Water electrolysis method
The described water electrolysis method using a nickel-metal hydride battery with controlled potential differences and a Ni2O3H coating on the negative electrode addresses inefficiencies and electrode degradation, enabling efficient generation of hydrogen and oxygen while promoting the reuse of used batteries.
Patent Information
- Application Number
- JP2023095892
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2023-06-09
- Publication Date
- 2025-11-18
- Estimated Expiration
- 2043-06-09
AI Technical Summary
Existing water electrolysis methods using nickel-metal hydride batteries face inefficiencies due to potential fluctuations that lead to electrode deterioration, particularly at the positive electrode, and the reusability of used nickel-metal hydride batteries is not effectively addressed.
A water electrolysis method utilizing a single nickel-metal hydride battery with controlled potential differences and electrochemical deactivation of lanthanum at the negative electrode, combined with a Ni2O3H coating on the negative electrode surface, to generate oxygen and hydrogen efficiently without electrode degradation.
The method achieves high energy conversion efficiency and improved durability of the electrolysis device by generating hydrogen and oxygen separately, allowing for the reuse of used nickel-metal hydride batteries and reducing electrode deterioration.
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Abstract
Description
[Technical Field]
[0001] The present disclosure relates to a water electrolysis method using a single nickel-metal hydride battery. [Background technology]
[0002] In recent years, demand for hydrogen (H2) gas has increased as an energy source for fuel cell vehicles and power generation, and research into H2 gas production methods is also underway. One method for producing H2 gas is to separate water (H2O) into hydrogen (H2) gas and oxygen (O2) gas through a water electrolysis reaction and then recover the gas.
[0003] For example, Patent Document 1 discloses a water electrolysis cell that uses platinum (Pt) for the negative electrode and nickel hydroxide (Ni(OH)2) for the positive electrode, in which oxygen is absorbed and released at the positive electrode, and oxygen is not released when hydrogen is generated at the negative electrode.
[0004] However, in Patent Document 1, platinum (Pt), which has a wide potential window, is used for the negative electrode. This means that the upper and lower limit potentials of the negative electrode during the electrochemical reaction can be greatly varied (the upper and lower limit potentials do not need to be considered). This means that the potential of the paired positive electrode can also be greatly varied. The nickel hydroxide (Ni(OH)2) used for the positive electrode continues to react reversibly as long as the valence of Ni fluctuates between divalent and trivalent. However, if the potential fluctuation is increased to, for example, between divalent and tetravalent, the positive electrode will irreversibly deteriorate (an oxide film will form on the positive electrode), which may reduce the efficiency of gas generation by water electrolysis.
[0005] Nickel-metal hydride batteries are already widely used in electric vehicles and hybrid vehicles, but the generation of used nickel-metal hydride batteries is expected in the future. Therefore, it is desirable to be able to reuse used nickel-metal hydride batteries as water electrolysis cells in a manner as close to reuse as possible. However, nickel-metal hydride batteries have a negative electrode containing LaNi5 and a positive electrode containing Ni(OH)2. In this system, when attempting to release oxygen from the positive electrode and hydrogen from the negative electrode, as in Patent Document 1, lanthanum (La) has hydrogen storage capacity, so it is necessary to first electrochemically deactivate lanthanum. However, no attention has been paid to the conditions for electrochemical deactivation of La that would not simultaneously degrade the positive electrode. [Prior art documents] [Patent documents]
[0006] [Patent Document 1] Special Publication No. 2017-534764 Summary of the Invention [Problem to be solved by the invention]
[0007] In light of such conventional demands, an object of the present disclosure is to provide a water electrolysis method using a single nickel-metal hydride battery, which has high energy conversion efficiency. [Means for solving the problem]
[0008] The means for solving the above problems include the following means. <1> Power supply and OH - an electrolyte in which ions can move; a single nickel-metal hydride battery having a positive electrode connected to the power source and a negative electrode including lantern and connected to the power source, the nickel-metal hydride battery being immersed in the electrolyte; A potential difference is applied by the power source such that the potential of the positive electrode is higher than the potential of the negative electrode, thereby generating oxygen gas from the positive electrode and hydrogen gas from the negative electrode. Water electrolysis method. <2> Before applying the potential difference, exposing the nickel-metal hydride battery to the atmosphere at 80°C or less; Thereafter, a voltage is applied to the negative electrode with a potential of −0.6 V or higher in a state where the pH of the electrolytic solution is adjusted to 7 or less, thereby oxidizing the lanthanum. <1> The water electrolysis method according to claim 1. [Effects of the Invention]
[0009] According to the present disclosure, it is possible to provide a water electrolysis method using at least one nickel-metal hydride battery, which has high energy conversion efficiency. [Brief explanation of the drawings]
[0010] [Figure 1] 1 is a schematic perspective view of an apparatus for carrying out a water electrolysis method according to an embodiment of the present disclosure. FIG. [Figure 2] FIG. 1 is a schematic perspective view of an apparatus for carrying out a water electrolysis method according to another embodiment of the present disclosure. [Figure 3] 3 is a schematic diagram illustrating a configuration in which a plurality of positive electrodes and a plurality of negative electrodes of a single battery module are connected to a power source in the water electrolysis apparatus shown in FIG. 2.
