Hydrogen storage materials, hydrogen storage containers, and hydrogen supply devices

Abstract

Provided is a hydrogen storage material which has hydrogen occlusion (storage) release properties suitable for hydrogen storage purposes even in a temperature range of 0°C or lower. Also provided are: a hydrogen storage container provided with the hydrogen storage material; and a hydrogen supply apparatus provided with the hydrogen storage container. More specifically provided are: a hydrogen storage material containing an alloy having an elemental formula represented by formula (1); a hydrogen storage container provided with the hydrogen storage material; and a hydrogen supply apparatus provided with the hydrogen storage container. [In formula (1), M represents at least one element selected from Mn, Co and Al and essentially contains Mn, and a satisfies the formula: 0.00 ≦ a ≦ 0.62, b satisfies the formula: 0.20 ≦ b ≦ 0.57, c satisfies the formula: 0.17 ≦ c ≦ 0.60, d satisfies the formula: 4.50 ≦ d ≦ 5.20, and e satisfies the formula: 0.15 ≦ e ≦ 0.70, in which a+b+c = 1, c+e satisfies the formula: 0.55 ≦ c+e ≦ 1.20, and d+e satisfies the formula: 5.13 ≦ d+e ≦ 5.40.]

Description

Technical Field

[0001] The present invention relates to a hydrogen storage material, a hydrogen storage container, and a hydrogen supply device.

Background Art

[0002] A hydrogen storage alloy is an alloy that can reversibly store and release hydrogen. It has already been used as the negative electrode material of a nickel-hydrogen secondary battery. In recent years, it is also expected as a material that can safely store hydrogen, which has attracted attention as an energy source, and research on its use in a hydrogen storage and supply system has been continued. There are various hydrogen storage alloys such as AB5 type, AB2 type, TiFe type, and BCC type such as TiVCr. Among them, the AB5 type alloy is easy to activate initially, and the plateau property of the hydrogen pressure-composition isotherm diagram (PCT curve) is relatively good. Therefore, it is being studied for practical use as a hydrogen storage material.

[0003] The usage environment of hydrogen storage materials is expected to become more diverse in the future. Currently, common hydrogen storage tanks store hydrogen near room temperature, raise the temperature to about 100 °C at the time of using hydrogen, and are used at a hydrogen release pressure of 10 atm or less. In the future, however, use in low-temperature regions below 0 °C such as recovery of boil-off gas of liquefied hydrogen and hydrogen storage in cold regions, or applications that require a high release pressure of 10 atm or more at room temperature (for example, hydrogen compressor applications) are also assumed. However, there are few reported examples of hydrogen storage alloys that operate in such environments. In addition, there are very few alloys that have good initial activation and also satisfy requirements such as a high hydrogen storage capacity, good plateau flatness, and hysteresis.

[0004] Patent Document 1 discloses: (1) a hydrogen storage material composed of an alloy represented by the general formula LmNi a-x , a-x , x A x (where Lm is a rare earth metal containing 40 to 70% of La, 0.1 to 2.0% of Ce, and other metals such as Nd, Pr, and Sm; A is a metal selected from the group of Al, Mn, Fe, and Cr; 4.8 < a < 5.5, x = 0.01 to 2.0), and (2) the general formula LmNi a-x ​y B z (In the formula, Lm is a rare earth metal containing 40 to 70% of La, 0.1 to 20% of Ce, and other metals such as Nd, Pr, Sm, etc.; A is a kind of metal selected from the group of Al, Mn, Fe; B is a kind of metal selected from the group of Mn (except when A is Mn), Co, Zr, V; 4.8 < a < 5.5, x = y + z, y, z = 0.01 to 2.0), a hydrogen storage material composed of an alloy is disclosed. Furthermore, by adopting the above configuration, it is disclosed that an activation at normal temperature is easy, the hydrogen storage amount is large, the absorption and release rates are fast, the hysteresis is small, and a hydrogen storage material having a flat plateau can be obtained.)

