WO2022209879A1 - Composé magnéto-calorique à base d'erco2 et dispositif frigorifique magnétique utilisant ledit composé - Google Patents

Composé magnéto-calorique à base d'erco2 et dispositif frigorifique magnétique utilisant ledit composé Download PDF

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WO2022209879A1
WO2022209879A1 PCT/JP2022/011748 JP2022011748W WO2022209879A1 WO 2022209879 A1 WO2022209879 A1 WO 2022209879A1 JP 2022011748 W JP2022011748 W JP 2022011748W WO 2022209879 A1 WO2022209879 A1 WO 2022209879A1
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magnetic
magnetic refrigeration
temperature
erco
phase transition
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PCT/JP2022/011748
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Japanese (ja)
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シン タン
ジャ ウェイ ライ
アミン ホセイン セペリ
忠勝 大久保
和博 宝野
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国立研究開発法人物質・材料研究機構
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B21/00—Machines, plants or systems, using electric or magnetic effects
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures

Definitions

  • the present invention relates to an ErCo2 - based magnetocaloric compound and a magnetic refrigerator using the same.
  • Patent Documents 1 to 3 and Non-Patent Document 1 are known as hydrogen liquefaction apparatuses.
  • Magnetocaloric hydrogen liquefaction requires a huge magnetocaloric effect ( Magnetic refrigeration materials with GMCE (giant magnetocaloric effect) are preferred.
  • a first-order ferromagnetism-paramagnetism transition of 37 J/cm 3 K is shown at 5 T, respectively.
  • ErCo2 which exhibits the largest entropy change and desirable Curie temperature Tc, is a strong candidate for the development of giant magnetic refrigeration materials for hydrogen liquefaction. is.
  • the Curie temperature T C increases to around 45-60 K, but these compounds still exhibit a first-order magnetic phase transition.
  • Co was replaced by 12.5% Fe the Curie temperature T C increased to above 85K, and the entropy change worsened to 0.03 J/cm 3 ⁇ K.
  • the non-stoichiometric ErCoMn x compound has a temperature of 0.0 at the Curie temperature of 150 K. Only 01 J/cm 3 K or less was obtained.
  • the phase transition from the primary magnetic phase transition (FOMT) to the secondary magnetic phase transition (SOMT) of ErCo2 can be adjusted in the range of 25K to 70K so as to have sufficient magnetic recording properties and the Curie temperature TC . is preferred. That is, it is important to tune the phase transition of ErCo2 to the second -order phase transition (SOPT). It is also important to raise the phase transition temperature to 25-70K. In this case, if a magnetic refrigeration material with a phase transition temperature of 45-70 K exists, for example, if a magnetic refrigeration material with a phase transition temperature of 25-45 K, which is about 20 K away from this on the lower temperature side, can be searched, the magnetocaloric value Suitable for hydrogen liquefaction applications.
  • ErCo2 - based compounds are known to provide enormous magnetocaloric effects for cryogenic magnetic refrigeration applications such as hydrogen liquefaction.
  • the magnetocaloric effect of this material is due to the first-order magnetic phase transition, the material exhibits hysteresis, resulting in a huge magnetocaloric effect during the magnetic refrigeration cycle and reduced mechanical stability, making it difficult to put into practical use.
  • the magnetic phase transition temperature T tr can be adjusted in the temperature range of 25-46K while maintaining the huge magnetocaloric effect. In addition, it can be said that there is substantially no hysteresis due to temperature cycles due to the continuous phase transition due to the secondary magnetic phase transition.
  • a magnetic refrigeration material suitable for liquefaction of natural gas, H 2 , He and the like is also provided.
  • a magnetic refrigeration material with ErCo2 compounds are one of the promising materials due to their desirable Curie temperature T C and large entropy change due to first-order magnetic phase transition (FOMT) accompanied by structural phase transition.
  • FMT first-order magnetic phase transition
  • ErCo2 compounds were expected to have low reversibility of magnetocaloric performance and low mechanical stability.