[0023] FIG. [Figure 4] This is a potential-pH diagram of Ni at 80°C. [Figure 5] This is a potential-pH diagram of Ni at 50°C. [Figure 6] FIG. 1 is a schematic diagram showing an example of the configuration of a nickel-metal hydride battery. DETAILED DESCRIPTION OF THE INVENTION
[0011] The water electrolysis method according to the present disclosure will be described in detail below with reference to the drawings. The drawings are schematic diagrams, and the size and shape of each part are appropriately exaggerated for ease of understanding.
[0012] In this disclosure, a "single nickel-metal hydride battery" may refer to a single battery cell or a single battery module having multiple battery cells. A "single battery cell" refers to a battery that is the smallest structural unit that functions as a single, independent battery. A "single battery module" refers to a battery that combines multiple cells and functions as a single, independent battery.
[0013] [Water electrolysis method] The water electrolysis method according to the present disclosure uses a power source, an electrolyte, and a single nickel-metal hydride battery. The nickel-metal hydride battery has a positive electrode connected to the power source and a negative electrode connected to the power source, and is immersed in the electrolyte. The power source applies a potential difference (voltage) such that the potential of the positive electrode is higher than the potential of the negative electrode, generating hydrogen gas (H) from the negative electrode and oxygen gas (O) from the positive electrode.
[0014] [Battery cell] One embodiment of the water electrolysis method according to the present disclosure will be described with reference to the apparatus illustrated in FIG. 1, in which a single nickel-metal hydride battery is used as a "battery cell." FIG. 1 is a schematic perspective view illustrating an example of a water electrolysis apparatus for implementing the water electrolysis method of the present disclosure. As shown in FIG. 1, the water electrolysis apparatus 20A includes a power source 3, a resistor 30 as an example of an electronic load, a housing 4 containing an electrolytic solution 40, a battery cell 100A immersed in the electrolytic solution 40 within the housing 4, and a distillation device 5. The power source 3 and the resistor 30 adjust the increase and decrease of voltage, enabling the desired voltage to be maintained. Note that a power source with a built-in electronic load function may also be used. The battery cell 100A has a positive electrode and a negative electrode, and the positive electrode is connected to the power source 3 and the resistor 30. The negative electrode is also connected to the power source 3 and the resistor 30. The battery cell 100A has a water supply port, to which a water supply pipe (not shown) equipped with a water supply pump 6 is connected. The water supply pump 6 is driven to supply water (H2O). The battery cell 100A also has a water outlet, to which a water outlet pipe (not shown) is connected, and excess water in the battery cell 100A is discharged from the outlet. The battery cell 100A has an oxygen (O2) gas outlet passage 101, which is connected to the distillation device 5. The battery cell 100A also has a hydrogen (H2) gas outlet passage 102 branching off from the outlet passage 101. The distillation device 5 contains an electrolyte, and the electrolyte in the distillation device 5 and the electrolyte 40 in the housing 4 are circulated through a circulation pipe (not shown) equipped with a liquid feed pump 7. The distillation device 5 has a water vapor (H2O) outlet 8. In FIG. 1, a gas flow meter (not shown), a gas pack (not shown), a flashback prevention valve (not shown), and the like may be attached to the outlet passage 102 as needed. In the above example, a resistor is used as the electronic load, but a variable resistor, for example, may be used instead of a resistor.
