Application of alloy material CePdAl, electrolytic hydrogen production method and hydrogen storage method
By using CePdAl alloy material as the cathode and storage material for electrolytic hydrogen production, the problem of efficient hydrogen storage and release by existing solid hydrogen storage materials is solved, realizing efficient hydrogen storage and release in the electrolytic hydrogen production process, which is suitable for a variety of hydrogen energy devices.
Patent Information
- Application Number
- CN202410957914.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-17
- Publication Date
- 2026-01-20
AI Technical Summary
Existing solid hydrogen storage materials require high-pressure hydrogen injection and are not easy to release hydrogen. They are also unsuitable for the process of producing hydrogen through water electrolysis, making it difficult to achieve efficient hydrogen energy storage and release.
The alloy material CePdAl is used as the cathode and hydrogen storage material for electrolytic hydrogen production. Taking advantage of its crystal structure of space group 189 P-62m, hydrogen is produced and stored by electrolysis in alkaline water electrolyte or ionic liquid. The wires are connected by wrapping bare wires without insulation or bonding them with conductive adhesive to achieve efficient storage and release of hydrogen.
It enables the simultaneous electrolytic hydrogen production and storage, and the hydrogen is easily released without the need for additional heating operations, thus improving the efficiency of electrolytic hydrogen production. The materials are reusable and suitable for both small and large hydrogen energy equipment.
Smart Images
Figure CN121362983A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the field of solid hydrogen storage materials. Specifically, the present application relates to the use of the alloy material CePdAl, i.e. as a cathode for the electrolytic production of hydrogen, and for the storage of hydrogen. BACKGROUND
[0002] Under the guidance of the "double carbon" strategy, the consumption of environmentally friendly renewable energy will gradually increase year by year. However, clean energy represented by wind and solar energy has uneven time and geographical location space distribution, and has the characteristics of randomness, seasonality and anti-peaking, which makes it difficult to efficiently utilize clean energy.
[0003] Hydrogen energy has the advantages of high calorific value and only water as the product after combustion, and is considered an ideal choice for energy storage and supply regulation. However, the preparation and storage of hydrogen are two important problems. Electrolysis of water to produce hydrogen can efficiently convert solar energy, wind energy and the like into chemical energy of hydrogen. Solid hydrogen storage has the advantages of small volume, greater safety and convenience compared to traditional gas tank hydrogen storage. However, existing solid hydrogen storage materials usually require high-pressure hydrogen injection and are not easy to release hydrogen, for example, MgH2 requires heating or water to release hydrogen, and existing solid hydrogen storage materials cannot store hydrogen during the electrolysis of water.
[0004] Although materials with lattice 189th space group P-62m, such as CeNiAl, are easy to absorb hydrogen (BOBET J L, CHEVALIER B, DARRIET B, et al. Hydrogen absorption properties of CeNiAl: influence on its crystal structure and magnetic behaviour [J]. Journal of Alloys & Compounds, 2001, 317: 67-70), however, CeNiAl is not easy to grow high-quality single crystals, and usually requires high-pressure hydrogen to inject hydrogen, and is not suitable for electrolytic hydrogen injection.
[0005] Therefore, there is an urgent need for a solid material that stores hydrogen and releases hydrogen more easily, and at the same time, the material can be used as an electrode for the electrolytic production of hydrogen to facilitate the conversion of electrical energy into hydrogen energy. SUMMARY
[0006] The purpose of the present application is to provide a solid material that stores hydrogen and releases hydrogen more easily, and at the same time, the material can be used as an electrode for the electrolytic production of hydrogen.
[0007] The above-mentioned purpose of the present application is achieved by the following technical solutions.
[0008] In a first aspect, the present application provides a use of an alloy material CePdAl in a cathode for electrolytic hydrogen production and / or in a hydrogen storage material.
[0009] Preferably, in the use of the present application, the alloy material CePdAl is a single crystal, a polycrystalline bulk or a powder.
[0010] Preferably, in the use of the present application, the alloy material CePdAl has a space group No. 189 P-62m with a lattice constant of γ = 120°.
