CN108736023B - Preparation of nickel-based catalyst additive for efficiently catalyzing direct oxidation of borohydride - Google Patents
Preparation of nickel-based catalyst additive for efficiently catalyzing direct oxidation of borohydride Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 35
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000000654 additive Substances 0.000 title abstract description 6
- 230000000996 additive effect Effects 0.000 title abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 39
- 229910002249 LaCl3 Inorganic materials 0.000 claims abstract description 38
- 230000008021 deposition Effects 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 9
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229940075397 calomel Drugs 0.000 claims abstract description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 5
- 241000080590 Niso Species 0.000 claims abstract description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 3
- 230000001965 increasing effect Effects 0.000 abstract description 16
- 239000000446 fuel Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007747 plating Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 22
- 229910000033 sodium borohydride Inorganic materials 0.000 description 14
- 239000012279 sodium borohydride Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910000474 mercury oxide Inorganic materials 0.000 description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- -1 lanthanum ions Chemical class 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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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
- H01M4/8853—Electrodeposition
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
A nickel-based catalyst additive for efficiently catalyzing direct oxidation of borohydride is prepared, which is characterized in that: (1) at normal temperature and pressure, 0.2mol/dm is prepared3Nickel sulfate NiSO of4，0.6g/dm3Lanthanum chloride LaCl3The solution is used as electrolyte, and the pH is adjusted to about 3; (2) at 2cm2The smooth Ni sheet is used as a working electrode and is placed in the solution, the carbon rod is used as a counter electrode, and the calomel electrode is used as a reference electrode; (3) depositing Ni on a metal nickel sheet by adopting a potentiostatic method to prepare a nickel-based catalyst; the deposition potential used was-1.0V, the deposition time was 110s, and the deposition temperature was 301.15K. Due to the addition of LaCl in the electrolyte3The catalyst has surface activity, is easy to adsorb on the surface of an electrode and cannot be reduced, so that micropores are formed on the surface of a plating layer after deposition is finished, the specific surface area of the catalyst is increased, and the activity of the catalyst is improved. Compared with the method without adding LaCl3Prepared catalyst of p-BH4 ‑The oxidation peak-to-peak current of (a) was increased to 0.2004A, so that the fuel utilization rate was improved to 41.46%.
Description
Technical Field
The invention belongs to the field of electrochemical application, and particularly relates to a method for preparing and improving boron hydrogen radical (BH) by an electrodeposition method by adding rare earth elements into electrolyte4 -) A nickel-based catalyst with direct oxidation properties.
Background
At present, in order to improve the performance of the anode of the direct borohydride fuel cell, expensive metal catalysts such as Pt, Ag, Pd and Au are generally adopted. For cost reduction, has catalytic capabilityAlso used as anode catalysts for direct borohydride fuel cells. However, when a nickel-based anode catalyst is used in the prior art, Ni is very easily corroded in an alkaline environment, thereby causing a decrease in catalytic activity, resulting in BH4 -The impedance of electrochemical reaction is increased during direct oxidation, the charge transfer resistance of electrode reaction is large, the reaction rate is slow, and BH4 -The direct oxidation performance of (2) is not high, and the fuel discharge efficiency is low.
Disclosure of Invention
The invention aims to remedy the above-mentioned shortcomings. The invention relates to a nickel-based catalyst additive for efficiently catalyzing direct oxidation of borohydride, which is characterized in that: (1) at normal temperature and pressure, 0.2mol/dm is prepared3Nickel sulfate (NiSO)4)，0.6g/dm3Lanthanum chloride (LaCl)3) The solution is used as electrolyte, and the pH value is adjusted to about 3; (2) assembling a three-electrode system: placing a smooth Ni sheet of 2cm multiplied by 1cm as a working electrode in the solution, wherein the working area of the Ni sheet is 1cm multiplied by 1cm, a carbon rod is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode; (3) in a constant temperature water bath at 301.15K, depositing Ni on the smooth Ni sheet by a potentiostatic method to prepare a nickel-based catalyst; wherein the deposition potential used in the process of preparing the nickel-based catalyst is-1.0V and the deposition time is 110 s.