[0005] Patent Document 2 discloses a hydrogen storage material characterized by containing a general formula R·Ni 5-(a+b+c) ·A a ·B b ·Co c , provided that R is a rare earth metal or a mixture of rare earth metals; A is one of Mn, Fe, Cr; B is one of Al, Sn; a, b, c are each 0.01 to 1.0 and contain one of Al or Sn and Co, and (2) a hydrogen storage material characterized by containing a general formula R·Ni 5-(a+b+c+d) ·A a ·B b ·C c ·Co d , provided that R is a rare earth metal or a mixture of rare earth metals; A and B are each one of Mn, Fe, Cr and are different metals; C is one of Al, Sn; a, b, c, d are each 0.01 to 1.0 and contain one of Al or Sn and Co. Furthermore, it is disclosed that by adding Co and Al or Sn together with one or two of Mn, Fe, Cr to the R-Ni-based alloy, the storage amount is large and the hysteresis is reduced.)

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] Although both Patent Document 1 and Patent Document 2 aim to improve various properties by adding elements, the assumed usage environment is around 0°C to 100°C. For use in a low-temperature environment of 0°C or lower, new technological development is considered necessary.

[0008] Therefore, an object of the present invention is to provide a hydrogen storage material having hydrogen absorption (storage) and release characteristics suitable for hydrogen storage in a low-temperature environment of 0°C or lower. In particular, it is to provide a hydrogen storage material having a large hydrogen absorption (storage) amount and hydrogen release amount, capable of absorbing and releasing hydrogen in the temperature range of -20°C, and having a small hysteresis of the PCT curve. Furthermore, in a low-temperature environment of 0°C or lower, it is to provide a hydrogen storage container including a hydrogen storage material having hydrogen absorption and release characteristics suitable for hydrogen storage, and a hydrogen supply device including the hydrogen storage container. [Means for Solving the Problems]

[0009] As a result of intensive studies to solve the above problems, the inventors of the present invention have found that an alloy having a composition containing specific rare earth elements and transition metal elements based on LaNi5 has sufficient hydrogen absorption and release ability at -20°C, has a small hysteresis, and in addition, the PCT curve shows a clear rectangularity, so that a large amount of hydrogen can be released and there is almost no pressure fluctuation until the end of hydrogen release. Based on this finding, the present invention has been completed.

[0010] That is, according to the present invention, there is provided a hydrogen storage material having an alloy with an element composition represented by the following formula (1). [Chemical Formula] [In equation (1), M is at least one selected from Mn, Co, and Al, and Mn is a required element. a is 0.00 ≤ a ≤ 0.62, b is 0.20 ≤ b ≤ 0.57, c is 0.17 ≤ c ≤ 0.60, d is 4.50 ≤ d ≤ 5.20, and e is 0.15 ≤ e ≤ 0.70. Therefore, a + b + c = 1, c + e is 0.55 ≤ c + e ≤ 1.20, and d + e is 5.13 ≤ d + e ≤ 5.40.]

[0011] According to another aspect of the present invention, a hydrogen storage container comprising the above-mentioned hydrogen storage material and a hydrogen supply device comprising the hydrogen storage container are provided. [Effects of the Invention]

[0012] Since the hydrogen storage material of the present invention has an alloy having the above-mentioned specific elemental composition, it exhibits excellent hydrogen absorption and release characteristics at temperatures below 0°C and can be suitably used for hydrogen storage. [Brief explanation of the drawing]

[0013] [Figure 1] These are the hydrogen pressure-composition isotherm (PCT curve) at -20°C for the alloy powder of Example 1 and the alloy powder of Comparative Example 1. The equilibrium pressure on the y-axis represents the hydrogen storage pressure during hydrogen storage and the hydrogen release pressure during hydrogen release. [Figure 2] These are the hydrogen pressure-composition isotherm (PCT curve) at -20°C for the alloy powder of Example 1 and the alloy powder of Comparative Example 3. The equilibrium pressure on the y-axis represents the hydrogen storage pressure during hydrogen storage and the hydrogen release pressure during hydrogen release. [Modes for carrying out the invention]