  • part of Co can be replaced with the third element M in order to enhance the reversibility of the magnetocaloric properties. It is believed that this is the reason why the magnetic phase transition is a secondary magnetic phase transition that does not substantially accompany the structural phase transition.
  • the third element M it is considered preferable to have properties similar to those of Co (cobalt), but at the same time have different properties.
  • Co cobalt
  • the present inventors have newly discovered that a specific element or combination of elements can have a desired Curie temperature T C by adding a predetermined amount as a substitution element for Co.
  • the inventors have newly found that the magnetic phase transition is substantially second-order magnetic phase transition. Specifically, the following can be provided.
  • the magnetic refrigeration material is composed of Er (erbium), Co (cobalt), Al (aluminum), Fe (iron), Ni (nickel) and unavoidable impurities, and has the following compositional formula: ErCo 2-xy (Al, Fe) x Ni y ; 0 ⁇ x ⁇ 0.1, 0 ⁇ y ⁇ 0.2.
  • the magnetic refrigeration material is composed of Er (erbium), Co (cobalt), Ni (nickel), Al (aluminum) and unavoidable impurities, and has the following compositional formula: ErCo 2-xy Al x Ni y ; 0.0 ⁇ x ⁇ 0.1, 0.0 ⁇ y ⁇ 0.2. Preferably, it may have a composition of 0.01 ⁇ x ⁇ 0.1 and 0.01 ⁇ y ⁇ 0.2.
  • any magnetic refrigeration material described above preferably includes: ErCo 2-xy Al x Ni y : 0.01 ⁇ x ⁇ 0.1, 0.12 ⁇ y ⁇ 0.2.
  • the transition temperature Ttr may fall significantly below 20K.
  • any one of the magnetic refrigeration materials described above is composed of Er (erbium), Co (cobalt), Ni (nickel), Fe (iron), and inevitable impurities, and has the following compositional formula: : ErCo 2-xy Fe x Ni y ; 0.035 ⁇ x ⁇ 0.1, 0.00 ⁇ y ⁇ 0.2.
  • any magnetic refrigeration material described above preferably includes: ErCo 2-xy Fe x Ni y : 0.035 ⁇ x ⁇ 0.1, 0.01 ⁇ y ⁇ 0.2. If x is less than 0.035, there is a risk of first-order magnetic phase transition ( FOPT ) occurring in the range of 20K around the transition temperature Ttr.
  • FOPT first-order magnetic phase transition
  • the transition temperature Ttr may exceed 70K. and may not be suitable for magnetic refrigeration in the desired temperature range.
  • y exceeds 0.2, the transition temperature Ttr may fall significantly below 20K. and may not be suitable for magnetic refrigeration in the desired temperature range.
  • y is less than 0.01, the Ni content may fall below the standard amount of unavoidable impurities. And there is a possibility that it is substantially indistinguishable from the ternary system ErCo 2-x Fe x .
  • the transition temperature T tr of the magnetic phase transition is in the temperature range of 25 K to 46 K, and in the range of 20 K before and after the transition temperature T tr It may exhibit a second order magnetic phase transition.
  • the secondary magnetic phase transition has a volume change rate (dV/V) of 0.4% in a range of 20 K around the transition temperature Ttr . It may be below. If the volume change rate (dV/V) is 0.4% or less, it can be evaluated as a secondary magnetic phase transition ( SOMT ) in the range of 20K around the transition temperature Ttr.
  • the entropy change is ⁇ S>0.05 J/cm 3 under a 5 T magnetic field in a range of 20 K around the transition temperature Ttr . - K may be obtained.
  • the magnetic refrigeration system may use any of the magnetic refrigeration materials described above.
  • the hydrogen liquefaction device or the helium liquefaction device may use any of the magnetic refrigeration devices described above.
  • the ErCo 2 -based magnetocaloric compound can sustain a giant magnetocaloric effect.
