nm in step S100.
4. The method of claim 1, wherein the method comprises the steps of: in step S100, the concentrations of the iron-phenanthroline complex and the copper-phenanthroline complex are both 0.2mol/L, and the concentration of the zinc acetate solution is 1 mol/L.
5. The method of claim 1, wherein the method comprises the steps of: in the hydrogen-argon mixed atmosphere described in step S200, the content of hydrogen is 3%, and the temperature rise rate is 5 ℃/min.
6. The method of claim 1, wherein the method comprises the steps of: the temperature of the hydrogel heating carbonization in the step S200 is 850-950 ℃.
7. Use of an aluminum air cell containing a bimetallic site carbon aerogel prepared by the method of any of claims 1-6, characterized in that: the method comprises the following steps:
s1, taking a 10% sodium chloride solution as an electrolyte of the liquid neutral aluminum-air battery;
s2, taking 20% polyacrylamide hydrogel as an electrolyte of the solid neutral aluminum-air battery;
s3, taking the aluminum sheet and the prepared carbon aerogel catalyst as an anode and a cathode of the aluminum-air battery respectively, wherein the cathode is formed by laminating a gas diffusion layer, a foam Ni layer and a catalyst layer, and mixing 60% of NCAG/Fe-Cu, 10% of acetylene black and 30% of polytetrafluoroethylene to prepare a catalyst layer;
s4, tabletting the prepared catalytic layer to 0.3-0.4mm, and vacuum drying at 60 ℃ for 2-4 h.
8. The use of an aluminum air cell containing a bimetallic in-situ carbon aerogel according to claim 7, wherein: the specific method for using 20% polyacrylamide hydrogel as the electrolyte of the solid neutral aluminum-air battery comprises the following steps: and (2) magnetically stirring an acrylamide monomer and deionized water with a screw bottle, adding a crosslinking agent MBAA and an initiator after the acrylamide monomer and the deionized water are completely dissolved, putting the solution into an oven after uniform stirring, and soaking the formed gel in a 10% sodium chloride solution for 48 hours.
9. The use of an aluminum air cell containing a bimetallic in-situ carbon aerogel according to claim 8, wherein: the initiator is potassium persulfate.
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