[0014] The present invention will now be described in detail. The hydrogen storage material of the present invention is a material having an alloy with an elemental composition represented by the following formula (1). Preferably, the material is made of this alloy. Hereafter, the alloy with the elemental composition represented by formula (1) may also be referred to as the alloy of the present invention. [ka] [In equation (1), M is at least one selected from Mn, Co, and Al, and Mn is a required element. a is 0.00 ≤ a ≤ 0.62, b is 0.20 ≤ b ≤ 0.57, c is 0.17 ≤ c ≤ 0.60, d is 4.50 ≤ d ≤ 5.20, and e is 0.15 ≤ e ≤ 0.70. Therefore, a + b + c = 1, c + e is 0.55 ≤ c + e ≤ 1.20, and d + e is 5.13 ≤ d + e ≤ 5.40.]

[0015] In formula (1), a, b, c, d, and e represent the atomic ratio of each element, and the details are as follows. Hereafter, this ratio may be referred to as "content" or "amount."

[0016] La is effective in increasing hydrogen storage capacity, and the value of a representing the La content in equation (1) is 0.00 ≤ a ≤ 0.62. The lower limit of a is preferably 0.01 ≤ a, and more preferably 0.02 ≤ a. The upper limit of a is preferably a ≤ 0.40. If the upper limit is exceeded, the equilibrium pressure may decrease.

[0017] Ce is effective in increasing equilibrium pressure, and the value of b representing the Ce content in equation (1) is 0.20 ≤ b ≤ 0.57. Preferably, the lower limit of b is 0.22 ≤ b. If it exceeds the upper limit, the hysteresis of the PCT curve may decrease.

[0018] Sm is effective in increasing the equilibrium pressure and in causing the PCT curve to exhibit a clear angularity. In equation (1), c, which represents the Sm content, is 0.17 ≤ c ≤ 0.60. The lower limit of c is preferably 0.20 ≤ c, more preferably 0.22 ≤ c, and particularly preferably 0.24 ≤ c. The upper limit of c is preferably c ≤ 0.55. If it is below the lower limit, the effect of increasing the equilibrium pressure may not be expected, and the effect of showing a clear angularity in the PCT curve may not be obtained. If it is above the upper limit, the hydrogen storage capacity may decrease. The angularity refers to the degree of shoulder (shoulder) exhibited by the shape at the end of the PCT release curve, and the more pronounced the shoulder, the better the angularity. Alloys with good angularity exhibit the performance of being able to release absorbed hydrogen at a constant release pressure until the end of the release. The index of this angularity in this application will be described later.

[0019] Ni is effective in improving the durability and reducing hysteresis of the hydrogen storage alloy according to the present invention, and the value of d, which represents the Ni content in formula (1), is 4.50 ≤ d ≤ 5.20. Preferably, the lower limit of d is 4.55 ≤ d, and preferably the upper limit of d is d ≤ 5.15. If it is below the lower limit, the expected effects of improving durability and reducing hysteresis may not be achieved, and if it is above the upper limit, the hydrogen storage capacity may decrease.

[0020] M is an element selected from Mn, Co, and Al, and is essentially composed of Mn, which is effective in reducing the hysteresis of the PCT curve. In formula (1), e, which represents the content of M, is 0.15 ≤ e ≤ 0.70. Preferably, the lower limit of e is 0.17 ≤ e. If it is below the lower limit, the effect of reducing the hysteresis of the PCT curve may not be expected, and if it is above the upper limit, the equilibrium pressure and hydrogen absorption / desorption rate may decrease.