[0015] The water electrolysis apparatus 20A uses a nickel-metal hydride battery cell as the battery cell 100A. This nickel-metal hydride battery cell may be a used nickel-metal hydride battery cell. The term "used" refers to a battery whose charging capacity is lower than that of the battery immediately after manufacture.
[0016] In the water electrolysis device 20A, a voltage is applied by the power supply 3 and resistor 30 so that the potential of the positive electrode of the battery cell 100A is higher than the potential of the negative electrode. This causes a water electrolysis reaction in the water (HO) supplied to the battery cell 100A, generating O gas from the positive electrode of the battery cell 100A and H gas from the negative electrode. The water electrolysis reaction is shown below. (Positive electrode) OH - → 1 / 2H2O+1 / 4O2+e - (negative electrode) H2O+e - →1 / 2H2+OH -
[0017] When O gas is generated from the positive electrode of the battery cell 100A and H gas is generated from the negative electrode, the gas can be extracted as oxyhydrogen (HHO) gas (a mixed gas of hydrogen and oxygen). From the viewpoint of efficiently causing a water electrolysis reaction in water (HO) supplied to the battery cell 100A, it is preferable to maintain the potential difference between the positive electrode and the negative electrode at 1.48 V or more. From the viewpoint of facilitating the water electrolysis reaction, the potential difference obtained by subtracting the negative electrode potential from the positive electrode potential in the battery cell 100A is more preferably in the range of 1.48 V to 2.00 V, and from the viewpoint of efficiency, it is even more preferably in the range of 1.55 V to 1.80 V. When the generated oxyhydrogen (HHO) gas is extracted, a flow path switching valve or the like (not shown) may be used to allow the generated gas to pass through the exhaust passage 102.
[0018] Alternatively, a voltage may be applied so that the potential difference between the positive electrode and the negative electrode of the battery cell 100A is a predetermined potential difference, thereby generating only hydrogen gas or only oxygen gas, which eliminates the need for a subsequent process to separate the hydrogen gas and the oxygen gas.
[0019] The above-mentioned predetermined potential difference varies depending on the type (combination) of electrodes, the pH and temperature of the electrolyte, and other conditions, so here we will explain an example in which the positive electrode of battery cell 100A is Ni(OH)2, the negative electrode is LaNi5, the pH of the electrolyte is 15, and the temperature is 30°C. Note that with regard to the predetermined potential difference, a potential difference that generates only hydrogen is sometimes called a first potential difference, and a potential difference that generates only oxygen is sometimes called a second potential difference. When oxygen is generated, the potential at which oxygen is generated is 1.48V or higher, preferably 1.8V. When hydrogen is generated, the potential at which hydrogen is generated is −0.9V or less, preferably −1.0V. Based on the above potential, a voltage is applied to both electrodes so as to generate only hydrogen, or a voltage is applied to both electrodes with the polarity reversed so as to generate only oxygen (so that the current flows in the opposite direction to that when hydrogen is generated). By repeatedly charging and discharging in this way, hydrogen gas and oxygen gas can be generated at separate times. The number of cycles of voltage application is not particularly limited, as long as it is at least one, with one cycle being one charge and one discharge. It may be 5, 10, 15, 20, or even 100 times. The electrochemical reactions during charge and discharge in a nickel-metal hydride battery are shown below. Charge→ / ←Discharge (Positive electrode)Ni(OH)2+OH - ←→NiOOH+H2O+e - (Negative electrode)M+H2O+e - ←→MH+OH - (Overall)Ni(OH)2+M←→NiOOH+MH Furthermore, the time for applying the voltage may be determined appropriately depending on the positive electrode capacity of the battery, for example, 72 seconds / Ah at 30 Acc when charging / discharging the positive electrode capacity of the battery to 20% to 80%, or 24 seconds / Ah at 30 Acc when charging / discharging the positive electrode capacity of the battery to 40% to 60%. The oxygen generating potential (Table 1) and hydrogen generating potential (Table 2) at an electrolyte pH of 15 and temperatures of −30° C. to 80° C. are shown below. The first potential difference and the second potential difference at each temperature may be appropriately determined with reference to the potentials shown in Tables 1 and 2. [Table 1] [Table 2]
[0020] 1 may be opened and exhaust passage 101 may be closed when H gas is generated. When O gas is generated, O gas may be sent to distillation apparatus 5 through exhaust passage 101, reduced in distillation apparatus 5, and extracted from outlet 8 as water vapor (H O).
