CN114921807A - Membrane electrode material for preparing sodium borohydride hydrogen storage by electrolyzing sodium metaborate and process - Google Patents

Membrane electrode material for preparing sodium borohydride hydrogen storage by electrolyzing sodium metaborate and process Download PDF

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Publication number
CN114921807A
CN114921807A CN202210620168.7A CN202210620168A CN114921807A CN 114921807 A CN114921807 A CN 114921807A CN 202210620168 A CN202210620168 A CN 202210620168A CN 114921807 A CN114921807 A CN 114921807A
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China
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membrane electrode
hydrogen storage
sodium borohydride
electrode material
sodium
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CN202210620168.7A
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Chinese (zh)
Inventor
魏永生
司司
付文英
卡盖·索音图
杜文晨
袁昀
梁宇欣
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Jiangsu Normal University
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Jiangsu Normal University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/34—Electroplating: Baths therefor from solutions of lead
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The invention discloses a membrane electrode material for preparing sodium borohydride hydrogen storage by electrolyzing sodium metaborate and a process thereof, wherein the process comprises the following steps: the lead-based membrane electrode is prepared in a flow cell by using a flow pump, the flow cell is made of polypropylene, two bilaterally symmetrical spaces are formed by separating a Nafion membrane, and the two formed chambers respectively carry out flow renewal on 50ml of metal ion solution and 50ml of NaBH4 alkaline solution. The catalyst is prepared by using the flow cell, the process is simple, the amplification is easy, and the method has popularization and application values.

