WO2023190558A1 - セラミックス - Google Patents

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WO2023190558A1
WO2023190558A1 PCT/JP2023/012593 JP2023012593W WO2023190558A1 WO 2023190558 A1 WO2023190558 A1 WO 2023190558A1 JP 2023012593 W JP2023012593 W JP 2023012593W WO 2023190558 A1 WO2023190558 A1 WO 2023190558A1
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electrocaloric effect
ceramic
electric field
temperature
voltage
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French (fr)
Japanese (ja)
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左京 廣瀬
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to CN202380021441.7A priority Critical patent/CN118871405A/zh
Priority to JP2024512591A priority patent/JP7718584B2/ja
Priority to DE112023000508.7T priority patent/DE112023000508T5/de
Publication of WO2023190558A1 publication Critical patent/WO2023190558A1/ja
Priority to US18/780,740 priority patent/US20240376013A1/en
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Definitions

  • the present disclosure relates to ceramics.
  • Non-Patent Document 1 examples include PbSc 0.5 Ta 0.5 O 3 (hereinafter, ceramics containing Pb, Sc and Ta are also referred to as "PST") (Patent Document 1, Non-Patent Documents 1 and 2), and PbMg 0 .5 W 0.5 O 3 (hereinafter, ceramics containing Pb, Mg, and W are also referred to as "PMW”) is known as a promising material.
  • Non-Patent Document 3 reports that PbMg 0.5 W 0.5 O 3 exhibits large positive and negative electrocaloric effects.
  • PMW is an antiferroelectric material, and has the characteristic that it transforms into a ferroelectric material by applying a voltage equal to or higher than a threshold voltage. Below this threshold voltage, the electrocaloric effect of PMW is very small, and when the threshold voltage is exceeded, the electrocaloric effect is exhibited depending on the magnitude of the applied voltage. That is, when using a PMW as a solid-state cooling element, it is necessary to apply a large voltage exceeding the threshold voltage of the PMW, and the electric field strength required to exhibit the electrocaloric effect also increases.
  • An object of the present disclosure is to provide ceramics that exhibit a larger electrocaloric effect in a lower electric field than before. More specifically, the purpose is to provide ceramics that exhibit a greater electrocaloric effect in a lower electric field than conventional PMW.
  • the present disclosure provides formula (1): (1-m) PbSc 0.5-x Ta 0.5+x O 3 -mPbMg 0.5-y W 0.5+y O 3 (1)
  • m satisfies 0.60 ⁇ m ⁇ 0.95, In the case of 0 ⁇ x, y, x, y ⁇ 0.1 and 0 ⁇ x+y ⁇ 0.13 are satisfied, If 0>x, 0 ⁇ y, -0.1 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.1, If 0 ⁇ x, 0>y, -0.1 ⁇ x,y and -0.13 ⁇ x+y ⁇ 0, In the case of 0 ⁇ x,0>y, 0 ⁇ x ⁇ 0.1 and ⁇ 0.1 ⁇ y ⁇ 0 are satisfied.
  • Formula (1) (1-m) PbSc 0.5-x Ta 0.5+x O 3 -mPbMg 0.5-y W 0.5+y O 3 (1)
  • m satisfies 0.60 ⁇ m ⁇ 0.95, In the case of 0 ⁇ x, y, x, y ⁇ 0.1 and 0 ⁇ x+y ⁇ 0.13 are satisfied, If 0>x, 0 ⁇ y, -0.1 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.1, If 0 ⁇ x, 0>y, -0.1 ⁇ x,y and -0.13 ⁇ x+y ⁇ 0, In the case of 0 ⁇ x,0>y, 0 ⁇ x ⁇ 0.1 and ⁇ 0.1 ⁇ y ⁇ 0 are satisfied.
  • the present disclosure it is possible to provide ceramics that exhibit a large electrocaloric effect in a low electric field. More specifically, it is possible to provide ceramics that exhibit a greater electrocaloric effect in a lower electric field than conventional PMW.
  • FIG. 1 shows the electric polarization-field strength curve of PMW at 15°C.
  • Figure 2 shows the electric polarization-field strength curve at -18°C for samples within the scope of the invention.
  • FIG. 3 is a schematic cross-sectional view of an electrocaloric effect element according to one embodiment of the present disclosure.
