CN110247068B - Preparation method and application of iron/copper aza graphene zinc air battery cathode catalyst - Google Patents
Preparation method and application of iron/copper aza graphene zinc air battery cathode catalyst Download PDFInfo
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- H—ELECTRICITY
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Abstract
The invention belongs to the field of zinc-air batteries and discloses iron/copperThe preparation method of the aza-graphene zinc air battery cathode catalyst comprises the following steps: (1) mixing iron oxyhydroxide, copper hydroxide, graphene oxide and graphite-phase carbon nitride (g-C)3N4) Mixing, adding sodium alginate to obtain gel; (2) putting the gel into a quartz tube with one closed end, vacuumizing by using a centrifugal pump, putting the quartz tube into a muffle furnace with the temperature of 750-950 ℃ for calcining for 10-20min, and then cooling at room temperature; (3) and (3) soaking the black solid obtained in the step in hydrochloric acid for 8-12h, keeping the temperature at 50-80 ℃, then washing the black solid with deionized water and ethanol to be neutral, drying the black solid, placing the dried black powder in a quartz tube with one closed end, vacuumizing the quartz tube, calcining the quartz tube at the temperature of 750-850 ℃ for 10-20min, and cooling the quartz tube to obtain the iron/copper aza graphene. The method is convenient and efficient, and the prepared catalyst is of an amorphous structure, has high electrocatalytic oxygen reduction activity and good stability, and has a very high application prospect.
Description
Technical Field
The invention belongs to the field of electrocatalysis materials, and relates to a preparation method and application of a cathode catalyst of an iron/copper aza graphene zinc air battery.
Background
With the rapid consumption of fossil energy and the increasing problem of global warming, much research into greener and cleaner energy conversion and storage devices, such as an electric water decomposition device, a fuel cell and a metal air battery (s.chu, y.cui, n.liu, Nat Mater 2016,16,16-22.) has been initiated. Zinc-air batteries have received much attention in recent years because of their advantages such as higher energy density, low price, and no pollution (U.L.Dong, P.xu, Z.P.Cano, A.G.Kashkooli, M.G.park, Z.Chen, J.Mater.chem.A,2016,4, 7107-7134.). The oxygen reduction (ORR) reaction occurring at the cathode of a zinc air battery determines the performance of the battery in actual use. Currently, platinum-carbon (Pt/C) catalysts based on the noble metal platinum are considered to be electrocatalysts having the highest oxygen reduction (ORR) activity. However, its high price, the scarce storage in the earth severely limits its mass production and commercial use. In recent years, researches show that nitrogen-doped carbon materials, such as aza-graphene and aza-carbon nanotubes, have better electrocatalytic oxygen reduction (ORR) activity under alkaline conditions, but the performances of the carbon materials are different from those of commercial platinum-carbon catalysts. Transition metal elements (such as iron, cobalt, nickel and the like) are introduced on the basis of the nitrogen-doped carbon material, and the electrocatalytic oxygen reduction performance of the obtained metal-nitrogen-carbon (M-N-C) composite material is further improved. However, the traditional preparation process of the catalyst material is very complicated, long-time high-temperature calcination under the protection of inert gas (such as nitrogen or argon) is required, and the electrocatalytic performance and stability of the catalyst material need to be improved urgently.
Graphene Oxide (GO) has a large specific surface area, excellent electrical conductivity and thermal stability, and is therefore often used as a carbon support in the synthesis of metal-supported aza-carbon catalysts. Graphite phase carbon nitride (g-C)3N4) It has high nitrogen content and simple preparation process, and may be used as one nitrogen source. Sodium alginate, as a biomass polymer extracted from brown algae, is abundant in resource, contains more carbonyl and hydroxyl in the structure, and can form gel with graphene oxide through hydrogen bond action. Transition metals of iron and copper are abundant in earth resources and low in price, and after the transition metals of iron and copper are loaded on the aza-carbon material, the obtained composite material shows excellent electrocatalytic oxygen reduction (ORR) activity. Different from the traditional method of high-temperature calcination under inert gas, the preparation of the electrocatalyst with high-efficiency oxygen reduction (ORR) activity by compounding the materials by a high-efficiency synthesis method is not reported, so that the method has very important significance.