  • the Curie temperature T C can be in the temperature range of 25-46K. And it can be a continuous transition due to a secondary magnetic phase transition. Moreover, it can be said that there is substantially no hysteresis due to temperature cycles. It is considered as a magnetic refrigeration material suitable for liquefaction of natural gas, H 2 , He and the like.
  • FIG. 1 illustrates the crystal structure of ErCo 2 , one example of a Laves phase compound that may constitute a magnetic refrigeration material that may be used in embodiments of the present invention
  • the composition of a compound that may constitute a magnetic refrigeration material that can be used is shown in the composition diagram of a ternary system of Co, Ni, and Al or Fe (Er is excluded from this composition diagram because it always exists in a constant amount. ).
  • Figure 2 shows the temperature dependence of the entropy change ⁇ Sm at 0-5T for ErCo2 compounds.
  • Figure 2 shows the temperature dependence of magnetization M at 1 T for ErCo 2-x Fe x compounds.
  • Figure 2 shows the temperature dependence of the magnetization M at 1 T for an ErCo 2-xy Al x Niy compound representing an embodiment of the present invention.
  • Figure 2 shows the temperature dependence of entropy change ⁇ Sm at 0-5T for ErCo 2-xy Al x Ni y compounds representing one embodiment of the present invention.
  • Figure 2 shows the temperature dependence of the magnetization M at 1 T for an ErCo 2-xy Fe x Ni y compound representing an embodiment of the present invention.
  • Figure 2 shows the temperature dependence of the entropy change ⁇ Sm at 0-5T for an ErCo 2-xy Fe x Ni y compound representing an embodiment of the present invention.
  • FIG. 3 is a schematic diagram illustrating each step of a magnetic refrigeration cycle in which the magnetic refrigeration material of the example of the present invention is used; 1 is a schematic diagram illustrating an active regenerative magnetic refrigeration (AMR) cycle; FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which shows an example of AMR which carried out the cascade arrangement of the magnetic refrigerating material, (A) is an apparatus schematic, (B) is explanatory drawing of the operating temperature range of a magnetic refrigerating material. It is a figure which shows a magnetic refrigerator typically.
  • a phase transition may be a change in an order parameter (eg, the magnetization of a ferromagnet) across the transition.
  • Phase transition of a magnetic substance (magnetic phase transition)
  • Magnetization is a macroscopic physical quantity, but it is derived from microscopic electron spins inside a magnetic material.
  • a first-order phase transition may mean that the order parameter changes discontinuously.
  • a second-order phase transition may also be referred to as a continuous phase transition and may refer to a continuous change in the order parameter.
  • discontinuities occur in the crystal entropy, volume, polarization, etc. in the first order transition, but in the second order transition, these quantities are continuous and the temperature differential shows discontinuous changes.
  • the order variable may be a macroscopic variable representing the order of the phase.
  • phase transition phenomena may be characterized by changes in the value of the order parameter.
  • the order parameter behaves as a function of external variables such as temperature and pressure. It has a value and may be zero in high temperature phases (symmetrical or disordered phases).
  • First-Order Magnetic Phase Transition (FOMT) in magnetic refrigeration materials refers to materials that have a magnetic phase transition at the transition temperature, accompanied by either a change in crystal structure or a change in crystal volume. .
  • the transition temperature is considered to substantially correspond to the Curie temperature.
  • Second-order magnetic phase transition (SOMT) in magnetic refrigeration materials is a magnetic phase transition (from ferromagnet to paramagnetism) at the transition temperature without substantial change in crystal structure or crystal volume metastases to the body, etc.).
  • the boundary value between the primary magnetic phase transition and the secondary magnetic phase transition is set at a volume change rate (dV/V) of 0.4% in the range around the transition temperature T tr (T tr ⁇ 20 K).
  • dV/V volume change rate
  • FIG. 1A illustrates the crystal structure of ErCo2 .
  • metal elements A and B having an atomic radius ratio of about 1.2:1 are combined at a composition ratio of AB2 to form a compound.
  • a crystal structure consisting of a large atom A and a small atom B can be considered as a packed structure of large and small spheres, and enters specific lattice positions, the A site and the B site.