[0011] In a second aspect, the present application provides a method for electrolytic hydrogen production, comprising the following steps:
[0012] (1) preparing an alloy material CePdAl into a cathode for electrolytic hydrogen production;
[0013] (2) providing an electrolyte and an anode;
[0014] (3) immersing the cathode and the anode into the electrolyte, and connecting the cathode and the anode to the negative pole and the positive pole of a power supply respectively, and then turning on the power supply to produce hydrogen by electrolysis.
[0015] Preferably, in the method for electrolytic hydrogen production of the present application, the alloy material CePdAl is a single crystal, a polycrystalline bulk or a powder.
[0016] Preferably, in the method for electrolytic hydrogen production of the present application, the alloy material CePdAl has a space group No. 189 P-62m with a lattice constant of γ = 120°.
[0017] Preferably, in the method for electrolytic hydrogen production of the present application, the electrolyte is an alkaline aqueous electrolyte or an ionic liquid.
[0018] Preferably, in the method for electrolytic hydrogen production of the present application, when the alloy material CePdAl is a single crystal, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the following steps:
[0019] cutting the single crystal alloy material CePdAl into a sheet, preferably a sheet with a thickness of 0.1-1 mm, and then connecting it to a wire by a method of winding the wire without an insulation layer to serve as a cathode for electrolytic hydrogen production.
[0020] Preferably, in the method for electrolytic hydrogen production of the present application, when the alloy material CePdAl is a polycrystalline bulk, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the following steps:
[0021] The polycrystalline alloy material CePdAl block is ground into powder, and the powder is bonded into a block with conductive glue to re-form a block.
[0022] Preferably, in the method for electrolytic hydrogen production of the present application, when the alloy material CePdAl is in powder form, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the following step: bonding the polycrystalline alloy material CePdAl powder into a block with conductive glue.
[0023] In a third aspect, the present application provides a method for hydrogen storage, comprising the following steps:
[0024] (1) preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production;
[0025] (2) providing an electrolyte and an anode;
[0026] (3) immersing the cathode and the anode into the electrolyte, and connecting the cathode and the anode to the negative pole and the positive pole of a power supply respectively, and then turning on the power supply to produce hydrogen by electrolysis, while storing the produced hydrogen in the cathode.
[0027] Preferably, in the method for hydrogen storage of the present application, the alloy material CePdAl is in the form of single crystal, polycrystalline block or powder.
[0028] Preferably, in the method for hydrogen storage of the present application, the alloy material CePdAl has a space group No. 189 P-62m and a lattice constant of γ = 120°.
[0029] In the method for hydrogen storage of the present application, the powder XRD pattern of the alloy material CePdAl is as shown in Figure 1 .
[0030] Preferably, in the method for hydrogen storage of the present application, the electrolyte is an alkaline aqueous electrolyte or an ionic liquid.
[0031] Preferably, in the method for hydrogen storage of the present application, when the alloy material CePdAl is in the form of single crystal, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the following steps: cutting the single crystal alloy material CePdAl into a sheet, preferably a sheet with a thickness of 0.1-1 mm, and then connecting it to a wire by a method of winding the wire without an insulation layer, to serve as a cathode for electrolytic hydrogen production.
[0032] Preferably, in the hydrogen storage method of the present application, when the alloy material CePdAl is a polycrystalline block, the preparation of the alloy material CePdAl into a cathode for electrolytic hydrogen production in step (1) is carried out by a method comprising the following steps: grinding the polycrystalline alloy material CePdAl block into powder, and then binding the powder into a block with conductive glue to re-form the block.
[0033] Preferably, in the hydrogen storage method of the present application, when the alloy material CePdAl is a polycrystalline block, the preparation of the alloy material CePdAl into a cathode for electrolytic hydrogen production in step (1) is carried out by a method comprising the following steps: grinding the polycrystalline alloy material CePdAl block into powder, and then binding the powder into a block with conductive glue to re-form the block.
[0034] In the electrolytic hydrogen production method of the present application or in the hydrogen storage method of the present application, if the CePdAl used is a single crystal, the single crystal needs to be first cut into a sheet with a thickness of about 0.1-1 mm, and then connected to a wire by a method of winding the wire without an insulating layer, and then connected to the negative pole of a power supply as a cathode for electrolytic hydrogen production.