  • FIG. 4 is a diagram for explaining the measurement sequence of the electrocaloric effect.
  • FIG. 5 shows the electric polarization-field strength curve of PMW of sample number 1 at 15°C.
  • FIG. 6 shows the relationship between the electrocaloric effect and electric field strength at 15° C. for PMW of sample number 1.
  • FIG. 7 shows the relationship between the electrocaloric effect and temperature at a PMW electric field strength of 20 MV/m for sample number 1.
  • FIG. 8 shows the relationship between the electrocaloric effect and temperature at a PST electric field strength of 15 MV/m for sample number 2.
  • FIG. 9 shows the relationship between the electrocaloric effect and temperature for the PST of sample number 2 and the sample number 6 at an electric field strength of 15 MV/m.
  • FIG. 10 is a diagram showing the results of characteristic tests for various x and y compositions.
  • the ceramic according to an embodiment of the present disclosure has Pb, Sc, Ta, Mg, and W as main components.
  • the ceramic is a composite oxide containing Pb, Sc, Ta, Mg, and W,
  • the content ratio of Pb is substantially equal to the total content ratio of Sc, Ta, Mg, and W,
  • the content ratio of Sc is "0.5-x”
  • the content ratio of Ta is "0.5+x”
  • the content ratio of Mg is "0.5-y”
  • the content ratio of W is The ratio is "0.5+y”
  • the range of x and y is In the case of 0 ⁇ x, y, x, y ⁇ 0.1 and 0 ⁇ x+y ⁇ 0.13 are satisfied, If 0>x, 0 ⁇ y, -0.1 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.1, If 0 ⁇ x, 0>y, -0.1 ⁇ x,y and -0.13 ⁇ x+y ⁇ 0, In the case of 0 ⁇ x,0>y, 0 ⁇ x ⁇ 0.1 and
  • the above-mentioned "the content ratio of Pb is substantially equal to the total content ratio of Sc, Ta, Mg, and W” means the content ratio of Pb and the total content of Sc, Ta, Mg, and W. It is not limited to the case where the ratios are completely equal.
  • the content ratio of Pb is substantially equal to the total content ratio of Sc, Ta, Mg, and W means that the content ratio of Pb is the same as the total content ratio of Sc, Ta, Mg, and W. This also includes cases where the difference in molar ratio is within 3%, for example.
  • composition of the ceramic of the present disclosure can be analyzed and measured by performing a composition analysis using, for example, high-frequency inductively coupled plasma emission spectroscopy, fluorescent X-ray analysis, or the like.
  • the electrocaloric effect is an absorption and heat generation phenomenon caused by a change in entropy when the electric dipole moments in a substance are aligned or disordered due to a change in the electric field.
  • the performance index of the electrocaloric effect in the present invention may be an adiabatic temperature change ( ⁇ T).
  • ⁇ T adiabatic temperature change
  • the electric calorie effect is large may mean that the adiabatic temperature change ( ⁇ T) is large.
  • the larger the adiabatic temperature change ( ⁇ T) the more preferable.
  • Adiabatic temperature change ⁇ T means a temperature change in ceramics caused by applying an electric field to ceramics and/or removing the electric field applied to ceramics. Specifically, it may be the difference between the temperature of the ceramic before the electric field is applied and the temperature of the ceramic immediately after the electric field is applied, or the difference between the temperature of the ceramic before the electric field is removed and the temperature of the ceramic immediately after the electric field is removed. It may be a difference from the temperature of ceramics.
  • the adiabatic temperature change ⁇ T increases as the electric field strength applied to the ceramic increases. Further, the adiabatic temperature change ⁇ T tends to increase as the temperature of the ceramic approaches the antiferroelectric transition temperature (or ferroelectric transition temperature) when an electric field is applied. For example, as the temperature of the ceramic becomes lower than the transition temperature, the electrocaloric effect decreases rapidly. Specifically, in the conventional PMW, which has a transition temperature of about 20 to 30°C, the electrocaloric effect tends to decrease significantly when the temperature of the ceramic is 0°C or lower.