  • the A site has 4 A atoms and 12 B atoms as neighboring atoms, and the B site is surrounded by 6 A atoms and 6 B atoms.
  • atoms are packed so that AA atoms and BB atoms are in contact with each other and there is no contact between AB atoms.
  • the A-site atoms are arranged in a diamond structure, and the B-site atoms form a tetrahedron around the A-site.
  • Laves phase compound is a kind of close-packed structure, cubic MgCu2 type (C15), hexagonal MgZn2 type (C14), MgNi It has three crystal structures of type 2 (C36).
  • Al, Fe, and/or Ni are considered to enter such crystal structures as they substitute for Co.
  • Table 1 is a table showing elemental compositions of ErCo 2-xy (Al, Fe) x Ni y based compounds showing experimental results relating to the present invention.
  • Experimental Example 1 shows the elemental composition of a sample using ErCo2 , which is the basic form of the binary alloy.
  • Experimental Examples 2 to 4 are elemental compositions of samples using ErCo 2-x Fe x , which is the basic form of a ternary alloy, and the Fe composition ratio x is swung in the range of 1.33 to 2.33%.
  • Experimental Example 5 the elemental composition of the ErCo 2-xy Al x Ni y compound of the quaternary alloy is expressed in atomic %, and the Al composition ratio is 1.67% and the Ni composition ratio is 5%. 0%.
  • the Al composition ratio is 1.00% and the Ni composition ratio is 5.67%.
  • the elemental composition of the ErCo 2-xy Fe x Ni y compound of the quaternary alloy is expressed in atomic %, the composition ratio of Fe is 1.33%, and the composition ratio of Ni is 1.33%.
  • the composition ratio ranges from 2.0% to 3.67%.
  • FIG. 1B illustrates the compositions of these experimental examples in a composition diagram of the ternary system of Co, Ni, and Al or Fe (here, Er is excluded from this composition diagram because it is always present in constant amounts). do. Since the total is 100%, if the total including Er is to be 100%, the stated numerical value should be multiplied by 2/3.
  • the range surrounded by the thick line is the target composition range.
  • Table 2 shows physical property values of ErCo 2-xy (Al, Fe) x Ni y compounds showing experimental results relating to the present invention.
  • the composition ratios of Al and Fe are represented by atomic %, but in Table 2, they are represented by chemical formulas.
  • FIG. 3 shows the temperature dependence of entropy change ⁇ Sm at 0-5T for ErCo 2 compounds.
  • FIG. 6 shows the temperature dependence of the entropy change ⁇ Sm at 0-5T at 0-80K for ErCo 2-xy Al x Ni y compounds showing experimental examples of the present invention.
  • the magnetic phase transition SOMT was shown in Experimental Examples 5 and 8 (Examples).
  • the thermal hysteresis ⁇ T hys (K) tends to appear at the primary magnetic phase transition and not at the secondary magnetic phase transition.
  • the thermal hysteresis ⁇ T hys (K) appears with a width of 1.8K
  • Experimental Example 5 is 0.65K
  • Experimental Example 8 is 0.2K.
  • the phase transition temperature T tr indicating the transition temperature from paramagnetism to ferromagnetism was measured under an external magnetic field of 1 T (Tesla) .
  • the rate of change of magnetization M per temperature dM/dT was 7.31 for ErCo 1.96 Fe 0.04 of Experimental Example 2 and 5 for ErCo 1.95 Fe 0.05 of Experimental Example 3. .2 , 2.8 for ErCo1.93Fe0.07 in Experimental Example 4 , 7.1 for ErCo1.9Ni0.06Fe0.04 in Experimental Example 6, and ErCo1.85Ni in Experimental Example 7 . It was 7.2 for 0.11 Fe 0.04 .
  • FIG. 4 shows the temperature dependence of magnetization M at 1 T for ErCo 2-x Fe x compounds.
  • FIG. 7 shows the temperature dependence of the magnetization M at 1 T at 0-80 K for ErCo 2-xy Fe x Ni y compounds showing experimental examples of the present invention.