The invention relates to a nickel-based catalyst additive for efficiently catalyzing direct oxidation of borohydride. During the electrodeposition process, the cathode of the substrate nickel electrode is negatively charged, and nickel ions in the solution can be attracted to the surface of the electrode to obtain electrons, so that the electrons are converted into nickel atoms to be deposited on the surface of the electrode. When nickel ions are adsorbed on the surface of the electrode to form an electric double layer, lanthanum ions added into the solution have good surface activity, and are also easily adsorbed on the surface of the electrode double-electrode layer. Due to La3+The standard electrode potential of/La is-2.52V, and the reduction deposition cannot be carried out in the electrodeposition process, so the electrode surface is separated after the experiment is finished, and a plurality of micropores are formed on the electrode surface. And BH4 -The B-H bond length in the ion was 110pm, the H-H bond length was 190pm, and La3+Has a diameter of 206 pm. Visible regular tetrahedron junctionStructural BH4 -The size of the electrode is close to the diameter of lanthanum ions, so that the electrode can be embedded in a vacancy formed by the lanthanum ions, the active specific surface area of the electrode is increased, and BH is enhanced4 -The direct oxidation performance of the fuel improves the discharge efficiency of the fuel obviously.
Drawings
FIG. 1 is a table of orthogonal experimental analyses;
FIG. 2 without addition of LaCl3SEM image of the prepared nickel-based catalyst;
FIG. 3 addition of 0.6g/dm3LaCl3SEM image of the prepared nickel-based catalyst;
FIG. 4LaCl3Effect of concentration on Nickel-based catalyst Performance
FIG. 5 BH in the presence of different Ni catalysts4 -Cyclic voltammogram of
FIG. 6LaCl3Effect of concentration on the stability of Nickel-based catalysts
1 a first period; 2a second period; 3 third period
FIG. 7LaCl3BH concentration under the action of Ni deposition4 -Influence of the AC impedance of
FIG. 8 BH in the presence of different Ni catalysts4 -Ac impedance spectrum of
FIG. 9 BH in the presence of different Ni catalysts4 -Discharge curve of
Detailed Description
The method of the invention is further illustrated below with reference to the figures and examples:
example 1:
at normal temperature and pressure, 0.2mol/dm is prepared3NiSO4，0.6g/dm3LaCl3The solution is used as electrolyte, and the pH value is adjusted to be about 3. 2cm in length2The smooth Ni sheet of (a) was placed in the above solution as a working electrode for electrodeposition. Determining optimized parameters of deposition temperature, deposition time and deposition voltage, wherein the horizontal number of the optimized parameters is three, and the specific values are 298.15K, 301.15K and 304.15K respectively; 90s, 100s, 110 s; -0.95V, -1.0V, -1.05V, thereby performing a three-factor three-level orthogonal realityThe preparation of Ni-based catalysts under different conditions was examined. Weighing appropriate amount of sodium borohydride (NaBH)4) And dissolving it in 2mol/dm3In NaOH solution of (2), to a concentration of 0.27mol/dm3NaBH4And uniformly mixing the solution to be used as the electrolyte of the direct sodium borohydride fuel cell. And respectively taking the Ni-based catalyst prepared under different parameter levels as a working electrode, a carbon rod as a counter electrode and a mercury/mercury oxide electrode as a reference electrode, and performing performance test by adopting Cyclic Voltammetry (CV).
In the embodiment, an orthogonal experiment method is adopted to optimize the electrodeposition parameters, and the influence of the deposition temperature, the deposition voltage and the deposition time on the performance of the nickel-based catalyst is researched. The experimental index measured is BH4 -Peak current value of oxidation (see fig. 1). It can be seen from fig. 1 that the temperature has a large influence on the plating. As the temperature increases, the thermal motion of the nickel ions in the bath is enhanced, resulting in more uniform deposition; however, the polarization of the electrode reaction is increased by increasing the temperature, and the overpotential is increased, and the deposition voltage is lowered, which in turn deteriorates the quality of the plating layer. It can also be seen that the deposition time does not have a significant effect on the peak current, and 110s was chosen to achieve the best possible coating. The effect of the deposition voltage is most pronounced, although increasing the voltage results in a greater increase in peak current. However, in the experimental process, it is found that the increase of the deposition voltage can cause the electrochemical oxidation peak potential to shift forward, which is probably because under the high deposition voltage, although the deposition amount is increased to increase the catalytic speed, the specific surface area of the electrode cannot be further increased, so that the polarization is increased under the high current density, an excessive overpotential is caused, and the comprehensive performance of the catalyst is not very good.
In summary, from the orthogonal experimental analysis, it can be determined that the optimal experimental conditions for preparing a high-efficiency nickel-based catalyst are: deposition temperature 301.15K, deposition time 110s, deposition voltage-1.0V.