Description

Membrane electrode material for preparing sodium borohydride hydrogen storage by electrolyzing sodium metaborate and process
Technical Field
The invention relates to a membrane electrode material for preparing sodium borohydride hydrogen storage by electrolyzing sodium metaborate and a process thereof. The material has excellent hydrogen storage performance, and the preparation device has a flowing special structure, and belongs to the field of hydrogen storage materials and sodium borohydride regeneration.
Background
Sodium borohydride (NaBH) 4 ) The hydrogen storage material is an excellent hydrogen storage material, the hydrogen storage density can reach 10.8 wt%, the regenerated product is pollution-free, the hydrogen discharge purity is high, and the hydrogen storage material is an ideal hydrogen source for fuel cells, and is a promising candidate hydrogen storage material in Proton Exchange Membrane Fuel Cells (PEMFC) and direct hydroboration fuel cell (DBFC) systems, but the hydrogen storage material is expensive, the hydrogen production cost is too high, the regeneration is difficult, a noble metal catalyst is needed, and the like, so that the development of the hydrogen storage material is restricted.
At present, scholars at home and abroad mainly use a chemical plating method for preparing a catalyst participating in a reaction in the research field of electro-reduction of sodium metaborate, such as Zhang Shimin chemically plating a Eu-Ni-B rare earth composite electrode by taking a copper sheet as a substrate and how to sensitively chemically plating a nickel-based and cobalt-based rare earth composite electrode by taking the copper sheet as the substrate. The process finds that the Nafion membrane has stronger acidity and stable performance in the long-term electrocatalysis process, which plays an extremely important role in reducing cost and energy consumption and improving electrolysis efficiency, so the inventor selects the Nafion membrane as the substrate. The metal catalyst is also a key material of the membrane electrode and has a decisive influence on the performance and stability of the membrane electrode. Therefore, in order to reduce polarization overpotential, electrolysis voltage and energy consumption, it is necessary to prepare an electrode catalytic material with high activity, low overpotential and stable performance. In the earlier work of the subject group of the inventor, several non-noble metals of Pb, Sn, Bi, Zn, Cd, Cu and the like are compared, and the Pb has better catalytic activity in the process of preparing sodium borohydride by electrically reducing sodium metaborate. In summary, the inventor selects to prepare the lead-based Nafion membrane electrode material, tries to adopt a preparation method such as an immersion reduction method, a two-chamber method and a flow plating method in the early stage, compares the preparation methods in sequence, optimizes and improves the performance gradually, finds that the flow cell can realize continuous circulation of the metal liquid and the reduction liquid compared with the former two, enables the liquid to react fully, and has good catalytic performance of the lead-based membrane electrode material which is plated in a flow mode.
Disclosure of Invention
The invention provides a membrane catalyst material for preparing sodium borohydride by electrochemically reducing sodium metaborate in a flowing electrolytic cell, aiming at the problems that the catalyst cost is high and the concentration of the generated sodium borohydride is low in the process of electrochemically reducing the sodium metaborate to prepare the sodium borohydride.
The technical purpose is achieved, the technical effect is achieved, and the invention is realized through the following technical scheme:
a membrane electrode material for hydrogen storage of sodium borohydride prepared by electrochemical reduction of sodium metaborate is characterized by comprising the following steps: 50ml of 0.025mol/L PbCl is respectively carried out on both sides of the flow cell 2 Solution and 50ml of 0.1mol/L NaBH 4 And (4) updating the flow of the alkali liquor for 12h, namely simultaneously performing the steps of metal ion exchange and reduction of the coating.
As a further improvement of the invention, the membrane electrode material for hydrogen storage of sodium borohydride prepared by electrochemical reduction of sodium metaborate is characterized in that: a Nafion membrane was used to prepare a lead-based membrane catalyst. .
As a further improvement of the invention, the membrane electrode material for hydrogen storage of sodium borohydride prepared by electrochemical reduction of sodium metaborate is characterized in that: the size of the membrane electrode is 30-100mm, and the actual size is matched with the mould.
As a further improvement of the invention, the membrane electrode material for hydrogen storage of sodium borohydride prepared by electrochemical reduction of sodium metaborate is characterized in that: the flow cell is made of two customized polypropylene plates, the upper part and the lower part of the corresponding two sides of each plate are respectively provided with a hole with the diameter of 2-5mm, and the hole is connected with a hose to refresh the solution through a flow pump. During preparation, the Nafion membrane is clamped between the two plates and the whole device is fixed by screws. Separated by Nafion film to form two bilaterally symmetrical spaces, and the two formed chambers are respectively filled with 50ml of PbCl 2 Solution and NaBH 4 And (4) flow updating of the alkali liquor.
As a further improvement of the invention, the membrane electrode material for hydrogen storage of sodium borohydride prepared by electrochemical reduction of sodium metaborate is characterized in that: the left and right chambers are rectangular with the same size, the length is 30-100mm, the width is 3-5mm, and the height is 30-100 mm.
As a further improvement of the invention, the membrane electrode material for hydrogen storage of sodium borohydride prepared by electrochemical reduction of sodium metaborate is characterized in that: the outer length of the two plates is 50-120mm, the outer width is 6-8mm, and the height is 50-120 mm.
Drawings
FIG. 1 is a three-dimensional schematic view of a flow cell (for plating);
FIG. 2 is a schematic diagram of a flow cell coating operation;
FIG. 3 is an SEM image of a flow cell lead film plated catalyst;