  • the entropy ⁇ S (J/cm 3 ⁇ K) per unit volume is 0.21 for ErCo 1.96 Fe 0.04 in Experimental Example 2, 0.17 for ErCo 1.95 Fe 0.05 in Experimental Example 3, and Not measured in Example 4.
  • FIG. 8 shows the temperature dependence of the entropy change ⁇ Sm at 0-5T at 0-80K for ErCo 2-xy Fe x Ni y compounds showing experimental examples of the present invention.
  • Experimental Examples 2 to 4 showed SOMT.
  • Examples 6 and 7 showed SOMT.
  • the thermal hysteresis ⁇ T hys (K) tends to appear at the primary magnetic phase transition and not at the secondary magnetic phase transition. In Experimental Examples 2 to 4, thermal hysteresis ⁇ T hys (K) does not appear, which is preferable.
  • Experimental example 6 appears with a width of 0.2K
  • experimental example 7 appears with a width of 0.2K.
  • a sharp with a narrow temperature span may mean a case where ⁇ dM/dT exceeds 18 Am 2 /kg ⁇ K. More preferably, it may be said that it exceeds 9 Am 2 /kg ⁇ K.
  • the volume change rate (dV/V) is 0.4% or less in the range of about 20 K of the transition temperature Ttr , it is a secondary magnetic phase transition, and if it exceeds 0.4%, it is a primary magnetic phase transition. It can be a phase transition.
  • ⁇ dM/dT can be used secondarily to determine the primary magnetic phase transition.
  • the second-order phase transition can occur when ⁇ dM/dT is 18 Am 2 /kg ⁇ K or less, more preferably 9 Am 2 /kg ⁇ K or less, but this is the case when the volume change rate cannot be obtained. can only be used.
  • the volume change rate (dV/V) before and after the Curie temperature was 0.4% or less, and a continuous and gentle volume change was obtained.
  • FIGS. 2 to 8 As experimental examples of the magnetic refrigeration material of the present invention, the experimental forms shown in FIGS. 2 to 8 are shown. The invention is not limited to this. Also, various embodiments are conceivable within the scope obvious to those skilled in the art. Such obvious scope is included in the scope of the present invention.
  • FIG. 10 is a schematic diagram explaining each step of the magnetic refrigeration cycle.
  • a thermal cycle similar to the vapor compression cycle is composed of repeated cycles of entropy change (temperature rise) due to excitation in a constant temperature environment and adiabatic temperature change (temperature decrease) due to demagnetization in an adiabatic state.
  • FIG. 11 is a schematic diagram illustrating an active regenerative magnetic refrigeration (AMR) cycle.
  • a magnetic refrigerator for the AMR cycle is composed of a packed bed of magnetic refrigerant material, an AMR bed that also serves as a heat exchanger, a magnet, a driving device (displacer), and a heat transfer medium (hydrogen, helium, air, etc.).
  • the drive is the controller that adjusts the relative positions of the magnetic refrigeration material and the AMR bed.
  • the AMR cycle consists of four steps: adiabatic excitation, transfer of heat transfer medium (transfer from low temperature end to high temperature end), adiabatic demagnetization, transfer of heat transfer medium (transfer from high temperature end to low temperature end). .
  • adiabatic excitation the magnetic refrigeration material is excited and the temperature of the entire AMR bed rises.
  • the driving device moves the heat transfer medium to the high temperature side. While the high temperature heat transfer medium in the AMR bed is transferred to the high temperature side, the inflow of the heat transfer medium from the low temperature side changes the temperature distribution in the AMR bed.
  • Adiabatic demagnetization reduces the temperature in the AMR bed due to the magnetocaloric effect.
  • the overall temperature drops with the temperature distribution in the AMR bed.
  • the driving device moves the heat transfer medium to the low temperature side. While the low temperature heat transfer medium in the AMR bed is transferred to the low temperature side, the inflow of the heat transfer medium from the high temperature side changes the temperature distribution in the AMR bed.