Example 2:
at normal temperature and pressure, respectively adding 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0g/dm3LaCl30.2mol/dm of3NiSO4Solution 100mL, and adjusting the pH value to be about 3. 2cm in length2The smooth Ni sheet is used as a working electrode and is placed in the solution, water bath is carried out at constant temperature of 301.15K, a carbon rod is used as a counter electrode, a calomel electrode is used as a reference electrode, and Ni is deposited on a metal nickel sheet by adopting a constant potential method to prepare a nickel-based catalyst; wherein, the deposition potential adopted in the process of preparing the nickel-based catalyst is-1.0V, and the deposition time is 110 s. Weighing appropriate amount of NaBH4And dissolving it in 2mol/dm3In NaOH solution to 0.27mol/dm3NaBH4The solution is mixed evenly to be used as direct NaBH4An electrolyte for a fuel cell. Different Ni catalysts prepared under the conditions are used as working electrodes, carbon rods are used as counter electrodes, mercury/mercury oxide electrodes are used as reference electrodes, and Cyclic Voltammetry (CV) is adopted for performance test.
The non-LaCl additive according to the present example3Prepared Ni-based catalyst and added LaCl3Scanning Electron Micrographs (SEM) of the prepared Ni-based catalyst are shown in fig. 2 and 3, respectively. As can be seen from FIG. 2, no LaCl was added3The surface of the prepared Ni-deposited catalyst is formed by a compact and fine flaky structure. And adding LaCl3The prepared Ni-based catalyst has an island-shaped surface formed by stacking sheet-shaped forms, and a plurality of micropores with different sizes are formed on the surface (see figure 3). The morphology changes the surface morphology of the catalyst, so that the specific surface area is obviously increased, the catalytic active sites are greatly increased, and the BH is enhanced4 -Direct oxidation performance of (2).
FIG. 4 compares the results obtained with the addition of different concentrations of LaCl3(0.1～1.0g/dm3) The electrodeposition bath of (2) has a catalytic ability of the Ni-based catalyst prepared. As can be seen from FIG. 4, with LaCl3Increase in the amount of addition, BH4 -The oxidation peak current value shows a trend of increasing first and then decreasing, wherein LaCl is added3The concentration is 0.6g/dm3When, BH4 -The oxidation peak current value of (a) is the largest, and the catalytic ability of the Ni-based catalyst is the strongest. This is because LaCl3The addition of (2) causes a plurality of pores with different sizes on the surface of the prepared nickel-based catalyst,make BH4 -Can be embedded in the pores, increases the contact area between the catalyst and the surface of the catalyst, improves the active specific surface area of the electrode and ensures that BH is embedded in the catalyst4 -Oxidation peak current of with LaCl3The concentration increases. However, when LaCl is used3When the concentration is too high, pores formed on the surface of the nickel-based catalyst are too large, so that the pores are partially overlapped, the formed pores are enlarged, and more La is contained3+The Ni is adsorbed on the surface of the electrode, so that the deposition amount of Ni is reduced, the active specific surface area of the electrode is reduced, and the peak current is reduced.
FIG. 5 shows the addition of 0.6mol/dm3Of LaCl3And no addition of LaCl3BH under the action of prepared Ni-based catalyst4 -Cyclic voltammograms of direct oxidation. By comparison with a blank experiment (without lanthanum chloride), it can be seen that no LaCl is added3Under the action of Ni-based catalyst of (4), BH4 -The direct oxidation peak current of (1) was 0.108A/cm2And 0.6g/dm3LaCl3Under the action of a deposited Ni catalyst, BH4 -The direct oxidation peak current reaches 0.226A/cm2. In the presence of LaCl3BH under the action of deposited Ni catalyst4 -The direct oxidation peak current of (1) is no addition of LaCl 32 times under the action of the deposited Ni catalyst. To illustrate the preparation of Ni-based catalysts, LaCl was added3Can remarkably enhance BH4 -Direct oxidation performance of (2).
FIG. 6 shows the addition of different concentrations of LaCl3BH under the action of prepared Ni-based catalyst4 -Comparison of peak currents of multiple cyclic voltammograms of direct oxidation. It can be seen that as the scan period increases, the BH4 -The direct oxidation peak current of (2) is gradually reduced because in an alkaline environment, a dense nickel hydroxide Ni (OH) is generated on the surface of Ni2Covering the surface of the deposited Ni catalyst to gradually reduce the catalytic activity. With addition of LaCl3Increase in concentration, BH4 -The oxidation peak current of the cyclic voltammetry scanning of three periods of direct oxidation is increased firstly and thenA reduced tendency. With no addition of LaCl3Compared with the prepared deposited Ni catalyst, 0.6mol/dm is added3LaCl3Under the action of the prepared Ni-based catalyst, BH is performed in the first cyclic voltammetry process4 -The oxidation peak current of (A) is remarkably increased, and no LaCl is added32 times of the time; in the second period, the oxidation peak current is still kept at a higher level, and the situation that lanthanum chloride LaCl is not added is achieved3A peak current value of a first period; in the third period, BH4 -The oxidation peak current value is still improved. To illustrate, in NaBH4Adding LaCl into the solution3The corrosion resistance of the prepared Ni-based catalyst is far stronger than that of LaCl without lanthanum chloride3The prepared Ni-based catalyst.