[0035] In the electrolytic hydrogen production method of the present application or in the hydrogen storage method of the present application, if the CePdAl used is a polycrystalline block or powder, the polycrystalline needs to be ground into powder, and then bound into a block with conductive glue, and then re-formed into a block by solidification. Preferably, to ensure a large proportion of working substance, the amount of conductive glue used should be as small as possible while ensuring good binding of the powder. When the conductive glue is mixed with the powder, in order to facilitate uniform mixing, an appropriate amount of volatile solvent such as alcohol can be added as a dispersant. The connection of the wire can be carried out by a method of embedding the wire in the conductive glue before drying, or by a method of winding a bare wire after drying.
[0036] In a specific embodiment of the present application, the conductive glue is not particularly limited, and a conventional conductive glue in the art can be used, such as silver glue or graphite glue.
[0037] In a specific embodiment of the present application, the electrode prepared in the present application can be used for electrolytic hydrogen production from alkaline aqueous electrolyte or from ionic liquid. For example, the prepared electrode is connected to the negative pole of a power supply as a cathode of an electrolytic cell, a platinum electrode is connected to the positive pole of the power supply as an anode of the electrolytic cell, and an alkaline aqueous electrolyte or an ionic liquid is used as the electrolyte, and an electrolysis voltage of 2.1-5 V is applied, and hydrogen is produced (hydrogen gas is emitted) at the cathode of the present application, and hydrogen is also injected into the CePdAl in the cathode.
[0038] In a specific embodiment of the present application, after the cathode is fully charged with hydrogen, the power supply is disconnected, and at this time hydrogen gas will continue to be emitted spontaneously from the cathode. After the hydrogen gas is released, the electrode can be repeatedly charged with hydrogen by applying power. Figure 2The hydrogen gas collected by the exhaust gas collection method after the power is turned off is shown.
[0039] The present application has the following advantages:
[0040] (1) The alloy material CePdAl of the present application can be used as a cathode for electrolytic hydrogen production, and can store hydrogen while producing hydrogen by electrolysis.
[0041] (2) When the alloy material CePdAl of the present application is used as a hydrogen storage material, hydrogen is easily released without the need for heating or other operations; after sufficient hydrogen absorption, hydrogen can be spontaneously released from the alloy material CePdAl.
[0042] (3) The method of the present application is expected to improve the efficiency of electrolytic hydrogen production.
[0043] (4) The alloy material CePdAl of the present application can be hydrogenated by the method of electrolyzing water, and the hydrogenation method is simple.
[0044] (5) The hydrogen production and storage electrode proposed in the present application can be reused.
[0045] (6) The alloy material CePdAl of the present application can be used in both small hydrogen production and storage equipment and large-scale water electrolysis hydrogen production projects. Specifically, this material can be used to solve the problem of uneven distribution of clean energy such as wind and solar energy in space and time by producing hydrogen and storing hydrogen at the same time through water electrolysis, and can be used in large-scale water electrolysis hydrogen production projects, and can be used in small hydrogen production equipment to continuously release hydrogen gas for a period of time after power failure. BRIEF DESCRIPTION OF DRAWINGS
[0046] Hereinafter, embodiments of the present application will be described in detail with reference to the accompanying drawings, in which:
[0047] Figure 1 The powder X-ray diffraction spectrum of single crystal CePdAl in one specific embodiment of the present application is shown.
[0048] Figure 2 The hydrogen gas collected by the exhaust gas collection method after the power is turned off is shown. DETAILED DESCRIPTION
[0049] The present application will be further described in detail below with reference to specific embodiments, and the examples given are only to illustrate the present application, and are not intended to limit the scope of the present application.
[0050] Example 1
[0051] This example uses CePdAl single crystal as cathode and 1 mol / L NaOH solution as electrolyte. This example can store hydrogen while producing hydrogen by electrolysis, which includes the following steps:
[0052] 1) Cut CePdAl single crystal into thin pieces of about 0.4 mm with wire saw, about 5 mm x 5 mm in size. Connect the thin pieces with platinum wire of 0.05 mm in diameter by winding method as the cathode of electrolytic cell. Connect the platinum wire to the negative pole of power supply with soldering tin.