  • the temperature distribution in the AMR bed is slightly lower than at the start of the cycle on the low temperature side, and slightly higher than at the start of the cycle on the high temperature side.
  • the temperature difference increases, and eventually the temperature distribution in the AMR bed becomes almost constant.
  • the temperature distribution within this AMR bed is determined by the properties of the magnetic refrigeration material that constitutes the AMR bed.
  • FIG. 12 is a schematic diagram showing an example of an AMR in which magnetic refrigeration materials are arranged in cascade.
  • A is a schematic diagram of the apparatus
  • B is an explanatory diagram of the operating temperature range of the magnetic refrigeration materials along the apparatus.
  • the Curie temperature TC is the temperature at which a ferromagnetic material exhibits paramagnetism and coincides with the temperature at which the maximum magnetocaloric effect occurs. Therefore, the AMR shown in FIG.
  • FIG. 13 is a schematic diagram showing the main part of the magnetic refrigerator.
  • Magnetic refrigeration materials can be used, including the materials in the examples above.
  • One form of the magnetic refrigeration material may be particles having a particle size in the range of 50 ⁇ m or more and 1000 ⁇ m or less.
  • it may be in the form of particles having a spherical approximate diameter of 50 ⁇ m or more, 100 ⁇ m or more, 200 ⁇ m or more, or 2000 ⁇ m or less, 1000 ⁇ m or less, or 500 ⁇ m or less.
  • these lower limits and upper limits may be appropriately combined to form a predetermined range.
  • Adopting a particle form can increase the filling rate of the AMR bed, and the particle diameter can change the cross-sectional area of heat exchange with the heat-transporting refrigerant and the pressure loss.
  • the actual magnitude of pressure loss depends not only on the particle size but also on the type of heat-transporting refrigerant and operating conditions.
  • the particle size is a volume-based median diameter (d50), and the volume-based average particle size can be measured by, for example, microtrack or laser scattering. More specifically, static image analysis methods and dynamic image analysis methods may be employed.
  • a magnetic refrigeration apparatus 200 with such a magnetic refrigeration material can be used for the production of ultra-low temperatures, such as the liquefaction of hydrogen.
  • the magnetic refrigeration apparatus 200 includes an AMR bed 220 filled with a magnetic refrigeration material 210, a magnetic field applying means 230 for applying a magnetic field to the AMR bed 220, a cooling stage 290 for cooling an object to be cooled by cold temperature, and a magnetic refrigeration in the AMR bed 220. It further includes a heat exchanger 240 for exhausting heat generated by work.
  • any means for applying a magnetic field to the AMR bed 220 can be applied to the magnetic field applying means 230.
  • a magnetic field with a strength of about 1 to 10 T (Tesla).
  • a superconducting magnet, a permanent magnet, or the like can be used as the magnetic field applying means 230 .
  • a driving mechanism not shown, the magnitude of the magnetic field applied to the AMR bed 220 can be changed.
  • a precooling stage 260 is provided on the high temperature side of the AMR bed 220, an 80K shield 270 is connected to the low temperature side of the precooling stage 260, and a 300K shield 280 is connected to the high temperature side of the precooling stage 260, respectively. Furthermore, a cooling stage 290 is provided on the cold side of the AMR bed 220, and a liquefaction vessel 250 is provided in thermal connection with the cooling stage 290. FIG. That is, the gas to be cooled is supplied to the liquefying container 250 and liquefied.
  • the AMR bed 220 is provided with an inflow/outlet port for the heat-transporting refrigerant so that the heat-transporting refrigerant can reciprocate inside the AMR bed 220 through the gaps of the magnetic refrigerating material 210 .
  • a gas 310 to be liquefied (eg, hydrogen, helium (He), etc.) is supplied to the liquefaction container 250 from a tank (not shown).