Disclosure of Invention
The invention provides a preparation method and application of an iron/copper aza graphene zinc air battery cathode catalyst, and the synthesis process does not need long-time high-temperature calcination and inert gas protection. The catalyst prepared at the calcination temperature of 850 ℃ shows better electrocatalytic oxygen reduction (ORR) activity, the initial potential of the ORR is 1.01V, the half-wave potential is 0.88V, and the catalyst has better performance when being applied to a zinc-air battery, and has simple preparation method and low cost. The invention provides a preparation method of the iron/copper aza graphene zinc air battery cathode catalyst, which comprises the following steps:
(1) dissolving ferric trichloride hexahydrate and sodium hydroxide in deionized water, carrying out ultrasonic treatment until the ferric trichloride hexahydrate and the sodium hydroxide are uniformly dispersed, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 2-6h at the temperature of 80-120 ℃, cooling to room temperature, washing and drying to obtain a FeOOH precursor;
(2) dissolving copper chloride dihydrate in deionized water, adding polyethylene glycol, stirring to dissolve, adding sodium hydroxide solution, stirring at room temperature for half an hour, washing, and drying to obtain copper hydroxide (Cu (OH)2) A precursor;
(3) the urea is placed in a tube furnace and calcined for 4-8h at the temperature of 500-700 ℃ under the atmosphere of argon to obtain graphite phase carbon nitride (g-C)3N4)；
(4) FeOOH and Cu (OH) were weighed out separately2Dispersing in deionized water, performing ultrasonic treatment for 20-40min, adding the graphene oxide aqueous dispersion, and performing ultrasonic dispersion; then g-C is weighed3N4Dispersing in deionized water, ultrasonic dispersing, and adding water3N4Adding FeOOH/Cu (OH) into the solution2Adding sodium alginate after uniformly stirring the mixed solution/GO, continuously stirring for 4-6h, and drying in an oven at 40-60 ℃ for 8-12h to obtain gel;
(5) putting the gel obtained in the step (4) into a quartz tube with one closed end, removing air in the quartz tube by using a centrifugal pump, putting the quartz tube into a muffle furnace with the temperature of 750 and 950 ℃ after closing, calcining for 10-25min, and cooling at room temperature to obtain a black solid;
(6) and (3) soaking the black solid obtained in the step (5) in a hydrochloric acid solution for 8-12h, keeping the temperature at 50-80 ℃, then washing the black solid with deionized water and ethanol to be neutral, drying the black solid, placing the dried black powder in a quartz tube with one closed end, vacuumizing the quartz tube, calcining the quartz tube at the temperature of 750-950 ℃ for 10-20min, and cooling the quartz tube to obtain the iron/copper aza graphene zinc air battery cathode catalyst.
In the step (1), the molar ratio of ferric trichloride hexahydrate to sodium hydroxide is 2: 3.
In the step (2), the mass ratio of the copper chloride dihydrate to the polyethylene glycol is as follows: 1.15:1, wherein the concentration of the sodium hydroxide solution is 3-6mol/L, the concentration of the copper chloride dihydrate solution is 0.92mg/mL, and the volume ratio of the sodium hydroxide solution to the copper chloride dihydrate solution is 1.2: 250.
FeOOH, Cu (OH) in step (4)2Graphene oxide dispersion liquid g-C3N4And the amount of the sodium alginate is in proportion0.089 g: 0.097 g: 10mL of: 0.2 g: 0.2g, wherein the concentration of the graphene oxide dispersion liquid is 1-5 mg/mL.
The iron/copper nitrogen-doped graphene zinc air battery cathode catalyst prepared by the invention is characterized in that 2-5nm of iron-copper nanoclusters are embedded into a nitrogen-doped graphene layer, and the iron-copper nanoclusters are in an amorphous structure.
The iron/copper aza graphene zinc air battery cathode catalyst prepared by the invention is applied to preparing an air cathode of a zinc air battery.