[0021] In equation (1), d+e represents the total content of Ni and M. This value affects the hysteresis of the PCT curve and the hydrogen storage capacity of the hydrogen storage material of the present invention. By adjusting it to the following range, it is possible to create an alloy with small hysteresis in the PCT curve while maintaining a sufficient hydrogen storage capacity for hydrogen storage. d+e is 5.13 ≤ d+e ≤ 5.40, and the lower limit of d+e is preferably 5.15 ≤ d+e.

[0022] In equation (1), Sm and M are elements that, as described above, are effective in increasing the equilibrium pressure during hydrogen absorption and release, improving the angularity of the PCT curve, and reducing the hysteresis of the PCT curve, respectively. However, a greater effect can be obtained by combining these elements. In equation (1), c+e is 0.55 ≤ c+e ≤ 1.20, and preferably 0.57 ≤ c+e ≤ 1.17.

[0023] The elemental composition of the alloy of the present invention represented by formula (1) above can be confirmed by quantitative analysis using an ICP (Inductively Coupled Plasma) analyzer. In this specification, when the term "alloy of the present invention" is used, unless otherwise specified, it refers to the alloy having the elemental composition represented by formula (1).

[0024] The alloy of the present invention may contain unavoidable impurities, such as those substantially derived from the raw materials. Examples of unavoidable impurities include, but are not limited to, Pr and Nd. The amount of unavoidable impurities in the alloy of the present invention is 0.5% by mass or less.

[0025] The alloy of the present invention can be obtained, for example, as an alloy slab as described below, but the grain size of the crystals in the alloy slab is preferably 25 to 250 μm as an average grain size, and more preferably 40 to 230 μm. The average grain size of the crystals can be measured as follows: The alloy slab is embedded in a room-temperature curing type resin (e.g., epoxy resin) and cured, then rough polishing and fine polishing are performed with a wet polishing machine, and finally the polished surface is finished to a mirror finish to form an alloy cross-section. Next, for example, the alloy cross-section is etched with a 0.1 M nitric acid aqueous solution, and then a polarizing microscope is used to measure the lengths of the major axis and minor axis perpendicular to the midpoint of each crystal in the field of view, and the grain size of the crystal is taken as "(length of major axis + length of minor axis) / 2". The grain size is measured in this way for any three crystals, and the average value is taken as the average grain size. There are no particular restrictions on the size of the alloy slab for measuring the grain size, but for example, 1 cm 3 A cast alloy slab of a certain size can be used. Alternatively, the grain size can be measured using an alloy slab of about 1 cm square, in which case the average grain size is preferably 25 to 250 μm.

[0026] The alloy of the present invention exhibits a hydrogen release pressure P at a hydrogen storage capacity of 0.3 wt (weight)% in the hydrogen pressure-composition isotherm (PCT curve) at -20°C. a1 And, the hydrogen release pressure P at a hydrogen storage capacity of 0.1 wt% a2 However, [{ln(P a1 )-ln(P a2 It is preferable that the relationship )} / 0.2] ≤ 4.20 is satisfied. This is because the PCT curve having the above characteristics clarifies the angularity of the curve, and more hydrogen can be released when hydrogen release is terminated at a predetermined pressure, making it a very suitable hydrogen storage material that can effectively utilize the stored hydrogen without leaving any behind in the alloy. a1 and P a2 [{ln(P a1 )-ln(P a2It is more preferable that the relationship )} / 0.2] ≤ 2.00 is satisfied. The relationship in the above equation is used as an indicator of "angularity". In addition, when measuring the PCT curve, it is preferable that there are two or more hydrogen release pressure measurement points between hydrogen storage amounts of 0.08 wt% and 0.12 wt%. a2 This is preferable for obtaining [the desired result].