  • the ceramic has the formula (1): (1-m) PbSc 0.5-x Ta 0.5+x O 3 -mPbMg 0.5-y W 0.5+y O 3 (1)
  • m satisfies 0.60 ⁇ m ⁇ 0.95, In the case of 0 ⁇ x, y, x, y ⁇ 0.1 and 0 ⁇ x+y ⁇ 0.13 are satisfied, If 0>x, 0 ⁇ y, -0.1 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.1, If 0 ⁇ x, 0>y, -0.1 ⁇ x,y and -0.13 ⁇ x+y ⁇ 0, In the case of 0 ⁇ x,0>y, 0 ⁇ x ⁇ 0.1 and ⁇ 0.1 ⁇ y ⁇ 0 are satisfied.
  • It may be a ceramic represented by By setting x, y, and m in the above ranges, a large electrocaloric effect in a low electric field (for example, 0.8 K or more when an electric field strength of 8 MV/m is applied) can be obtained.
  • Substances that exhibit a large electrocaloric effect include PMW, which is an antiferroelectric material, and PbSc 0.5 Ta 0.5 O 3 , which is a ferroelectric material (hereinafter, ceramics containing Pb, Sc, and Ta are also referred to as "PST").
  • PMW and PST exhibit antiferroelectricity and ferroelectricity, respectively, which have a large latent heat during transition due to alignment of B-site cations (Mg and W in PMW, Sc and Ta in PST).
  • the practically used electrical calorie effect may be either a positive electrical calorie effect or a negative electrical calorie effect.
  • a large electric field strength of 10 MV/m or more is required to obtain a large negative electrocaloric effect, and only a very small electrocaloric effect is shown below 10 MV/m.
  • PMW the difference in the ionic radius between Mg and W is greater than in PST, so the B site is more likely to align.
  • ions at the B site can be aligned without a long heat treatment.
  • the threshold voltage of an antiferroelectric material was successfully lowered by adding PST to PMW. This is considered to be due to a moderate decrease in the alignment of the PMW B site.
  • the threshold voltage refers to a voltage at which electrical polarization suddenly increases (approximately 18 MV/m). Below the threshold voltage, the electrical polarizations are arranged so as to cancel each other out, and above the threshold voltage, the electrical polarizations begin to align in the direction of the electric field. In a stronger electric field, the polarization is all aligned in one direction, similar to a general ferroelectric material. That is, the antiferroelectric material is induced to have the same electric polarization as the ferroelectric material by applying a voltage higher than the threshold voltage.
  • Antiferroelectric materials do not exhibit an electrocaloric effect because their electric polarizations are aligned so that they cancel each other out (state A in Figure 1) below a threshold voltage, and when the threshold voltage is exceeded, their electric polarizations align (state A in Figure 1).
  • Condition B in 1) shows a positive or negative electrocaloric effect depending on the magnitude of the voltage.
  • the threshold voltage is reduced.
  • the ceramic of the present disclosure can exhibit an electrocaloric effect even in a low electric field. Note that once an electric field is applied to a ferroelectric material, a portion of the polarization remains (referred to as residual polarization), and accordingly, the entropy change during application and removal of the electric field becomes smaller, resulting in a loss in the electrocaloric effect. On the other hand, in antiferroelectric materials, when the electric field is removed, the electric polarization completely returns to zero, so there is no loss in the electrocaloric effect.
  • the ceramic of the present disclosure can obtain an excellent electrocaloric effect even at temperatures below 0° C. (for example, ⁇ 15° C.).
  • the present invention also makes it possible to prevent the polarity reversal of the electrocaloric effect in the temperature range of actual use (for example, -20 to 0°C), relatively low electric field strength, and 8 MV/m or more. Therefore, compared to conventional PMWs, the ceramics of the present disclosure have improved controllability of electrocaloric effects and do not require complex control when using the ceramics of the present disclosure as a cooling system.
  • the range of x and y is In the case of 0 ⁇ x, y, x, y ⁇ 0.1 and 0 ⁇ x+y ⁇ 0.12 are satisfied, If 0>x, 0 ⁇ y, -0.1 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.1, If 0 ⁇ x, 0>y, -0.1 ⁇ x,y and -0.12 ⁇ x+y ⁇ 0, In the case of 0 ⁇ x,0>y, 0 ⁇ x ⁇ 0.1 and ⁇ 0.1 ⁇ y ⁇ 0 are satisfied.