  • the magnetic refrigerator 200 may operate as follows. A magnetic field is applied by the magnetic field applying means 230 to the AMR bed 220 filled with the magnetic refrigeration material 210 to raise the temperature of the magnetic refrigeration material 210 . Next, the heat transport refrigerant is caused to flow in the direction 300A from the low temperature end side of the AMR bed 220 toward the high temperature end side.
  • the heat-transporting refrigerant exchanges heat with the magnetic refrigeration material 210 filled inside the AMR bed 220 and receives heat, flows through the gaps in the magnetic refrigeration material 210 , and flows out from the high temperature end of the AMR bed 220 .
  • the heat-transporting refrigerant flowing out from the high-temperature end of the AMR bed 220 flows through the pre-cooling stage 260 into the heat exchanger 240 that exhausts the warm heat, and excess heat is exhausted to the outside. Then, the magnetic field with which the magnetic refrigeration material 210 is charged is removed (reduced) to lower the temperature of the magnetic refrigeration material 210 .
  • the heat transport refrigerant is made to flow in the direction 300B from the high temperature end side of the AMR bed 220 toward the low temperature end side.
  • the heat-transporting refrigerant flows through the pre-cooling stage 260 into the high-temperature end of the AMR bed 220, exchanges heat with the magnetic refrigeration material 210 filled inside, and flows through the gaps of the magnetic refrigeration material 210 while being cooled. , reaches the cold end of the AMR bed 220 .
  • the flow of the heat-transporting refrigerant is driven by refrigerant driving means (not shown).
  • the refrigerant driving means is not particularly limited as long as it can drive an oscillating flow in which the heat-transporting refrigerant reciprocates in synchronization with the AMR cycle.
  • the hydrogen gas supplied to the liquefaction vessel 250 is cooled to the cooling stage provided on the cold end of the AMR bed 220. It is cooled by heat exchange with 290 and condensed and liquefied. Such processes are repeated to periodically liquefy or cool the gas inside the liquefying container 250 .
  • a magnetic refrigeration material useful for a hydrogen liquefaction apparatus using the AMR cycle can be provided.
  • the ErCo 2 -based magnetocaloric compounds of the present invention can open new horizons in the application of RECo 2 -based materials for cryogenic magnetic refrigeration applications.
  • magnetic refrigerator 220 AMR bed 230 magnetic field applying means 240 heat exchanger 250 liquefaction vessel 260 pre-cooling stage 270 80K shield 280 300K shield 290 cooling stage 300A movement direction of heat transport refrigerant 300B movement direction of heat transport refrigerant

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Abstract

Un matériau magnéto-calorique selon la présente invention est adapté à liquéfier du gaz naturel, de l'H2, de l'He et analogues ; permet à sa température de Curie TC de se trouver dans une plage de températures comprise entre 25 et 46 K, maintenant en même temps son effet magnéto-calorique massif ; effectue des transitions en continu en raison d'une transition de phase magnétique secondaire ; et présente une faible hystérésis dans un cycle de température. Un exemple est (1) un matériau de réfrigération magnétique comprenant de l'Er (erbium), du Co (cobalt), du Ni (nickel) et de l'Al (aluminium), et des impuretés imprévues, et présentant une composition représentée par la formule de composition : ErCo2-x-yAlxNiy, dans laquelle les inégalités 0,0<x≤0,1 et 0≤y≤0,2 sont satisfaites. De préférence, la composition satisfait aux inégalités 0,01≤x≤0,1 et 0,12≤y≤0,2. Un autre exemple est (2) un matériau de réfrigération magnétique comprenant de l'Er (erbium), du Co (cobalt), du Ni (nickel) et du Fe (fer), et des impuretés imprévues, et présentant une composition représentée par la formule de composition : ErCo2-x-yFexNiy, dans laquelle les inégalités 0,035 ≤ x ≤ 0,1 et 0,00 ≤ y ≤ 0,2 sont satisfaites.
PCT/JP2022/011748 2021-03-30 2022-03-15 Composé magnéto-calorique à base d'erco2 et dispositif frigorifique magnétique utilisant ledit composé WO2022209879A1 (fr)

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