[0027] Furthermore, the alloy of the present invention exhibits a hydrogen release pressure P at a hydrogen storage capacity of 0.3 wt% in a hydrogen pressure-composition isotherm at -20°C. a1 And, the hydrogen release pressure P at a hydrogen storage capacity of 1.1 wt% a3 However, [{ln(P a3 )-ln(P a1 It is preferable that the relationship [{ln(P a3 )-ln(P a1 It is more preferable that the relationship )} / 0.8] ≤ 0.28 is satisfied. This is because, in the PCT curve's release curve, if the relationship between hydrogen release pressure satisfies the above equation, it is easier to maintain the necessary hydrogen pressure at the hydrogen supply destination, and it is advantageous that as much usable hydrogen as possible can be secured. The relationship in the above equation is used as an indicator of "plateau flatness during hydrogen release".

[0028] Furthermore, in the hydrogen pressure-composition isotherm diagram at -20°C, the alloy of the present invention exhibits a hydrogen storage pressure P at a hydrogen storage capacity of 0.8 wt%. b1 and hydrogen release pressure P b2 However, ln(P b1 / P b2 It is preferable that the relationship ) ≤ 0.60 is satisfied. In the PCT curve, when the relationship between hydrogen storage pressure and hydrogen release pressure satisfies the above equation, hysteresis is small, so there is no need to create a large pressure difference or temperature difference between hydrogen storage and release, and efficient operation is possible. The relationship in the above equation is used as an indicator of "PCT curve hysteresis".

[0029] Furthermore, the alloy of the present invention exhibits a hydrogen release pressure P at a hydrogen storage capacity of 0.8 wt% in a hydrogen pressure-composition isotherm at -20°C. b2P is preferably 0.05 MPa or higher, and more preferably 0.10 MPa or higher, because hydrogen release is better in the temperature range of -20 to 0°C. b2 There is no specific upper limit, but in practice it is around 4.00 MPa at -20°C.

[0030] It is particularly preferable that all of the alloys constituting the hydrogen storage material of the present invention satisfy the above relationship in the PCT curve, but it is also acceptable if only a part of the alloy satisfies the above relationship.

[0031] Next, a method for producing the hydrogen storage material of the present invention will be described. First, methods for preparing the alloy include, for example, strip casting methods such as the single-roll method, double-roll method, or disk method, and die casting methods.

[0032] For example, in the strip casting method, raw materials are prepared by blending them to achieve the desired alloy composition. Then, under an inert gas atmosphere such as Ar, the blended raw materials are heated and melted to form a molten alloy. This molten alloy is then poured onto a copper water-cooled roll and rapidly cooled and solidified to obtain an alloy slab. In the die casting method, a molten alloy is obtained in the same manner, and then the molten alloy is poured into a water-cooled copper mold and cooled and solidified to obtain an ingot. The cooling rates differ between the strip casting method and the die casting method, and generally, the strip casting method is preferred when obtaining an alloy with less segregation and a uniform compositional distribution. Since the alloy constituting the hydrogen storage material of the present invention preferably has less segregation and a uniform compositional distribution, the strip casting method is a preferred method in the present invention.

[0033] However, when manufacturing alloy slabs, the cooling rate of the molten alloy is controlled as follows: The cooling rate from the starting temperature of the molten alloy (for example, the temperature when the molten metal comes into contact with the roll) until the alloy temperature reaches 1000°C is set to 300°C / second or more. Preferably, it is set to 700°C / second or more, more preferably 1000°C / second or more, and particularly preferably 4000°C / second or more. There is no particular upper limit to this cooling rate, but in practice it is around 20000°C / second or less. The starting temperature of the molten alloy varies depending on the alloy composition, but is in the range of approximately 1300 to 1500°C.

[0034] There are no particular restrictions on the cooling rate below 1000°C. For example, in the case of the strip casting method, after detaching from the roll, the temperature of the alloy slab can be recovered by air cooling to, for example, 100°C or below.

[0035] Furthermore, in order to obtain an alloy with a more uniform composition distribution, the alloy slab obtained by the above cooling may be heat-treated. The heat treatment can be carried out in an inert gas atmosphere such as Ar at a temperature of 700°C to 1200°C. The heat treatment temperature is preferably 950°C to 1150°C, and the heat treatment time is 1 hour to less than 24 hours, preferably 3 hours to less than 15 hours.