FIG. 4 shows different PbCl in example 1 2 Performance optimization plots of the catalysts prepared at solution concentrations.
FIG. 5 is a linear voltammogram for 0.5h of electrolysis at different voltages in example 2.
FIG. 6 is a linear voltammogram of flowing electrolysis at an electrolysis voltage of 3V for different times in example 3.
FIG. 7 shows NaBH flowing and electrolyzing at 3V for different periods of time in example 3 4 A velocity map and a faraday efficiency map are generated.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention is described in detail below with reference to the attached drawing figures:
as shown in FIG. 1, the preparation device of the present invention comprises two customized polypropylene plates and screws, a flow pipe connects the flow pump and the device (as shown in FIG. 2), each plate has a hole with a diameter of 2-5mm at the upper and lower parts corresponding to two sides, and the hole connecting hose carries out solution renewal through the flow pump. During preparation, a Nafion membrane is clamped between two plates, and the whole device is fixed by screws. Separated by a Nafion membraneTwo bilaterally symmetrical spaces are formed, and 50ml of PbCl is respectively carried out in the two chambers 2 Solutions and NaBH 4 And (4) flow updating of the alkali liquor. Fig. 3 is an SEM image of a lead film catalyst, showing that a uniform structure of a lamellar sheet shape has been prepared. .
Example 1: the catalyst was prepared using Nafion membrane lead plating, 40 x 40mm in size, prepared by sandwiching the Nafion membrane between two plates and fixing the entire device internally with screws. 50ml of PbCl were placed on both sides of the flow cell 2 The solution and 50ml NaBH of 0.1mol/L concentration 4 Alkali liquor is used for flowing and updating the solution on the two sides for 12 hours by using a flow pump to fix the flow rate, namely the steps of metal ion exchange and reduction of the coating are carried out simultaneously, wherein PbCl 2 The concentrations of the solutions were 0.0119, 0.0148, 0.0178, 0.0237, 0.025, 0.027, 0.030mol/L, respectively. Then a two-electrode system is adopted to electrolyze NaBO by a flow electrolytic cell at 3.0V under normal temperature and pressure 2 Alkali liquor.
Example 2: the catalyst was prepared using Nafion membrane plated with lead, 40 x 40mm in size, and prepared by sandwiching Nafion membrane between two plates and fixing the whole device inside with screws. 50ml of 0.025mol/L PbCl are respectively arranged at the two sides of the flow cell 2 Solution and 50ml NaBH concentration of 0.1mol/L 4 And (3) alkali liquor, wherein the flowing pump is used for flowing and updating the solution on the two sides for 12 hours, namely the steps of metal ion exchange and reduction of the coating are carried out simultaneously. Then, a two-electrode system is adopted, CHI660B electrochemical workstation manufactured by Shanghai Chenghua instruments company is used as a power supply to supply power, and NaBO is respectively electrolyzed by a flow electrolytic cell at 2.6V, 2.8V, 3.0V, 3.2V and 3.4V at normal temperature and normal pressure 2 Alkali liquor.
Example 3: the catalyst was prepared using Nafion membrane lead plating, 40 x 40mm in size, prepared by sandwiching the Nafion membrane between two plates and fixing the entire device internally with screws. 50ml of 0.025mol/L PbCl are respectively arranged at both sides of the flow cell 2 Solution and 50ml NaBH concentration of 0.1mol/L 4 And (3) alkali liquor, wherein the solution on the two sides flows and updates for 12h by using a flow pump, namely the steps of metal ion exchange and reduction of the coating are simultaneously carried out. Then, two-electrode system was adopted, and electrochemical reaction was carried out using CHI660B manufactured by Shanghai Chenghua instrumentsThe workstation is used as power supply, the electrolytic voltage is 3V at normal temperature and normal pressure, and NaBO is respectively electrolyzed by a flowing electrolytic cell at 0.5, 1, 1.5, 2, 2.5, 3.5, 4, 4.5, 5, 5.5, 6.5, 7.5, 8 and 20h 2 Alkali liquor.
Performance test
The method for measuring the reduced sodium borohydride comprises the following steps: after the electrolysis is finished, a gold electrode is used as a working electrode, a mercury-mercury oxide electrode is used as a reference electrode, a graphite electrode is used as a counter electrode, the three electrodes are arranged in a cathode chamber, the concentration of sodium borohydride in the electrolyzed solution is tested by using a linear voltammetry method or a cyclic voltammetry method, the test voltage range is-0.8-0V, the scanning speed is 0.05V/s, and whether the sodium borohydride is generated or not is judged by whether an oxidation peak exists at the position of about-0.5V of a scanning curve or not.
Different PbCl was used corresponding to example 1 as shown in FIG. 4 2 The performance optimization plot of the catalyst prepared at solution concentration, it can be seen that the membrane prepared at 0.025mol/L concentration performs optimally.
As shown in FIG. 5, which is a graph of Lsv electrolyte obtained by electrolysis at different voltages corresponding to example 2, it can be seen that the peak current of electrolysis is the largest and the concentration of sodium borohydride is the highest at 3V.
As shown in fig. 6 corresponding to the effect of different electrolysis times on the electrolysis in example 2, it can be seen that the longer the electrolysis time is, the higher the current is, and the higher the concentration of sodium borohydride is, indicating that the prepared lead film catalyst material has good performance.
As shown in fig. 7, which is a graph of the generation rate and the faraday efficiency corresponding to different electrolysis times in example 2, it can be seen that the concentration of sodium borohydride increases as the electrolysis time increases within 8 h. However, when the electrolysis time reaches 20h, the concentration of sodium borohydride is increased to a certain extent at the moment, but the faradaic efficiency is obviously reduced, which indicates that most of current is not used for electrolyzing sodium metaborate at the moment. The longer the electrolysis time is, the higher the concentration of the generated sodium borohydride is, and the good performance of the prepared lead film catalyst material is shown.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (6)