[0021] According to the present disclosure, by applying a voltage so that the potential difference between the positive electrode and the negative electrode is the predetermined potential difference, oxygen gas and hydrogen gas can be generated in a manner that does not cause deterioration of the positive electrode and the negative electrode, which leads to improved durability of the water electrolysis device.
[0022] Next, another embodiment will be described.
[0023] [Battery module] Another embodiment of the water electrolysis method according to the present disclosure will be described with reference to the device shown in Fig. 2, in which a "battery module" is used as a single nickel-metal hydride battery. Note that the same components as those in the device shown in Fig. 1 are designated by the same reference numerals, and redundant description will be omitted. FIG. 2 is a schematic perspective view illustrating a water electrolysis apparatus for implementing the water electrolysis method of the present disclosure. As shown in FIG. 2, the water electrolysis apparatus 20B includes a power source 3, a resistor 30, a housing 4 containing an electrolytic solution 40, a battery module 100B immersed in the electrolytic solution 40 within the housing 4, and a distillation apparatus 5. The water electrolysis apparatus 20B uses multiple nickel-metal hydride battery cells (six connected nickel-metal hydride battery modules in FIG. 2) as the battery module 100B. Each of the six nickel-metal hydride battery cells in the battery module 100B has a positive electrode and a negative electrode, and the positive electrodes are all connected to the power source 3 and the resistor 30. Furthermore, the negative electrodes are all connected to the power source 3 and the resistor 30. The battery module 100B has a water supply port connected to a water supply pipe (not shown) equipped with a water supply pump 6, and water (H2O) is supplied by driving the water supply pump 6. The battery module 100B has an oxygen (O2) gas discharge passage 101 connected to the distillation apparatus 5. Furthermore, the battery module 100B has a discharge passage 102 for hydrogen (H 2 ) gas separate from the discharge passage 101.
[0024] FIG. 3 shows an example of the connection between the power source 3 and the multiple (six pairs in FIG. 2) nickel-metal hydride battery cells included in the battery module 100B in the water electrolysis apparatus 20B shown in FIG. 2. Note that FIG. 3 omits components other than the battery module 100B and the power source 3, and also omits the illustration of an electronic load. As shown in FIG. 3, the positive and negative electrodes included in each of the multiple nickel-metal hydride battery cells included in the battery module 100B are all connected (short-circuited) to the power source 3. For example, the power source 3 may be connected to the positive and negative terminals of the battery module 100B, respectively.
[0025] In the water electrolysis apparatus 20B, the nickel-metal hydride battery modules used in the battery module 100B may be used nickel-metal hydride battery modules. Furthermore, in the water electrolysis apparatus 20B, the applied voltage may be the voltage of the water electrolysis apparatus 20A multiplied by the number of cells.
[0026] (Preferred embodiment) [Electrolyte] From the viewpoint of efficiently causing the water electrolysis reaction, the electrolyte in which the nickel-metal hydride battery is immersed preferably has a pH of 14 or higher, more preferably a pH of 15 or higher, and even more preferably a pH of 16 or higher. The pH is a value measured at 25°C using a pH meter.
[0027] The electrolyte is not particularly limited, but is preferably an aqueous electrolyte. For example, an alkaline aqueous solution can be suitably used as the aqueous electrolyte. The alkaline aqueous solution contains, for example, water and an alkali metal hydroxide dissolved in the water. The alkali metal hydroxide may have a concentration of, for example, 1 mol / L to 45 mol / L. Examples of the alkali metal hydroxide include potassium hydroxide (KOH), sodium hydroxide (NaOH), and lithium hydroxide (LiOH).
[0028] [temperature] From the viewpoint of facilitating the water electrolysis reaction, the temperature of the entire water electrolysis apparatus is preferably higher with an upper limit of 80° C., and is, for example, preferably 20° C. or higher and 80° C. or lower, more preferably 40° C. or higher and 80° C. or lower, and even more preferably 50° C. or higher and 80° C. The temperature of the entire water electrolysis apparatus is measured by measuring the temperature of the electrolytic solution.