Compared with the existing synthesis method, the method has the following advantages:
(1) the synthetic raw materials (such as sodium alginate, ferric chloride hexahydrate, copper chloride dihydrate and the like) used by the invention are rich in earth content and low in cost;
(2) the method of the invention is vacuum fast calcination, the reaction condition is easy to obtain, the reaction time is short, inert protective gas is not needed to be introduced, and the time and energy consumption required by material synthesis are reduced. The synthesis process is simple and has strong controllability;
(3) the catalyst prepared by the method of the invention shows excellent electrocatalytic oxygen reduction (ORR) performance, the initial potential of the ORR is 1.01V, the half-wave potential is 0.88V, and the initial potential (0.98V) and the half-wave potential (0.86V) are higher than those of a commercial grade 20 wt% Pt/C catalyst;
(4) the stability of the catalyst prepared by the method is superior to that of a commercial grade 20 wt% Pt/C catalyst under an alkaline condition;
(5) the air cathode is prepared by applying the catalyst and assembled into a zinc-air battery, 6M potassium hydroxide (KOH) solution is used as electrolyte, and the loading capacity of the catalyst is 1mg/cm2When the power density is up to 164.2mW/cm2138.2mW/cm higher than commercial grade 20 wt% Pt/C catalyst2And has high stability.
Drawings
FIG. 1 shows the prepared FeOOH, Cu (OH)2、g-C3N4And the X-ray diffraction (XRD) pattern of FeCu/NG-850;
FIG. 2 is a Transmission Electron Microscope (TEM) image (inset is selected area electron diffraction) of the FeCu/NG-850 electrocatalyst prepared;
FIG. 3 is a graph comparing ORR polarization curves for the as-synthesized material and a 20 wt% Pt/C catalyst in 0.1M KOH solution saturated with oxygen;
FIG. 4 is a graph of the chronoamperometric response of FeCu/NG-850 and 20 wt% Pt/C catalyst in 0.1M KOH solution saturated with oxygen;
FIG. 5 is a graph of discharge polarization curves and corresponding power densities for a zinc-air cell with FeCu/NG-850 and 20 wt% Pt/C as the cathode catalyst;
FIG. 6 shows a zinc-air cell with FeCu/NG-850 as cathode catalyst at 5mA/cm2Long time discharge plot at current density.
Detailed Description
The present invention will be further described in the following examples in order to better understand the present invention for those skilled in the art, but the scope of the present invention is not limited to the following examples.
Example 1:
(1) dissolving 1.1g of ferric chloride hexahydrate and 0.24g of sodium hydroxide in 20mL of deionized water, carrying out ultrasonic treatment until the solutions are uniformly dispersed, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 4 hours, cooling to room temperature, washing and drying to obtain a FeOOH precursor;
(2) dissolving 0.23g of copper chloride dihydrate in 250mL of deionized water, adding 200mg of polyethylene glycol, stirring until the copper chloride dihydrate is dissolved, adding 1.2mL of sodium hydroxide solution, stirring at room temperature for half an hour, washing and drying to obtain copper hydroxide (Cu (OH)2) A precursor;
(3) 4g of urea is placed in a tube furnace and calcined for 6 hours at 600 ℃ under the atmosphere of argon to obtain graphite-phase carbon nitride g-C3N4；
(4) 89mg of FeOOH and 97mg of Cu (OH) were weighed out respectively2Dissolving in 10mL of deionized water, performing ultrasonic treatment for 30min, adding into 10mL of graphene oxide aqueous dispersion (2mg/mL), and performing ultrasonic dispersion; then 0.2g of g-C was weighed3N4Dissolving the mixture in 10mL of deionized water for ultrasonic dispersion, and then dissolving g-C3N4Adding FeOOH/Cu (OH) into the solution2Mixing the/GO mixed solution, stirring, adding 0.2g of seaContinuously stirring sodium alginate for 4-6h, and drying in an oven at 40-60 deg.C for 8-12h to obtain gel;
(5) putting the gel into a quartz tube with one closed end, removing air in the tube by using a centrifugal pump, putting the quartz tube into a muffle furnace with the temperature of 850 ℃ after closing, calcining for 15min, and cooling at room temperature;
(6) and (3) soaking the black solid obtained in the previous step in 1mol/L hydrochloric acid for 12h, keeping the temperature at 60 ℃, then washing the black solid with deionized water and ethanol to be neutral, drying the black solid, placing the dried black powder in a quartz tube with one closed end, vacuumizing the quartz tube, calcining the black powder at 850 ℃ for 20min, and cooling the quartz tube to obtain FeCu/NG-850.