[0036] Next, the alloy slab obtained by casting is crushed to obtain alloy powder. The crushing can be carried out using a known crushing machine. The particle size of the alloy powder is preferably 1000 μm or less, and more preferably 500 μm or less. There is no need to specifically define the lower limit of the particle size of the alloy powder, but it is practically about 0.1 μm. Here, the particle size of the alloy powder refers to the diameter measured by a sieve shaker (rotap type).

[0037] The hydrogen storage material of the present invention may be the powdered alloy itself, a composite formed by mixing the alloy powder with a resin or the like and molding it into any shape such as granules, or a composite fixed to a temperature-controllable material. In this case, the resin functions as a binder for the alloy powder. Mixing can be carried out by known methods. For example, mixing can be done using a mortar and pestle, or using rotary mixers such as double cone or V-type mixers, or agitator mixers such as blade or screw-type mixers. It is also possible to mix the alloy slab and the binder while crushing them using a pulverizer such as a ball mill or attritor mill.

[0038] The hydrogen storage container of the present invention is equipped with a hydrogen storage material manufactured as described above, and the material and shape of the container can be those of known origin.

[0039] The hydrogen supply device of the present invention is equipped with the hydrogen storage container, and other components can be those known. [Examples]

[0040] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these. In the description of these examples, both the alloy of the present invention in the examples and the alloy outside the present invention in the comparative examples will be referred to as "alloy." Furthermore, an alloy obtained in the form of a slab by the strip casting method will be referred to as an alloy slab, and the material obtained by crushing the alloy slab will be referred to as alloy powder.

[0041] (Example 1) The raw metals were weighed so that the elemental composition of the final alloy would be as shown in Table 1, and melted in an argon gas (Ar) atmosphere in a high-frequency induction melting furnace to obtain a molten alloy. Subsequently, the molten alloy was poured at a temperature of 1500°C and rapidly cooled and solidified using a strip casting method with a single-roll casting apparatus using a copper water-cooled roll to obtain an alloy slab with an average thickness of approximately 0.3 mm. The cooling start temperature of the molten alloy, i.e., the temperature at which it came into contact with the copper water-cooled roll, was approximately 1450°C. There was a difference in the cooling rate between the side of the molten alloy that was in contact with the roll and the side that was not, and the cooling rate from 1450°C to 1000°C was between 6000°C / second and 9000°C / second.

[0042] The alloy slab obtained above was heat-treated in a heat treatment furnace under an Ar atmosphere at 1030°C for 10 hours. After heat treatment, the alloy slab was embedded in epoxy resin and hardened. Rough and fine polishing were performed using a wet polishing machine, and finally the polished surface was finished to a mirror finish to form the alloy cross-section. After etching the alloy cross-section with a 0.1M nitric acid aqueous solution, the average grain size of the crystals was measured using a polarizing microscope (manufactured by Olympus Corporation) by the method described above. The average grain size was 93 μm.

[0043] Furthermore, the heat-treated alloy slabs were crushed in a stainless steel mortar, and a 500 μm pass alloy powder was obtained using a sieve with a mesh size of 500 μm.

[0044] The hydrogen absorption and release characteristics of the obtained alloy powder were measured using an automatic high-pressure Sieberts PCT measurement apparatus (manufactured by Hughes Technonet Co., Ltd.), and a PCT curve was obtained. Prior to the measurement, the mixture was first vacuumed at 80°C for 1 hour, then pressurized with a hydrogen pressure of approximately 2.5 MPa, and hydrogen was absorbed until the hydrogen pressure stabilized at -20°C. Subsequently, the mixture was activated by repeating the process of vacuuming at 80°C for 0.5 hours, pressurizing with a hydrogen pressure of approximately 2.5 MPa, and absorbing hydrogen until the hydrogen pressure stabilized at -20°C, twice. Then, after vacuuming at 80°C, the hydrogen pressure was varied between 0.01 MPa and 2.0 MPa at -20°C, and the equilibrium pressures for hydrogen absorption and release (hydrogen absorption pressure and hydrogen release pressure) were measured. Figure 1 shows the hydrogen pressure-composition isotherm (PCT curve).