[0029] [Ni2O3H coating] The background art of the present application discloses that the valence change of Ni between divalent and trivalent continues reversibly, but when the potential change is increased to cause the valence change between divalent and tetravalent, an oxide film (Ni2O3H film) is formed on the positive electrode, adversely affecting the efficiency of gas generation. However, in the present disclosure, the valence of Ni in the negative electrode may be intentionally changed between divalent and tetravalent to form a Ni2O3H film on the surface of the negative electrode. In a nickel-metal hydride battery, the negative electrode contains a hydrogen storage alloy containing a misch metal. The hydrogen storage alloy is characterized by absorbing and reversibly releasing hydrogen. Therefore, in order to prevent the hydrogen storage alloy from absorbing hydrogen generated on the negative electrode side during water electrolysis, a Ni2O3H coating may be formed on the surface of the negative electrode. The Ni2O3H coating contains Ni2O3H as the main component (the component with the largest mass) and is corrosion-resistant and conductive. The thickness of the coating is not particularly limited, but is, for example, 100 to 200 nm. For details of the Ni2O3H coating, refer to JP 2022-45695 A.
[0030] [Film formation method] In the film formation method, the material on which the film is to be formed (for example, LaNi5) is exposed to the atmosphere. Next, the material on which the coating is to be formed (e.g., LaNi5) is immersed in an acidic solution (pH 7 or less), and a first potential (upper potential) and a second potential (lower potential) are repeatedly applied to the LaNi5, thereby forming a Ni2O3H coating on the surface of the LaNi5. The first potential is within a potential range in which Ni is tetravalent in the Ni-H2O system. The second potential is within the potential range in which Ni becomes divalent in the Ni-H2O system.
[0031] The first potential (upper potential) and the second potential (lower potential) vary depending on the temperature and pH of the solution. Figure 4 shows the potential-pH diagram of Ni (Ni-HO system) at 80°C (a diagram showing the existence regions of each chemical species of Ni in water on a two-dimensional coordinate system of electrode potential and pH). The case of an alkaline solution will be described with reference to Figure 4. The same applies to an acidic solution. For example, when using an 8 M KOH aqueous solution (pH 14.9) at 80°C, the first potential (the potential at which Ni becomes tetravalent) is higher than approximately 0.48 V (SHE reference potential). The second potential (the potential at which Ni becomes divalent) is a potential within a range of approximately 0.27 V (SHE reference potential) or less.
[0032] The first potential is preferably about 0.48 V or more. If the first potential is too low within this range, the formation rate will be slow, and if the first potential is too high in combination with the second potential, the formation efficiency will be poor, so it is preferable to set the first potential appropriately.
[0033] The second potential is preferably about 0.27 V or less, and within this range, if it is too high the formation rate will be slow, and if it is too low the ratio of Ni2O3H to LaNi5 will be small, so it is preferable to set it appropriately.
[0034] Figure 5 is a potential-pH diagram of Ni at 50°C. As shown in Figure 5, for example, when an 8 M KOH aqueous solution is used at 50°C, the first potential is a potential higher than about 0.57 V. The second potential is a potential lower than about 0.37 V.
[0035] As shown in Figures 4 and 5, the ranges of the first and second potentials used in the coating formation method change depending on the pH, temperature, etc. of the solution. Therefore, it is desirable to apply potentials within appropriate ranges of the first and second potentials that satisfy the above conditions depending on the pH, temperature, etc. of the solution. The temperature of the solution is preferably 40 to 90°C, more preferably 45 to 85°C. In the case of an alkaline solution, the pH is preferably 10 or higher, more preferably 12 or higher, and even more preferably 14 or higher.
[0036] Specific examples of the alkaline solution include KOH solution, NaOH solution, LiOH solution, etc., and KOH solution and NaOH solution are preferred. The concentration of the alkaline solution is preferably a concentration that provides the aforementioned pH.
[0037] The application times of the first voltage and the second voltage are, for example, 5 seconds for the first voltage and 10 seconds for the second voltage, and are set appropriately for each solution condition (solution type, pH, temperature). The total application time of the first voltage and the second voltage is set appropriately so as to obtain a desired thickness of the Ni2O3H coating.