1. A membrane electrode material for hydrogen storage of sodium borohydride prepared by electrochemical reduction of sodium metaborate is characterized by comprising the following steps: 50ml of 0.025mol/L PbCl is respectively carried out on both sides of the flow cell 2 Solution and 50ml of NaBH with a concentration of 0.1mol/L 4 And (4) updating the flow of the alkali liquor for 12h, namely simultaneously performing the steps of metal ion exchange and reduction of the coating.
2. The membrane electrode material for hydrogen storage and preparation of sodium borohydride by electrochemical reduction of sodium metaborate as claimed in claim 1, wherein: a Nafion membrane was used to prepare a lead-based membrane catalyst.
3. The membrane electrode material for hydrogen storage and preparation of sodium borohydride by electrochemical reduction of sodium metaborate as claimed in claim 1, wherein: the size of the membrane electrode is 30-100mm, and the actual size is matched with the mould.
4. The membrane electrode material for hydrogen storage and preparation of sodium borohydride by electrochemical reduction of sodium metaborate as claimed in claim 1, wherein: the flow cell is made of two customized polypropylene plates, the upper part and the lower part of the corresponding two sides of each plate are respectively provided with a hole with the diameter of 2-5mm, and the hole is connected with a hose to refresh the solution through a flow pump. During preparation, a Nafion membrane is clamped between two plates, and the whole device is fixed by screws. Two bilaterally symmetrical spaces are formed by separating Nafion films, and 50ml of PbCl is respectively carried out in the two formed chambers 2 Solutions and NaBH 4 And (4) flow updating of the alkali liquor.
5. The membrane electrode material for hydrogen storage and preparation of sodium borohydride by electrochemical reduction of sodium metaborate as claimed in claim 1, wherein: the left and right chambers are rectangular with the same size, the length is 30-100mm, the width is 3-5mm, and the height is 30-100 mm.
6. The membrane electrode material for hydrogen storage and preparation of sodium borohydride by electrochemical reduction of sodium metaborate as claimed in claim 1, wherein: the outer length of the two plates is 50-120mm, the outer width is 6-8mm, and the height is 50-120 mm.
CN202210620168.7A 2022-06-02 2022-06-02 Membrane electrode material for preparing sodium borohydride hydrogen storage by electrolyzing sodium metaborate and process Withdrawn CN114921807A (en)

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CN202210620168.7A CN114921807A (en) 2022-06-02 2022-06-02 Membrane electrode material for preparing sodium borohydride hydrogen storage by electrolyzing sodium metaborate and process

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Application Number Priority Date Filing Date Title
CN202210620168.7A CN114921807A (en) 2022-06-02 2022-06-02 Membrane electrode material for preparing sodium borohydride hydrogen storage by electrolyzing sodium metaborate and process

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Application publication date: 20220819