[0045] Table 1 shows the results of reading the effective hydrogen amount, which is the difference between the hydrogen storage amount at an equilibrium pressure of 2.0 MPa and the hydrogen storage amount at an equilibrium pressure of 0.1 MPa, and the hydrogen release pressure at a hydrogen storage amount of 0.8 wt%, from the release curve of the obtained PCT curve.

[0046] As an indicator of the angularity of the PCT curve, the release pressure P at a hydrogen storage capacity of 0.3 wt% is obtained from the PCT curve. a1 and the release pressure P at a hydrogen storage capacity of 0.1 wt% a2 Read the value of {ln(P a1 )-ln(P a2 The value obtained by calculating )} / 0.2 was used. The results are shown in Table 1.

[0047] As an indicator of the plateau flatness of the PCT curve (during hydrogen release), the release pressure P at a hydrogen storage capacity of 0.3 wt% is used to analyze the PCT curve. a1 and the release pressure P at a hydrogen storage capacity of 1.1 wt% a3 Read the value of {ln(P a3 )-ln(P a1 The value obtained by calculating )} / 0.8 was used. The results are shown in Table 1.

[0048] As an indicator of hysteresis in the PCT curve, the storage pressure P at a hydrogen storage capacity of 0.8 wt% is obtained from the PCT curve. b1 and the release pressure P at a hydrogen storage capacity of 0.8 wt% b2 Read the value of ln(P b1 / P b2 The value obtained by calculating ( ) was used. The results are shown in Table 1.

[0049] (Examples 2-8, 10-23) Except for changing the elemental composition of the final alloy as shown in Table 1, alloy slabs and alloy powders were prepared in the same manner as in Example 1, and hydrogen storage and release characteristics (such as prism shape) were measured. The pouring temperature, cooling start temperature, and cooling rate of the alloy molten material in these examples were approximately the same as in Example 1, at 1500°C, 1450°C, and between 6000°C / sec and 9000°C / sec. In Examples 11, 17, and 18, the hydrogen pressure was varied from 0.01 MPa to 3.0 MPa, and in Example 12, the hydrogen pressure was varied from 0.01 MPa to 4.0 MPa, and the equilibrium pressure for hydrogen storage and release (hydrogen storage pressure and hydrogen release pressure) was measured. The effective hydrogen amount in Examples 2-8, 10, 13-16, and 23 was the difference between the hydrogen storage amount at an equilibrium pressure of 2.0 MPa and the hydrogen storage amount at an equilibrium pressure of 0.1 MPa, as in Example 1. The effective hydrogen amount in Examples 11, 17, and 18 was defined as the difference between the hydrogen storage amount at an equilibrium pressure of 3.0 MPa and the hydrogen storage amount at an equilibrium pressure of 0.1 MPa. The effective hydrogen amount in Example 12 was defined as the difference between the hydrogen storage amount at an equilibrium pressure of 4.0 MPa and the hydrogen storage amount at an equilibrium pressure of 0.1 MPa. The effective hydrogen amount in Examples 19 to 22 was defined as the difference between the hydrogen storage amount at an equilibrium pressure of 2.0 MPa and the hydrogen storage amount at an equilibrium pressure of 0.01 MPa. The results of various measurements are shown in Table 1.

[0050] (Example 9) Except for not performing heat treatment after alloy casting, alloy slabs and alloy powders were prepared in the same manner as in Example 2, and hydrogen absorption and release characteristics (such as prism shape) were measured. The pouring temperature, cooling start temperature, and cooling rate of the alloy molten material in Example 9 were approximately the same as in Example 1, at 1500°C, 1450°C, and between 6000°C / sec and 9000°C / sec. The results of the various measurements are shown in Table 1.