  • the range of x and y is In the case of 0 ⁇ x, y, x, y ⁇ 0.1 and 0 ⁇ x+y ⁇ 0.11 are satisfied, If 0>x, 0 ⁇ y, -0.1 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.1, If 0 ⁇ x, 0>y, -0.1 ⁇ x,y and -0.11 ⁇ x+y ⁇ 0, In the case of 0 ⁇ x,0>y, 0 ⁇ x ⁇ 0.1 and ⁇ 0.1 ⁇ y ⁇ 0 are satisfied.
  • the range of x and y is In the case of 0 ⁇ x,y, 0 ⁇ x+y ⁇ 0.1 is satisfied, If 0>x, 0 ⁇ y, -0.1 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.1, If 0 ⁇ x, 0>y, satisfy -0.1 ⁇ x+y ⁇ 0, In the case of 0 ⁇ x,0>y, 0 ⁇ x ⁇ 0.1 and ⁇ 0.1 ⁇ y ⁇ 0 are satisfied.
  • the range of x and y is In the case of 0 ⁇ x,y, 0 ⁇ x+y ⁇ 0.08 is satisfied, If 0>x, 0 ⁇ y, satisfy -0.08 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.08, If 0 ⁇ x, 0>y, satisfy -0.08 ⁇ x+y ⁇ 0, In the case of 0 ⁇ x, 0>y, 0 ⁇ x ⁇ 0.08 and ⁇ 0.08 ⁇ y ⁇ 0 are satisfied.
  • the range of x and y is In the case of 0 ⁇ x,y, satisfy 0 ⁇ x ⁇ 0.05 and 0 ⁇ y ⁇ 0.05, If 0>x, 0 ⁇ y, satisfy -0.05 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.05, If 0 ⁇ x, 0>y, satisfy -0.05 ⁇ x ⁇ 0 and -0.05 ⁇ y ⁇ 0, In the case of 0 ⁇ x,0>y, 0 ⁇ x ⁇ 0.05 and ⁇ 0.05 ⁇ y ⁇ 0 are satisfied.
  • the range of x and y is In the case of 0 ⁇ x,y, 0 ⁇ x+y ⁇ 0.05 is satisfied, If 0>x, 0 ⁇ y, satisfy -0.05 ⁇ x ⁇ 0 and 0 ⁇ y ⁇ 0.05, If 0 ⁇ x, 0>y, -0.05 ⁇ x+y ⁇ 0, In the case of 0 ⁇ x,0>y, 0 ⁇ x ⁇ 0.05 and ⁇ 0.05 ⁇ y ⁇ 0 are satisfied.
  • the ranges of x and y include the above-mentioned "0 ⁇ x, y", “0>x, 0 ⁇ y”, “ ⁇ x, 0>y”, and The range may be determined by arbitrarily combining the ranges of x and y in the case of 0 ⁇ x, 0>y.
  • x and y are 0. That is, the formula represented by (1-m)PbSc 0.5-x Ta 0.5+x O 3 -mPbMg 0.5-y W 0.5+z O 3 is (1-m)PbSc 0.5 Ta 0 .5 O 3 -mPbMg 0.5 W 0.5 O 3 .
  • m may be 0.60 ⁇ m ⁇ 0.95.
  • the range of m is preferably 0.60 ⁇ m ⁇ 0.90, more preferably 0.70 ⁇ m ⁇ 0.90, even more preferably 0.70 ⁇ . m ⁇ 0.80.
  • the range of m is preferably 0.60 ⁇ m ⁇ 0.90, more preferably 0.65 ⁇ m ⁇ 0.90, even more preferably 0.65 ⁇ . m ⁇ 0.85.
  • the range of m may be 0.90 ⁇ m ⁇ 0.95.
  • the range of m may be 0.60 ⁇ m ⁇ 0.80.
  • the crystal structure of the ceramic according to one embodiment of the present invention may be a perovskite structure.
  • Ceramics having a perovskite structure include not only ceramics having a "perovskite-type crystal structure” but also ceramics having a "perovskite-type crystal structure".
  • a ceramic having a perovskite structure may have a crystal structure that can be recognized as a perovskite crystal structure by a person skilled in the ceramics field in X-ray diffraction.