[0053] 2) Cut platinum foil of 0.1 mm in thickness into about 1 cm x 2 cm with an elongated tail as lead wire, and connect to the positive pole of power supply.
[0054] 3) Immerse the electrodes prepared in steps 1), 2) into 1 mol / L NaOH solution, and connect the power supply; provide 4 V voltage between the anode and the cathode.
[0055] 4) Turn off the power supply after 3 hours, and immediately collect the hydrogen continuously emitted from CePdAl cathode by drainage gas collection method. The volume of hydrogen collected after half an hour is about 12 times the volume of CePdAl used.
[0056] Example 2
[0057] This example uses CePdAl single crystal as cathode and DEME-TFSI ionic liquid (diethylmethyl-(2-methoxyethyl) ammonium bis(trifluoromethylsulfonyl) imide) as electrolyte. This example can store hydrogen while producing hydrogen by electrolysis, which includes the following steps:
[0058] 1) Cut CePdAl single crystal into thin pieces of about 0.15 mm with wire saw, about 3 mm x 3 mm in size. Connect the thin pieces with platinum wire of 0.05 mm in diameter by winding method as the cathode of electrolytic cell. Connect the platinum wire to the negative pole of power supply with soldering tin.
[0059] 2) Cut platinum foil of 0.1 mm in thickness into about 1 cm x 2 cm with an elongated tail as lead wire, and connect to the positive pole of power supply.
[0060] 3) Immerse the electrodes prepared in steps 1), 2) into DEME-TFSI ionic liquid, and connect the power supply; provide 4.5 V voltage between the anode and the cathode.
[0061] 4) Turn off the power supply after 7 days, and hydrogen will continuously emit from CePdAl single crystal, and the bubbling can last for up to 2 days.
[0062] Example 3
[0063] This example uses polycrystalline CePdAl powder as the electrode and 1 mol / L NaOH solution as the electrolyte. This example electrolyzes to produce hydrogen while also storing hydrogen, which includes the following steps:
[0064] 1) Put about 0.1 g of polycrystalline CePdAl powder into a container, and introduce a small amount of alcohol to make it a whole liquid that can flow.
[0065] 2) Mix the H20E 1OZ AB type conductive silver paste according to the A paste and B paste 1:1 ratio (volume ratio) uniformly, and then take about 0.1 g and put it into the container in step 1), and stir it uniformly. After a period of time when the alcohol evaporates, the mixture becomes viscous, at which time the mixture is transferred to a glass slide. One end of a platinum gold wire with a diameter of 0.05 mm is buried in the mixture, and then it is shaped into a shape of about 3 mm x 3 mm x 1 mm. Place the glass slide on a hot plate and heat it at 120°C for 20 minutes to solidify the silver paste. Take the finished electrode from the glass slide, connect the free end of the platinum gold wire to the negative electrode of the power supply, and use the solidified electrode as the cathode of the electrolytic cell.
[0066] 3) Cut the platinum gold sheet with a thickness of 0.1 mm into about 1 cm x 2 cm and leave an elongated tail as a wire connected to the positive electrode of the power supply.
[0067] 4) Immerse the electrodes prepared in steps 2) and 3) into 1 mol / L NaOH solution, and connect the power supply to provide a voltage of 4V between the anode and the cathode.
[0068] 5) After 3 hours, disconnect the power supply, and hydrogen gas will continue to emerge from the cathode.
[0069] 6) After half an hour, connect the power supply, and after another 3 hours, disconnect the power supply, and hydrogen gas will continue to emerge from the CePdAl cathode.
[0070] Comparative Example 1
[0071] This comparative example uses CeNiAl single crystals as the cathode and DEME-TFSI ionic liquid as the electrolyte, which includes the following steps:
[0072] 1) Cut the CeNiAl single crystal into a thin sheet of about 0.3 mm with a wire cutting machine, and the size is about 3 mm x 3 mm. Use a platinum gold wire with a diameter of 0.05 mm to connect it by winding, as the cathode of the electrolytic cell. Connect the platinum gold wire to the negative electrode of the power supply with solder.