Example 2:
(1) dissolving 1.1g of ferric chloride hexahydrate and 0.24g of sodium hydroxide in 20mL of deionized water, carrying out ultrasonic treatment until the solutions are uniformly dispersed, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 4 hours, cooling to room temperature, washing and drying to obtain a FeOOH precursor;
(2) dissolving 0.23g of copper chloride dihydrate in 250mL of deionized water, adding 200mg of polyethylene glycol, stirring until the copper chloride dihydrate is dissolved, adding 1.2mL of sodium hydroxide solution, stirring at room temperature for half an hour, washing and drying to obtain copper hydroxide (Cu (OH)2) A precursor;
(3) 4g of urea is placed in a tube furnace and calcined for 6 hours at 600 ℃ under the atmosphere of argon to obtain graphite-phase carbon nitride g-C3N4；
(4) 89mg of FeOOH and 97mg of Cu (OH) were weighed out respectively2Dissolving in 10mL of deionized water, performing ultrasonic treatment for 30min, adding into 10mL of graphene oxide aqueous dispersion (2mg/mL), and performing ultrasonic dispersion; 0.2g of g-C is weighed3N4Dissolving the mixture in 10mL of deionized water for ultrasonic dispersion, and then dissolving g-C3N4Adding FeOOH/Cu (OH) into the solution2The GO mixed solution is uniformly stirred, 0.2g of sodium alginate is added, the mixture is continuously stirred for 4 to 6 hours and then dried for 8 to 12 hours in an oven at the temperature of between 40 and 60 ℃ to obtain gel;
(5) putting the gel into a quartz tube with one closed end, removing air in the tube by using a centrifugal pump, putting the quartz tube into a muffle furnace with the temperature of 850 ℃ after closing, calcining for 15min, and cooling at room temperature;
(6) and (3) soaking the black solid obtained in the previous step in 1mol/L hydrochloric acid for 12h, keeping the temperature at 60 ℃, then washing the black solid with deionized water and ethanol to be neutral, drying the black solid, placing the dried black powder in a quartz tube with one closed end, vacuumizing the quartz tube, calcining the black powder at 750 ℃ for 20min, and cooling the black powder to obtain FeCu/NG-750.
Example 3:
(1) dissolving 1.1g of ferric trichloride hexahydrate and 0.24g of sodium hydroxide in 20mL of deionized water, carrying out ultrasonic treatment until the solutions are uniformly dispersed, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 4 hours, cooling to room temperature, washing and drying to obtain a FeOOH precursor;
(2) dissolving 0.23g of copper chloride dihydrate in 250mL of deionized water, adding 200mg of polyethylene glycol, stirring until the copper chloride dihydrate is dissolved, adding 1.2mL of sodium hydroxide solution, stirring at room temperature for half an hour, washing and drying to obtain copper hydroxide (Cu (OH)2) A precursor;
(3) 4g of urea is placed in a tube furnace and calcined for 6 hours at 600 ℃ under the atmosphere of argon to obtain graphite-phase carbon nitride g-C3N4；
(4) 89mg of FeOOH and 97mg of Cu (OH) were weighed out respectively2Dissolving in 10mL of deionized water, performing ultrasonic treatment for 30min, adding into 10mL of graphene oxide aqueous dispersion (2mg/mL), and performing ultrasonic dispersion; 0.2g of g-C is weighed3N4Dissolving the mixture in 10mL of deionized water, and ultrasonically dispersing the mixture to obtain g-C3N4Adding FeOOH/Cu (OH) into the solution2The GO mixed solution is uniformly stirred, 0.2g of sodium alginate is added, the mixture is continuously stirred for 4 to 6 hours and then dried for 8 to 12 hours in an oven at the temperature of between 40 and 60 ℃ to obtain gel;
(5) putting the gel into a quartz tube with one closed end, removing air in the quartz tube by using a centrifugal pump, putting the quartz tube into a muffle furnace with the temperature of 850 ℃ after closing, calcining for 15min, and cooling at room temperature;
(6) and (2) soaking the black solid obtained in the previous step in 1mol/L hydrochloric acid for 12 hours, keeping the temperature at 60 ℃, then washing the black solid with deionized water and ethanol until the black solid is neutral, drying the black solid, placing the dried black powder in a quartz tube with one closed end, vacuumizing the quartz tube, calcining the quartz tube at 950 ℃ for 20min, and cooling the quartz tube to obtain FeCu/NG-950.