  • the electrocaloric effect element of the present disclosure has a laminate in which electrode layers and ceramic layers containing the ceramic of the present disclosure as a main component are alternately laminated.
  • the electrocaloric effect element 1 has electrode layers 2a and 2b (hereinafter also collectively referred to as “electrode layers 2”) and a ceramic layer 4 stacked alternately. It has a laminate 6 and external electrodes 8a and 8b (hereinafter also collectively referred to as “external electrodes 8") connected to the electrode layer 2.
  • the electrode layers 2a and 2b are electrically connected to external electrodes 8a and 8b arranged on the end faces of the laminate 6, respectively.
  • the electrode layer 2 is a so-called internal electrode. In addition to the function of applying an electric field to the ceramic layer 4, the electrode layer 2 may also have the function of transporting heat between the ceramic layer 4 and the outside.
  • the above electrode layer may be an electrode layer whose main component is a noble metal.
  • the "main component" in the electrode layer means that the electrode layer consists of 80% by mass or more of a noble metal, for example, 95% by mass or more of the electrode layer, more preferably 98% by mass or more, and even more preferably means that 99% or more, even more preferably 99.5% by mass or more, particularly preferably 99.9% by mass or more is noble metal.
  • the "noble metal” may be, for example, Au, Ag, Pt, or Pd.
  • the main component of the electrode layer used in the present disclosure may be Pt or Pd. That is, it may be a Pt or Pd electrode layer.
  • the noble metal electrode layer may be made of an alloy of Pt and/or Pd and other elements (such as Ag, Pd, Rh, Au, etc.) (such as Ag-Pd). alloy, etc.) or a mixture. Similar effects can be obtained even if the Pt or Pd electrode layer is composed of an alloy or a mixture thereof. It may also contain other elements that may be mixed in as impurities, particularly unavoidable elements (eg, Fe, Al 2 O 3 , etc.). In this case as well, similar effects can be obtained.
  • the thickness of the electrode layer 2 is preferably 0.2 ⁇ m or more and 10 ⁇ m or less, more preferably 1.0 ⁇ m or more and 5.0 ⁇ m or less, for example, 2.0 ⁇ m or more and 5.0 ⁇ m or less, or 2.0 ⁇ m or more and 4.0 ⁇ m or less. .
  • the thickness of the electrode layer By setting the thickness of the electrode layer to 0.5 ⁇ m or more, the resistance of the electrode layer can be reduced and the heat transport efficiency can be increased. Further, by setting the thickness of the electrode layer to 10 ⁇ m or less, the thickness (and thus the volume) of the ceramic layer can be increased, and the amount of heat that can be handled by the electric calorie effect of the entire device can be increased. Furthermore, the element can be made smaller.
  • the ceramic layer 4 may contain one type of ceramic as a main component, or may contain two or more types of ceramics as a main component.
  • the "main component" in the ceramic layer means that the ceramic layer essentially consists of the target ceramic, for example, 90% by mass or more, more preferably 95% or more, even more preferably 95% or more by mass of the ceramic layer. This means that 98% by mass or more, even more preferably 99% by mass or more, particularly preferably 99.5% by mass or more is the subject ceramic.
  • Other components may include a crystalline phase having a structure different from the perovskite structure called a pyrochlore structure, other elements mixed as impurities, and particularly unavoidable elements (for example, Zr, C, etc.).
  • the composition of the ceramic layer 4 can be determined by high-frequency inductively coupled plasma emission spectroscopy, fluorescent X-ray analysis, or the like. Further, the structure of the ceramic layer 4 can be determined by powder X-ray diffraction.
  • the thickness of the ceramic layer 4 is preferably 5 ⁇ m or more and 100 ⁇ m or less, more preferably 5 ⁇ m or more and 50 ⁇ m or less, even more preferably 10 ⁇ m or more and 50 ⁇ m or less, even more preferably 20 ⁇ m or more and 50 ⁇ m or less, and particularly preferably 20 ⁇ m or more and 40 ⁇ m or less. .
  • the amount of heat that the element can handle can be increased.
  • By making the thickness of the ceramic layer thinner a higher ⁇ T can be obtained and the withstand voltage can also be improved.