[0073] 2) Cut the platinum gold sheet with a thickness of 0.1 mm into about 1 cm x 2 cm and leave an elongated tail as a wire connected to the positive electrode of the power supply.
[0074] 3) The electrodes prepared in step 1), 2) were immersed in DEME-TFSI ionic liquid and power was turned on to provide a voltage of 4.5 V between the anode and the cathode.
[0075] 4) After about two days, the CeNiAl single crystal was broken into pieces.
[0076] The results of this comparative example show that the CeNiAl single crystal was broken into pieces, indicating that the CeNiAl single crystal is not suitable for the method proposed in the present application (i.e. hydrogen can be produced by electrolysis while also being stored).
Claims
1. Use of the alloy material CePdAl in a cathode for electrolytic hydrogen production and / or in a hydrogen storage material.
2. Use according to claim 1, wherein, The alloy material CePdAl is a single crystal, a polycrystalline block or a powder; Preferably, the alloy material CePdAl has a space group No. 189, P-62m, with a lattice constant of γ = 120°.
3. A method for electrolytic hydrogen production, comprising the following steps: (1) preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production; (2) providing an electrolyte and an anode; (3) immersing the cathode and the anode into the electrolyte, and connecting the cathode and the anode to the negative and positive poles of a power supply respectively, and then turning on the power supply to produce hydrogen by electrolysis.
4. The method of claim 3, wherein, The alloy material CePdAl is a single crystal, a polycrystalline block or a powder; Preferably, the alloy material CePdAl has a space group No. 189, P-62m, with a lattice constant of γ = 120°.
5. The method of claim 3, wherein, The electrolyte is an alkaline aqueous electrolyte or an ionic liquid.
6. The method of claim 4, wherein, When the alloy material CePdAl is a single crystal, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the following steps: cutting the single crystal alloy material CePdAl into a sheet, preferably a sheet with a thickness of 0.1-1 mm, and then connecting it to a wire by a method of winding the sheet with a bare wire without an insulating layer to serve as a cathode for electrolytic hydrogen production.
7. The method of claim 4, wherein, When the alloy material CePdAl is a polycrystalline block, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the following steps: grinding the polycrystalline alloy material CePdAl block into a powder, and then binding the powder into a block with conductive glue to re-form a block.
8. The method of claim 4, wherein, When the alloy material CePdAl is a powder, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the following steps: binding the polycrystalline alloy material CePdAl powder into a block with conductive glue.
9. A method for hydrogen storage, comprising the following steps: (1) preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production; (2) providing an electrolyte and an anode; (3) immersing the cathode and the anode into the electrolyte, and connecting the cathode and the anode to the negative and positive poles of a power supply respectively, and then turning on the power supply to produce hydrogen by electrolysis, and storing the produced hydrogen in the cathode.
10. The method of claim 9, wherein, The alloy material CePdAl is a single crystal, a polycrystalline block or a powder; Preferably, the alloy material CePdAl has a space group No. 189, P-62m, with a lattice constant of γ = 120°; Preferably, the electrolyte is an alkaline aqueous electrolyte or an ionic liquid. Preferably, when the alloy material CePdAl is a single crystal, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the following steps: cutting the single crystal alloy material CePdAl into a sheet, preferably a sheet with a thickness of 0.1-1 mm, and then connecting it to a wire by a method of winding the sheet with a bare wire without an insulating layer to serve as a cathode for electrolytic hydrogen production. Preferably, when the alloy material CePdAl is a polycrystalline block, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the following steps: grinding the polycrystalline alloy material CePdAl block into a powder, and then binding the powder into a block with conductive glue to re-form a block. Preferably, when the alloy material CePdAl is in the form of a powder, the step (1) of preparing the alloy material CePdAl into a cathode for electrolytic hydrogen production is performed by a method comprising the step of: binding the alloy material CePdAl powder into a block with conductive glue.