Example 4:
dissolving 3mg of catalyst in a mixed solution containing 500 mu L of ethanol, 500 mu L of deionized water and 20 mu L of 10% nafion, carrying out ultrasonic treatment in an ultrasonic machine for 10-30min to form slurry, transferring 5 mu L of the slurry by using a liquid transfer gun, uniformly coating the slurry on a glassy carbon electrode with the diameter of 3mm, and naturally drying the glassy carbon electrode;
introducing oxygen into 0.1M KOH for 30-50min, taking a glassy carbon electrode coated with a catalyst as a working electrode, taking an Ag/AgCl electrode and a platinum wire as a reference electrode and a working electrode respectively, and measuring ORR polarization curves of FeCu/NG-850, FeCu/NG-750 and FeCu/NG-950 by using a CHI760E electrochemical workstation at the rotating speed of 1600 rpm;
example 5:
dissolving 3mg FeCu/NG-850 catalyst in a mixed solution containing 500 μ L ethanol, 500 μ L deionized water and 20 μ L10% nafion, performing ultrasonic treatment in an ultrasonic machine for 10-30min to form slurry, and uniformly spreading on 1cm2On a hydrophobic carbon cloth (load is 1 mg/cm)2) And naturally airing to prepare the air cathode. A zinc-air battery with FeCu/NG-850 catalyst as cathode was assembled with a zinc plate as anode and 6M KOH solution as electrolyte. The discharge polarization curve was tested using CHI760E electrochemical workstation. At a current density of 5mA/cm2The zinc-air battery was subjected to a long-time discharge test.
Comparative example 1:
the ORR polarization curve was determined using a commercial grade 20 wt% Pt/C catalyst coated glassy carbon electrode as working electrode, an Ag/AgCl electrode and a platinum wire as reference electrode and working electrode, respectively, at 1600rpm using a CHI760E electrochemical workstation
Comparative example 2:
a zinc plate is used as an anode, 6M KOH is used as electrolyte to assemble a zinc-air battery with a commercial grade of 20 wt% Pt/C catalyst as a cathode. The discharge polarization curve was tested using the CHI760E electrochemical workstation.
As can be seen from the XRD pattern in FIG. 1, the characteristic peak of FeCu/NG-850 produced at 26.3 ℃ corresponds to the (002) crystal plane of carbon.
As can be seen from the TEM image of fig. 2, metal nanoclusters of 2-5nm are embedded in the carbon layer with a blurred lattice spacing. The circles in the selected zone electron diffraction pattern demonstrate that iron-copper is present in the catalyst in an amorphous form.
As shown in fig. 3, the sample prepared at 850 ℃ had the best ORR catalytic activity. The ORR of FeCu/NG-850 has an onset potential of 1.01V, a half-wave potential of 0.88V, which is higher than the onset potential (0.98V) and half-wave potential (0.86V) of a commercial grade 20 wt% Pt/C catalyst, indicating that FeCu/NG-850 has an ORR catalytic activity superior to 20 wt% Pt/C.
The stability of FeCu/NG-850 and 20 wt% Pt/C was determined by a chronoamperometric response method using an electrochemical workstation. The results are shown in FIG. 4, where after 12 hours, the current for FeCu/NG-850 catalyst decayed only 10.8%, while the current for 20 wt% Pt/C catalyst decayed 23.2%, indicating that FeCu/NG-850 had better stability than 20 wt% Pt/C catalyst under alkaline conditions.
The polarization curve and the corresponding power density of the cell are shown in FIG. 5 at room temperature, and the maximum power density of a zinc-air cell using FeCu/NG-850 catalyst as cathode can reach 164.2mW/cm2Is better than 138.2mW/cm of a zinc-air battery taking 20 wt% of Pt/C catalyst as a cathode2。
As shown in FIG. 6, the battery was operated at 5mA/cm by changing the zinc plate and the electrolyte at 40 hours after the test time was progressed to 20 hours2The discharge voltage is always kept above 1V under the current density of FeCu/NG-850, and after 60 hours, the discharge voltage still has no great attenuation, which shows that the FeCu/NG-850 catalyst has higher stability.