  • the withstand voltage of the ceramic layer 4 may be preferably 15 MV/m or more, more preferably 20 MV/m or more, even more preferably 25 MV/m or more. By increasing the withstand voltage of the ceramic layer, a larger voltage (electric field) can be applied, and a larger ⁇ T can be obtained.
  • Materials constituting the pair of external electrodes 8a, 8b include, but are not limited to, Ag, Cu, Pt, Ni, Al, Pd, Au, or alloys thereof (for example, Ag-Pd, etc.).
  • the electrode may be made of metal and glass or may be made of metal and resin. Among the metals, Ag is preferred.
  • the electrode layers 2 and the ceramic layers 4 are alternately laminated, but in the electrocaloric effect element of the present disclosure, the number of laminated electrode layers and ceramic layers is not particularly limited. Further, all of the internal electrodes do not need to be connected to external electrodes, and internal electrodes that are not connected to external electrodes may be included as necessary for heat transfer or stress relaxation due to piezoelectricity or electrostriction.
  • the internal electrode and the ceramic layer are in contact with each other on substantially the entire surface, but the electrocaloric effect element of the present disclosure is not limited to such a structure, and a voltage (electric field) is applied to the ceramic layer. It is not particularly limited as long as it has a structure that can apply .
  • the electrocaloric effect element 1 has a rectangular parallelepiped block shape, the shape of the electrocaloric effect element of the present disclosure is not limited to this, and may be, for example, cylindrical or sheet-like, and may also have unevenness or through holes. etc. may be included.
  • internal electrodes may be exposed on the surface for heat transport and heat exchange with the outside.
  • the ceramics and electrocaloric effect element of this embodiment described above are manufactured, for example, as follows.
  • high-purity lead oxide (Pb 3 O 4 ), tantalum oxide (Ta 2 O 5 ), scandium oxide (Sc 2 O 3 ), magnesium carbonate (MgCO 3 ), and tungsten oxide (WO 3 )) were calcined. Afterwards, it is weighed to obtain the desired composition ratio.
  • the above raw materials are pulverized and mixed with partially stabilized zirconia (PSZ) balls, pure water, a dispersant, etc. in a ball mill. Thereafter, the pulverized and mixed slurry is dried, sized, and then calcined, for example, at 800° C. to 900° C.
  • PSZ partially stabilized zirconia
  • the obtained calcined powder is mixed with PSZ balls, ethanol, toluene, a dispersant, etc., and pulverized.
  • a binder solution dissolved in the obtained pulverized powder is added and mixed to prepare a slurry for sheet molding.
  • the prepared slurry is formed into a sheet on a support, and a Pt electrode paste is printed on it.
  • the green chips are heat-treated at 500°C to 600°C in the atmosphere to remove the binder.
  • the binder-removed chip is fired at 800° C.
  • the electrocaloric effect element of the present disclosure exhibits an excellent electrocaloric effect, it can be used as a heat management element, especially a cooling element (including cooling/heat pump elements for air conditioners such as air conditioners, refrigerators, and freezers).
  • a cooling element including cooling/heat pump elements for air conditioners such as air conditioners, refrigerators, and freezers.
  • the present disclosure also provides an electronic component comprising the electrocaloric effect element of the present disclosure, and an electronic device comprising the electrocaloric effect element or electronic component of the present disclosure.
  • Examples of electronic components include, but are not limited to, electronic components used in air conditioners, refrigerators, or freezers; electronic components (e.g., batteries) used in air conditioning of electric vehicles and hybrid cars; and central processing units (CPUs).
  • ICs integrated circuits
  • HDDs hard disks
  • PMICs power management ICs
  • PAs power amplifiers
  • transceiver ICs and voltage regulators (VRs)
  • light-emitting elements such as light-emitting diodes (LEDs), incandescent light bulbs, and semiconductor lasers.
  • components that can be heat sources such as field effect transistors (FETs), and other components such as lithium ion batteries, substrates, heat sinks, casings, and other components commonly used in electronic devices.
  • FETs field effect transistors
  • Examples of electronic devices include, but are not limited to, air conditioners, refrigerators, or freezers; air conditioners used as heat pumps, air conditioners for electric vehicles or hybrid cars, mobile phones, smartphones, personal computers (PCs), tablet terminals, and hard disk drives. Examples include small electronic devices such as drives and data servers.