Example 3:
at normal temperature and pressure, respectively adding 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0g/dm3LaCl30.2mol/dm of3NiSO4The solution is 100mL, and the pH value is adjusted to about 3. 2cm in length2The smooth Ni sheet is used as a working electrode and is placed in the solution, a carbon rod is used as a counter electrode, a calomel electrode is used as a reference electrode, and Ni is deposited on a metal nickel sheet by adopting a potentiostatic method at the water bath temperature of 301.15K to prepare a nickel-based catalyst; wherein, the deposition potential adopted in the process of preparing the nickel-based catalyst is-1.0V, and the deposition time is 110 s. Weighing appropriate amount of NaBH4And dissolving it in 2mol/dm3In NaOH solution to 0.27mol/dm3NaBH4And uniformly mixing the solution to be used as the electrolyte of the direct sodium borohydride fuel cell. And (3) taking different Ni-based catalysts prepared under the conditions as working electrodes, carbon rods as counter electrodes and mercury/mercury oxide electrodes as reference electrodes, and carrying out alternating current impedance spectrum test.
FIG. 7 compares the results obtained with the addition of different concentrations of LaCl3(0.1～0.9g/dm3) The electrochemical ac impedance of the Ni-based catalyst prepared by the electrodeposition bath of (1). Wherein, the intersection point of the impedance atlas and the real axis is the size of the solution resistance, and the diameter of the alternating current impedance atlas represents the size of the electrochemical polarization resistance. As can be seen from FIG. 7, when LaCl is used3The concentration is 0.6g/dm3The diameter of the ac impedance profile is smallest. Therefore, 0.6g/dm was added3LaCl3Prepared nickel-based catalyst catalyzes BH4 -The electrochemical polarization resistance of the direct oxidation reaction of (1) is minimal.
FIG. 8 shows no addition and 0.6g/dm addition3LaCl3BH under the action of prepared Ni-based catalyst4 -Direct oxidation ac impedance spectroscopy. As can be seen from the figure, BH is effected by two Ni-based catalysts4 -There are significant differences in the electrochemical impedance spectra of direct oxidation. Adding LaCl3Prepared Ni-based catalyst, BH4 -The diameter of the electrochemical impedance of direct oxidation is obviously smaller than that of the electrochemical impedance without adding LaCl3The value of the prepared Ni-based catalyst was only half of that of the latter, indicating that the addition of LaCl was sufficient3BH under the action of prepared Ni-based catalyst4 -The direct oxidation reaction is easier, and the resistance which needs to be overcome by the electrochemical reaction is smaller, thereby enhancing the charge transfer of the electrode reaction and obviously improving the BH4 -Oxidation performance of (2). The conclusion reached in example 2 is also confirmed.
Example 4:
at normal temperature and pressure, 0.2mol/dm is prepared3NiSO4，0.6g/dm3LaCl3The solution is used as electrolyte, and the pH value is adjusted to be about 3. 2cm in length2The smooth Ni sheet is used as a working electrode and is placed in the solution, a carbon rod is used as a counter electrode, a calomel electrode is used as a reference electrode, and Ni is deposited on a metal nickel sheet by adopting a potentiostatic method at the water bath temperature of 301.15K to prepare the nickel-based catalyst. Wherein, the deposition potential adopted in the process of preparing the nickel-based catalyst is-1.0V, and the deposition time is 110 s. Weighing appropriate amount of NaBH4And dissolving it in 2mol/dm3In NaOH solution to 0.27mol/dm3NaBH4The solution is mixed evenly to be used as direct NaBH4An electrolyte for a fuel cell. The different Ni-based catalysts prepared under the above conditions are used as working electrodes, carbon rods are used as counter electrodes, and mercury/mercury oxide electrodes are used as reference electrodes to perform constant current discharge.