Claims (5)
1. A preparation method of a cathode catalyst of an iron/copper aza graphene zinc air battery is characterized by comprising the following steps:
(1) dissolving ferric trichloride hexahydrate and sodium hydroxide in deionized water, carrying out ultrasonic treatment until the ferric trichloride hexahydrate and the sodium hydroxide are uniformly dispersed, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 2-6h at the temperature of 80-120 ℃, cooling to room temperature, washing and drying to obtain a FeOOH precursor;
(2) dissolving copper chloride dihydrate in deionized waterAdding polyethylene glycol into water, stirring to dissolve, adding sodium hydroxide solution, stirring at room temperature for half an hour, washing and drying to obtain copper hydroxide Cu (OH)2A precursor;
(3) the urea is placed in a tube furnace and calcined for 4 to 8 hours at the temperature of 500-700 ℃ under the atmosphere of argon to obtain the graphite-phase carbon nitride g-C3N4；
(4) FeOOH and Cu (OH) were weighed out separately2Dissolving in deionized water, performing ultrasonic treatment for 20-40min, adding the solution into graphene oxide dispersion, and performing ultrasonic dispersion; then weighing g-C3N4Dissolving in deionized water, ultrasonic dispersing, and mixing with water3N4Adding FeOOH/Cu (OH) into the solution2Adding sodium alginate into the GO mixed solution after uniformly stirring, continuously stirring for 4-6h, and drying in an oven at 40-60 ℃ for 8-12h to obtain gel;
FeOOH、Cu(OH)2graphene oxide dispersion liquid, g-C3N4And the dosage proportion of sodium alginate is 0.089 g: 0.097 g: 10mL of: 0.2 g: 0.2g, wherein the concentration of the graphene oxide dispersion liquid is 1-5 mg/mL;
(5) putting the gel obtained in the step (4) into a quartz tube with one closed end, removing air in the tube by using a centrifugal pump, putting the quartz tube into a muffle furnace with the temperature of 750-950 ℃ for calcining for 10-25min after closing, and then cooling at room temperature;
(6) and (3) soaking the black solid obtained in the step (5) in a hydrochloric acid solution for 8-12h, keeping the temperature at 50-80 ℃, then washing the black solid with deionized water and ethanol to be neutral, drying the black solid, placing the dried black powder in a quartz tube with one closed end, vacuumizing the quartz tube, calcining the quartz tube at the temperature of 750-950 ℃ for 10-20min, and cooling the quartz tube to obtain the iron/copper aza graphene zinc air battery cathode catalyst.
2. The preparation method of the iron/copper aza graphene zinc air battery cathode catalyst according to claim 1, wherein in the step (1), the molar ratio of ferric trichloride hexahydrate to sodium hydroxide is 2: 3.
3. The preparation method of the iron/copper aza graphene zinc air battery cathode catalyst according to claim 1, wherein in the step (2), the mass ratio of copper chloride dihydrate to polyethylene glycol is as follows: 1.15:1, wherein the concentration of the sodium hydroxide solution is 3-6mol/L, the concentration of the copper chloride dihydrate solution is 0.92mg/mL, and the volume ratio of the sodium hydroxide solution to the copper chloride dihydrate solution is 1.2: 250.
4. the iron/copper nitrogen-doped graphene zinc air battery cathode catalyst is prepared by the preparation method of any one of claims 1-3, and is characterized in that iron-copper nanoclusters with the structure of 2-5nm are embedded into a nitrogen-doped graphene layer and are amorphous.
5. Use of the iron/copper aza graphene zinc-air cell cathode catalyst of claim 4 for the preparation of an air cathode of a zinc-air cell.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514450A (en) * | 2015-12-20 | 2016-04-20 | 青岛科技大学 | Nitrogen-doped graphene-ferronickel hydrotalcite difunctional oxygen catalyst and preparation method and application thereof |
| CN105870460A (en) * | 2016-03-31 | 2016-08-17 | 常州大学 | Preparation method of co-doped graphene gel by bonding of metal and nitrogen |
| CN106992304A (en) * | 2017-03-23 | 2017-07-28 | 江苏大学 | It is a kind of to nitrogenize the Preparation method and use that carbon-based composite oxygen reduction electro-catalyst modifies disk electrode |
-
2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514450A (en) * | 2015-12-20 | 2016-04-20 | 青岛科技大学 | Nitrogen-doped graphene-ferronickel hydrotalcite difunctional oxygen catalyst and preparation method and application thereof |
| CN105870460A (en) * | 2016-03-31 | 2016-08-17 | 常州大学 | Preparation method of co-doped graphene gel by bonding of metal and nitrogen |
| CN106992304A (en) * | 2017-03-23 | 2017-07-28 | 江苏大学 | It is a kind of to nitrogenize the Preparation method and use that carbon-based composite oxygen reduction electro-catalyst modifies disk electrode |
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