  • the electrocaloric element of the present disclosure can be used as a thermal management system (or temperature management system) that manages heat (temperature) of the electronic component and the electronic device.
  • thermal management system or temperature management system
  • examples of the thermal management system include a cooling system that cools the electronic components and electronic equipment.
  • the obtained calcined powder was mixed with PSZ balls having a diameter of 5 mm, ethanol, toluene, and a dispersant for 16 hours, and then pulverized.
  • a dissolved binder solution was added to the obtained pulverized powder and mixed for 4 hours to prepare a slurry for sheet molding.
  • the produced slurry was formed into a sheet shape with a thickness corresponding to the thickness of a predetermined ceramic layer on a PET film by a doctor blade method, and after cutting into strips, a platinum internal electrode paste was screen printed. Note that the sheet thickness of the laminated element to be produced was controlled by changing the gap of the doctor blade used during sheet forming.
  • a green chip was produced by laminating a predetermined number of sheets printed with platinum internal electrode paste and sheets without printing, then press-bonded with a pressure of 150 MPa, and cut.
  • the green chips were heat-treated at 550° C. for 24 hours in the air to remove the binder.
  • the green chip was sealed in an alumina sealed sheath together with PbZrO 3 powder for creating a Pb atmosphere, and fired at 900 to 1300° C. for 4 hours. Samples within the scope of the present invention could be fired satisfactorily at temperatures between 900 and 1250°C.
  • Sample number 1 as a comparative example shown in Table 1 was fired at a high temperature of 1400°C and then heat treated at 1000°C for 1000 hours.
  • the size of the obtained element was approximately L10.2 mm x W7.2 mm x T0.88 for an element in which the thickness of the ceramic layer was 40 ⁇ m.
  • the number of ceramic layers sandwiched between the internal electrode layers was 19, the electrode area was 49 mm 2 /layer, and the total electrode area was 49 mm 2 ⁇ 19 layers.
  • the thickness of the ceramic layer of the element obtained above was confirmed using a scanning electron microscope after cross-sectional polishing of the element.
  • composition The ceramic composition of the obtained element was confirmed using high frequency inductively coupled plasma emission spectroscopy and fluorescent X-ray analysis.
  • Crystal structure In order to evaluate the crystal structure of the obtained device, powder X-ray diffraction measurement was performed. One element was randomly selected from each lot, ground in a mortar, and then an X-ray diffraction profile was obtained. From the obtained X-ray diffraction profile, it was confirmed whether the crystal structure of the ceramic was a perovskite structure, and the presence or absence and abundance ratio of impurity phases (mainly pyrochlore phase) were estimated from the intensity ratio. When the abundance ratio of perovskite structure was 0.95 or more, it was determined that the main component had a perovskite structure, and when it was less than 0.95, it was determined that there was a different phase.
  • the electrocaloric effect was evaluated by applying voltage to the sample in the sequence shown in the graph of FIG. 4(a). That is, first, a voltage was applied to the sample, the voltage was maintained as it was, then the applied voltage was removed and the voltage was maintained as it was, and this operation was repeated to measure changes in the electrocaloric effect.
  • the adiabatic temperature change ⁇ T was determined by applying a predetermined voltage, keeping it applied for 50 seconds and measuring the temperature, and then removing the voltage and keeping it in a state without applying it for 50 seconds to measure the temperature. .
  • This sequence was repeated three times. During the sequence of voltage application and voltage removal, the temperature of the element was constantly measured, and the adiabatic temperature change ⁇ T was determined from the temperature change. Further, when the absolute value of the adiabatic temperature change ⁇ T when applying an electric field of 8 MV/m and 15 MV/m at -15° C. was 0.8 K or more and 1.5 K or more, respectively, it was determined as Go.
  • Tables 1 to 4 The results are shown in Tables 1 to 4.
  • the conventional PMW is characterized by an antiferroelectric material in which the electric polarization increases rapidly from the threshold voltage (approximately 15 MV/m) when the electric field intensity increases, and the electric polarization saturates at even higher electric field intensity. It shows double hysteresis.
  • the threshold voltage is approximately 15 MV/m at 15° C., but as the temperature decreases, the threshold voltage increases and a larger electric field is required.
  • FIG. 6 shows the adiabatic temperature change ⁇ T measured while changing the electric field strength at 15° C.