FIG. 9 shows the current density at 10mA/cm2At a molar ratio of 0.27mol/dm3NaBH40.6g/dm of electrolyte solution is not added or added3LaCl3BH of prepared Ni-based catalyst4 -Discharge curve of (1). As can be seen from the figure, no LaCl was added3BH under the action of prepared Ni-based catalyst4 -Initial discharge potential E ofDeposition of Ni-0.88V; under the same conditions, 0.6g/dm is added3LaCl3BH under the action of prepared Ni-based catalyst4 -Initial discharge potential E ofLanthanum chloride + deposited Ni-0.92V vs. no addition of LaCl3The prepared Ni-based catalyst reduces 40 mV. It can also be seen that 0.6g/dm is added3LaCl3BH under the action of prepared deposited Ni catalyst4 -In the discharge potential plateau ratio of the electrode without addition of LaCl3The prepared deposited Ni catalyst is lower and more stable under the action. As can be seen from the above, in addition to LaCl3BH under the action of prepared deposited Ni catalyst4 -The initial potential of (a) is more negative and the operating voltage of the battery is higher. Under the same conditions, without addition of LaCl3BH under the action of prepared Ni-based catalyst4 -Has a discharge time of 8.6h, 0.6g/dm3LaCl3BH under the action of prepared Ni-based catalyst4 -The discharge time of (2) was 12 hours. By the formula:
eta: discharge efficiency;
t': actual discharge time;
t: a theoretical discharge time;
n：BH4 -the electron transfer number of the direct oxidation reaction is 8;
f: faraday electric quantity, which is 96500C/mol;
z: active substance BH4 -The amount of substance (d) is 2.7×10-3mol；
i: the current set value in the chronopotentiometric test is 0.02A.
The calculation can obtain: without addition of LaCl3BH under the action of prepared Ni-based catalyst4 -The discharge efficiency of (2) was 29.71%, and LaCl was added3BH under the action of prepared Ni-based catalyst4 -The discharge efficiency of (2) is 41.46%, and the discharge efficiency is improved by 11.75%.
Claims (1)
1. A preparation method of a nickel-based catalyst for catalyzing direct oxidation of borohydride comprises the following steps:
(1) at normal temperature and pressure, 0.2mol/dm is prepared3Nickel sulfate NiSO of4，0.6g/dm3Lanthanum chloride LaCl3The solution is used as electrolyte, and the pH is adjusted to 3;
(2) at 2cm2The smooth Ni sheet is used as a working electrode and is placed in the solution, the carbon rod is used as a counter electrode, and the calomel electrode is used as a reference electrode;
(3) depositing Ni on a metal nickel sheet by adopting a potentiostatic method to prepare a nickel-based catalyst; the preparation of the nickel-based catalyst is completed after the deposition is finished by adopting the deposition potential of-1.0V, the deposition time of 110s and the deposition temperature of 301.15K.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006210281A (en) * | 2005-01-31 | 2006-08-10 | Tama Tlo Kk | Method of manufacturing fuel electrode of fuel cell and fuel cell |
| CN105070926A (en) * | 2015-07-13 | 2015-11-18 | 重庆大学 | Nickel-based catalyst for improving performance of direct borohydride fuel cell |
| CN105826576A (en) * | 2016-05-31 | 2016-08-03 | 重庆大学 | Additive for improving nickel anode catalyst performance of direct borohydride fuel cell |
| CN106400059A (en) * | 2016-09-26 | 2017-02-15 | 河南理工大学 | Electrolyte additive used for electroforming high hardness and low stress nickel workpiece |
-
2018
- 2018-05-18 CN CN201810481383.7A patent/CN108736023B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006210281A (en) * | 2005-01-31 | 2006-08-10 | Tama Tlo Kk | Method of manufacturing fuel electrode of fuel cell and fuel cell |
| CN105070926A (en) * | 2015-07-13 | 2015-11-18 | 重庆大学 | Nickel-based catalyst for improving performance of direct borohydride fuel cell |
| CN105826576A (en) * | 2016-05-31 | 2016-08-03 | 重庆大学 | Additive for improving nickel anode catalyst performance of direct borohydride fuel cell |
| CN106400059A (en) * | 2016-09-26 | 2017-02-15 | 河南理工大学 | Electrolyte additive used for electroforming high hardness and low stress nickel workpiece |
Non-Patent Citations (2)
| Title |
|---|
| Influence of LaCl3 addition on microstructure and properties of nickel-electroplating coating;WANG Dan等;《Journal of Rare Earths》;20130228;第31卷(第2期);第209-213页 * |
| 基于稀土LaCl3的精密电铸工艺研究;蒋军涛 等;《机械制造与研究》;20050630;第34卷(第3期);第22页第2段至第24页第6段及附图1-4页 * |
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