[0051] (Comparative Examples 1-5) Except for changing the elemental composition of the final alloy as shown in Table 1, alloy slabs and alloy powders for each comparative example were prepared in the same manner as in Example 1, and hydrogen storage and release characteristics (such as prism shape) were measured. The pouring temperature, cooling start temperature, and cooling rate of the alloy molten material for these comparative examples were approximately the same as in Example 1, at 1500°C, 1450°C, and between 6000°C / sec and 9000°C / sec. The results of the various measurements are shown in Table 1. For Comparative Example 2, the hydrogen storage amount did not reach 1.1 wt% during PCT curve measurement, so plateau flatness could not be calculated. The hydrogen pressure-composition isotherm (PCT curve) for Comparative Example 1 is shown in Figure 1. The hydrogen pressure-composition isotherm (PCT curve) for Comparative Example 3 is shown in Figure 2.

[0052] [Table 1]

[0053] As is clear from the table, the alloys of each example exhibit better angularity of the PCT curve and sufficient hydrogen storage capacity compared to the alloys of each comparative example. Furthermore, the hydrogen release pressure at a hydrogen storage capacity of 0.8 wt% is 0.05 MPa or higher in all cases, indicating that hydrogen storage and release are sufficiently possible in the temperature range below 0°C. Moreover, it can be seen that excellent hydrogen storage materials with small PCT curve hysteresis can be obtained.

Claims

1. A hydrogen storage material having an alloy with a composition represented by the following formula (1). [C1] [In equation (1), M is at least one selected from Mn, Co, and Al, and Mn is essential. a is 0.00 ≤ a ≤ 0.62, b is 0.20 ≤ b ≤ 0.57, c is 0.17 ≤ c ≤ 0.60, d is 4.50 ≤ d ≤ 5.20, and e is 0.15 ≤ e ≤ 0.

70. a + b + c = 1, c + e is 0.55 ≤ c + e ≤ 1.20, and d + e is 5.13 ≤ d + e ≤ 5.40.]

2. The hydrogen storage material according to claim 1, wherein in formula (1), M is Mn, or both Mn and Co, a is 0.00 ≤ a ≤ 0.40, and c is 0.20 ≤ c ≤ 0.

60.

3. In the hydrogen pressure-composition isotherm diagram of the aforementioned alloy at -20°C, the hydrogen release pressure P at a hydrogen storage capacity of 0.3 wt% is shown. ａ１ and hydrogen release pressure P at a hydrogen storage capacity of 0.1 wt% ａ２ However, [{ln(P ａ１ ) - ln(P ａ２ A hydrogen storage material according to claim 1, satisfying the relationship} / 0.2 ≤ 4.

20.

4. The hydrogen storage material according to Claim 2, wherein in the hydrogen pressure-composition isotherm diagram of the alloy at -20°C, the hydrogen release pressure P a1 at a hydrogen storage capacity of 0.3 wt% and the hydrogen release pressure P a2 at a hydrogen storage capacity of 0.1 wt% satisfy the relationship [{ln(P a1) - ln(P a2)} / 0.2] ≤ 4.

20.

5. The aforementioned P ａ１ and P ａ２ ga [{ln(P ａ１ ) - ln(P ａ２ A hydrogen storage material according to claim 3, satisfying the relationship} / 0.2 ≤ 2.

00.

6. The hydrogen storage material according to claim 4, wherein P a1 and P a2 satisfy the relationship [{ln(P a1) - ln(P a2)} / 0.2] ≤ 2.

00.

7. A hydrogen storage container comprising the hydrogen storage material described in any one of claims 1 to 6.

8. A hydrogen supply device comprising the hydrogen storage container described in claim 7.

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