  • FIG. 7 shows the adiabatic temperature change ⁇ T measured while changing the temperature with the electric field strength fixed at 20 MV/m.
  • a negative calorific value effect was obtained in which heat was absorbed when an electric field was applied and heat was generated when an electric field was removed.
  • the adiabatic temperature change ⁇ T gradually increases from near the threshold voltage.
  • FIG. 8 shows the electrocaloric effect of the conventionally known PST shown in sample number 2.
  • PST had a positive caloric effect in all temperature ranges, and the adiabatic temperature change ⁇ T was maximized near the transition temperature of 20°C, resulting in an extremely excellent caloric effect.
  • the effect rapidly decreased below 0°C, and sufficient effects could not be obtained at low temperatures.
  • Table 1 shows the characteristics test results of the samples prepared above. Specifically, Table 1 shows the electrocaloric effect of samples in which the values of x and y in equation (1) are fixed to 0, and m is changed to various values. As a result of XRD measurement, all of the samples having the compositions shown in Table 1 had the desired perovskite structure as a main component and had few foreign phases.
  • the conventionally known PMW shown in sample number 1 and PST shown in sample number 2 had a low electrocaloric effect at -15°C, and the adiabatic temperature change was smaller than 1.5K.
  • the absolute values of adiabatic temperature changes were 0.8 K and 1.5 K or more when electric fields of 8 MV/m and 15 MV/m were applied, respectively.
  • m is within the range of 0.6 ⁇ m ⁇ 0.8
  • an electric field strength of 15 MV/m when an electric field strength of 15 MV/m is applied, a positive calorific value effect is exhibited in the range of -20°C to 0°C, and the sign is reversed in that temperature range. There was no.
  • Samples in which m was within the range of 0.8 ⁇ m ⁇ 0.95 exhibited a negative calorific value effect in that temperature range and electric field strength, but there was no sign reversal.
  • FIG. 9 shows the temperature dependence of the adiabatic temperature change when applying an electric field of 15 MV/m for Sample No. 2 and Sample No. 6.
  • the adiabatic temperature change of sample number 1 was measured at a higher electric field strength (20 MV/m), and the electrocaloric effect was small in the temperature range below 0°C. (The comparison has been omitted.)
  • the ferroelectric transition temperature has not been lowered sufficiently, and if m is larger than 0.95, the transition temperature has not been lowered sufficiently, and the antiferroelectric transition temperature has not been lowered sufficiently. It is thought that the adiabatic temperature change at low temperatures and low electric fields became small because the threshold voltage could not be lowered.
  • the ratio of substances having the desired crystal structure was nearly 100%, with both x and y being most stable near 0. Even when both x and y are not around 0, no foreign phase is generated, but when they deviate significantly from 0, the proportion of foreign phases increases or the insulation property decreases, causing element breakdown when an electric field is applied (see Tables 2 to 4). (See crystal structure section).
  • the main components will have the desired structure, and the absolute values of the adiabatic temperature changes will be 0.8 K and 1.0 K when electric fields of 8 MV/m and 15 MV/m are applied at -15°C, respectively. It was over 5K.
  • FIG. 10 shows the composition ranges of x and y in Table 2 that were determined to be Go as a result of the characteristic test. As shown in FIG. 10, it was confirmed that the ceramics within the scope of the present invention were judged as Go in the characteristic test. Note that Tables 3 and 4 also show the same results as FIG. 10.
  • the electrocaloric effect element of the present disclosure can exhibit a high electrocaloric effect, it can be used, for example, in electric vehicles or hybrid cars, air conditioners (e.g., air conditioners used in electric cars or hybrid cars, air conditioners used as heat pumps, etc.), refrigerators, etc. It can also be used as a heat management element in a freezer, etc., and can also be used in various electronic devices, such as small electronic devices such as mobile phones, smartphones, tablet terminals, hard disk drives, or data servers, where heat countermeasure problems are becoming more prominent. Alternatively, it can be used as a cooling device for a personal computer (PC) or the like.
  • PC personal computer
  • Electrocaloric effect element 2a, 2b Electrode layer 4
  • Ceramic layer 6 Ceramic layer 6
  • Laminated body 8a, 8b External electrode

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