[0038] [Nickel-metal hydride battery] Here, a nickel-metal hydride battery that can be used in the water electrolysis method of the present disclosure will be described. The nickel-metal hydride battery (hereinafter sometimes abbreviated as "battery") may be a used nickel-metal hydride battery that has been used, for example, as a battery for portable devices, an in-vehicle battery, or a battery for renewable energy power generation.
[0039] FIG. 6 is a schematic diagram showing an example of the configuration of a nickel-metal hydride battery cell. The battery cell 1 is a nickel-metal hydride battery cell. The battery cell 1 includes a housing 2. The housing 2 is a cylindrical case. The housing 2 is made of metal. However, the housing 2 may have any shape. The housing 2 may be, for example, a rectangular case. The housing 2 may be, for example, a pouch made of aluminum laminate film. The housing 2 may be, for example, made of resin.
[0040] The housing 2 houses an electricity storage element 10 and an electrolyte. The electricity storage element 10 includes a positive electrode 11, a negative electrode 12, and a separator 13. The illustrated electricity storage element 10 is a wound type. The electricity storage element 10 is formed by spirally winding strip-shaped electrodes. The electricity storage element 10 may be, for example, a laminated type. The electricity storage element 10 may be formed, for example, by laminating sheet-shaped electrodes.
[0041] [Negative electrode] The negative electrode 12 is in the form of a sheet. The negative electrode 12 may have a thickness of, for example, 10 μm to 1 mm. The negative electrode 12 has a lower potential than the positive electrode 11.
[0042] The negative electrode includes, for example, a negative electrode current collector and a negative electrode active material. The negative electrode current collector can be, for example, a nickel mesh. The negative electrode active material can be, for example, a hydrogen storage alloy. The composition of the hydrogen storage alloy is not limited as long as it can store and release hydrogen. Examples of hydrogen storage alloys include Mm-Ni-Mn-Al-Co alloys. "Mm" refers to a mixture of rare earth elements known as misch metal. Specific examples include La-Ni alloys such as LaNi5.
[0043] [Positive electrode] The positive electrode 11 is in the form of a sheet. The positive electrode 11 may have a thickness of, for example, 10 μm to 1 mm. The positive electrode 11 has a higher potential than the negative electrode 12. The positive electrode 11 includes a positive electrode active material. The positive electrode active material may include any component. Examples of the positive electrode active material include nickel hydroxide (Ni(OH)2), cobalt hydroxide (Co(OH)2), manganese dioxide, and silver oxide. The positive electrode active material is preferably nickel hydroxide.
[0044] The positive electrode 11 may be substantially composed of only a positive electrode active material. The positive electrode 11 may further include a current collector, a conductive material, a binder, and the like in addition to the positive electrode active material. The current collector may include, for example, a porous metal sheet. The current collector is made of, for example, Ni.
[0045] For example, the positive electrode 11 can be formed by applying a positive electrode active material, a conductive material, and a binder to a current collector. The conductive material has electronic conductivity. The conductive material can contain any component. The conductive material may contain, for example, carbon black, Co, cobalt oxide, etc. The amount of the conductive material may be, for example, 0.1 to 10 parts by mass per 100 parts by mass of the positive electrode active material. The binder binds the current collector and the positive electrode active material. The binder can contain any component. The binder may contain, for example, ethylene vinyl acetate (EVA), etc. The amount of the binder may be, for example, 0.1 to 10 parts by mass per 100 parts by mass of the positive electrode active material.
[0046] [Separator] The separator 13 is in a sheet form. The separator 13 is disposed between the positive electrode 11 and the negative electrode 12. The separator 13 physically separates the positive electrode 11 and the negative electrode 12. The separator 13 may have a thickness of, for example, 50 μm to 500 μm. The separator 13 is porous. The separator 13 may include, for example, a stretched porous film, a nonwoven fabric, or the like. The separator 13 is electrically insulating. The separator may be made of, for example, polyolefin, polyamide, or the like.
[0047] [Electrolyte] The electrolyte is not particularly limited, but is preferably an aqueous electrolyte. For example, an alkaline aqueous solution can be suitably used as the aqueous electrolyte. The alkaline aqueous solution contains, for example, water and an alkali metal hydroxide dissolved in the water. The alkali metal hydroxide may have a concentration of, for example, 1 mol / L to 20 mol / L. Examples of the alkali metal hydroxide include potassium hydroxide (KOH), sodium hydroxide (NaOH), and lithium hydroxide (LiOH).
[0048] As described above, the water electrolysis method according to the present disclosure allows reuse of used nickel-metal hydride batteries to efficiently and safely extract high-purity H gas and O gas. Furthermore, since the generation of O gas and the generation of H gas can be separated in time, high-purity H gas and O gas can be safely extracted separately. Furthermore, according to the present disclosure, when the negative electrode contains an oxygen-storing substance such as lanthanum, it is possible to oxidize only the negative electrode (i.e., deactivate the lanthanum at the negative electrode) at a potential difference that does not cause deterioration of the positive electrode. In other words, a Ni2O3H coating can be formed only on the negative electrode. Then, hydrogen can be generated from the electrode containing lanthanum during subsequent water electrolysis. [Example]
[0049] Here, the generation of hydrogen gas and oxygen gas in the water electrolysis method according to the embodiment of the present disclosure was confirmed by experiment.
[0050] [Example 1] The experiment was carried out using a water electrolysis apparatus having the same configuration as the water electrolysis apparatus 20B shown in Fig. 2. The following electrolytes and battery modules were used. Electrolyte: Potassium hydroxide (KOHaq, pH 15) Battery module: Used battery module NP2, manufactured by Primearth EV Energy Co., Ltd.
[0051] The water electrolysis device, like the water electrolysis device 20B shown in FIG. 2, had one power source and a battery module (NP2) with six battery cells. NP2 was used with the top cover removed, leaving each battery cell open. The positive and negative terminals of NP2 were both connected to the power source. The positive and negative terminals were also connected to a resistor as an electronic load in addition to the power source.
[0052] In this water electrolysis device, water (H2O) was supplied to NP2 from a water supply pump at room temperature (20°C), and the voltage was maintained by a power supply and a resistor so that the potential of the positive electrode in NP2 was higher than the potential of the negative electrode. After the voltage was maintained, it was confirmed that oxygen (O2) gas was introduced and hydrogen (H2) gas was discharged.
[0053] When water electrolysis was performed using used NP2, an extremely high energy conversion efficiency (68.0%) was observed, as shown in Table 3, even though the measurement was performed at room temperature (20°C). [Table 3]
[0054] As described above, hydrogen (H) gas can be recovered highly efficiently through a water electrolysis reaction using battery modules, particularly used battery modules. Thus, the water electrolysis method according to the present disclosure can achieve excellent effects and contribute to the transition to a circular economy society. Furthermore, in the water electrolysis method according to the present disclosure, by applying a voltage to achieve a predetermined potential difference, hydrogen (H2) gas and oxygen (O2) gas can be separately recovered from a single battery module, eliminating the need for a downstream process to separate hydrogen gas. Furthermore, by using this predetermined potential difference, hydrogen (H2) gas and oxygen (O2) gas can be generated at a potential difference that does not cause deterioration of the positive and negative electrodes, thereby improving the durability of the water electrolysis cell. [Explanation of symbols]
[0055] 1 battery 10. Energy storage element 11 Positive electrode 12 Negative electrode 13 Separator 2. Case 3 Power supply 4. Cabinet 40 Electrolyte 5. Distillation apparatus 6. Water supply pump 7 Liquid transfer pump 8 Outlet 20A, 20B water electrolysis equipment 30 resistor 100A battery cell 100B battery module 101, 102 Discharge passage
Claims
[Claim 1] Power supply and OH - an electrolyte in which ions can move; a single nickel-metal hydride battery having a positive electrode connected to the power source and a negative electrode containing lanthanum and nickel connected to the power source, the single nickel-metal hydride battery being immersed in the electrolyte; a potential difference is applied by the power source such that the potential of the positive electrode is higher than the potential of the negative electrode, thereby generating oxygen gas from the positive electrode and hydrogen gas from the negative electrode; Before applying the potential difference, exposing the negative electrode containing lanthanum and nickel to the air at 80°C or less, and then immersing the negative electrode in an acidic solution of pH 7 or less, and repeatedly applying a first potential and a second potential to the negative electrode alternately; The first potential is Ni—H 2 It is within a potential range in which Ni becomes tetravalent in an O system, The second potential is Ni—H 2 It is within the potential range in which Ni becomes divalent in the O system. Water electrolysis method.
Citation Information
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