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US-12617991-B2 - Microcapsule for latent heat storage materials, method for producing same, powder containing microcapsules for latent heat storage materials, and heat storage device comprising said powder

US12617991B2US 12617991 B2US12617991 B2US 12617991B2US-12617991-B2

Abstract

A microcapsule for latent heat storage materials includes a metal core containing Zn and Al and a shell covering the metal core. The shell of the microcapsule includes an oxide film containing Zn and O, and an oxide film containing Al and O adjacent to an inner side of the oxide film containing Zn and O. In the microcapsule, a mass ratio of ZnAl 2 O 4 is 4% or less. The mass ratio is determined by analyzing the microcapsule by an XRD (X-ray diffractometer) device and subjecting results to quantitative analysis using a RIR (Reference Integrity Ratio) method.

Inventors

  • Takahiro Nomura
  • Takahiro Kawaguchi
  • Hiroki Sakai
  • Shunsuke Cho
  • Kohei Kashiyama
  • Kenji Sato
  • Kazuyuki Miya
  • Yoshitaka Shibuya

Assignees

  • NATIONAL UNIVERSITY CORPORATION HOKKAIDO UNIVERSITY

Dates

Publication Date
20260505
Application Date
20200820
Priority Date
20190823

Claims (13)

  1. 1 . A microcapsule for latent heat storage materials, the microcapsule comprising a metal core containing Zn and Al and a shell covering the metal core, wherein the shell of the microcapsule comprises an oxide film containing Zn and O, and an oxide film containing Al and O adjacent to an inner side of the oxide film containing Zn and O; wherein the microcapsule comprises 60 to 95 parts by mass of Zn, and 5 to 40 parts by mass of Al, when the total mass of Al and Zn in the microcapsule is 100 parts by mass; and wherein, when the microcapsule is analyzed by an XRD (X-ray diffractometer) and results are subjected to quantitative analysis using a RIR (Reference Integrity Ratio) method, a mass ratio of ZnAl 2 O 4 in the microcapsule is 4% or less.
  2. 2 . The microcapsule for latent heat storage materials according to claim 1 , wherein the oxide film containing Al and O has an average thickness of 100 to 1000 nm.
  3. 3 . The microcapsule for latent heat storage materials according to claim 1 , wherein the oxide film containing Zn and O has an average thickness of 100 to 1000 nm.
  4. 4 . The microcapsule for latent heat storage materials according to claim 1 , wherein the core has a melting point of 300 to 550° C.
  5. 5 . The microcapsule for latent heat storage materials according to claim 1 , wherein the microcapsule has a latent heat amount of 0.3 to 1.2 GJm −3 .
  6. 6 . The microcapsule for latent heat storage materials according to claim 1 , wherein a volume expansion coefficient of the metal core is 5 to 9% during melting of the microcapsule.
  7. 7 . A powder comprising a plurality of the microcapsules for latent heat storage materials according to claim 1 .
  8. 8 . The powder according to claim 7 , wherein the powder has an average particle size of 20 to 80 μm.
  9. 9 . The powder according to claim 8 , wherein the powder has an average particle size of 20 to 38 μm.
  10. 10 . A heat storage device comprising the powder according to claim 7 .
  11. 11 . An exhaust gas passage of an automobile comprising, on an outer periphery thereof, the heat storage device of claim 10 .
  12. 12 . A method for producing the microcapsule for latent heat storage materials according to claim 1 , comprising: providing Zn-Al alloy particles, subjecting the Zn-Al alloy particles to a boehmite treatment and an oxidation treatment in this order, wherein the oxidation treatment includes increasing a temperature of the particles to a retention temperature under a condition of a temperature increasing rate of 10° C./min or more, and maintaining the particles at the retention temperature and in an oxygen-containing atmosphere, wherein the retention temperature is 700° C. to 830° C.
  13. 13 . The method according to claim 12 , wherein the temperature increasing rate to the retention temperature is 30° C./min or more.

Description

The present application is a U.S. National Stage of PCT International Patent Application No. PCT/JP2020/031517, filed Aug. 20, 2020, which claims priority to JP Application No. 2019-153237, filed Aug. 23, 2019, both of which are hereby incorporated herein by reference. FIELD OF THE INVENTION The present invention relates to a microcapsule for latent heat storage materials, a method for producing the same, a powder containing microcapsules for latent heat storage materials, and a heat storage device comprising said powder. BACKGROUND OF THE INVENTION Techniques for storing heat include, for example, sensible heat storage and latent heat storage. The sensible heat storage uses a temperature change of a heat storage material. On the other hand, the latent heat storage uses a phase change of the heat storage material, for example, from a solid phase to a liquid phase. Patent Literature 1 discloses a latent heat storage body, wherein the latent heat storage body comprises core particles of an Al-Si alloy and a shell of Al oxide film covering the core particles. With regard to the shell, Patent Literature 1 discloses that the core particles are subjected to a chemical coating treatment, and further to a thermal oxidation treatment, thereby enabling an oxide film to be formed. Patent Literature 2 discloses that core particles of a latent heat storage body are made of an alloy of at least one alloy component A selected from the following group A and at least one alloy component B selected from the following group B (A-B alloy): Group A: Ca, Si, Bi, Mg, Sb, In, Sn, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, Au, Pb; and Group B: Al, Cr, Mn, Si, Mg, Co, Ni. Furthermore, Patent Literature 2 discloses that the following relationship is satisfied: ΔGA0 ≥ΔGB0 (ΔGA0): standard free energy of oxide formation of the alloy component A; and(ΔGB0): standard free energy of oxide formation of the alloy component B Non-Patent Literature 1 discloses the following three alloys: Zn84Al8.7Mg7.3; Zn88.7Al11.3; and Zn92.2Mg7.8, in which each number represents at. %. Further, Non-Patent Literature 1 discloses that these alloys were evaluated for their potential to be used as phase changing materials for latent heat storage. Furthermore, this literature discloses that those alloys have melting points of 344° C., 382° C., and 371° C., respectively, and heat of fusion of 132 Jg−1, 118 Jg−1, and 106 Jg−1, respectively. CITATION LIST Patent Literatures [Patent Literature 1] WO 2015/162929 A1 [Patent Literature 2] WO 2017/200021 A1 Non-Patent Literature [Non-Patent Literature 1] E. Risue et al., “Zinc-rich eutectic alloys for high energy density latent heat storage applications”, Journal of Alloys and Compounds 705 (2017), p. 714-721 SUMMARY OF THE INVENTION Technical Problem For example, the present inventors have considered that the core-shell type latent heat storage body as described above is used for temperature control of an automobile exhaust gas. The automobile exhaust gas has a wide temperature range, for example, about 200° C. at the time of idling and about 800° C. at the time of full load operation. An exhaust system of an automobile is equipped with an exhaust purification catalyst. However, an excessively high temperature of the exhaust gas may cause decreased and/or deteriorated performance of the exhaust purification catalyst. Therefore, for the purpose of suppressing an excessive increase in the exhaust gas temperature, it is considered that the latent heat storage body is arranged in the exhaust system of the automobile to exchange heat. On the other hand, an excessively low temperature of the exhaust gas does not lead to sufficient performance of the exhaust purification catalyst. From the above viewpoints, the use of the latent heat storage body having an appropriate operating temperature of about 300 to 550° C. and a good latent heat amount may allow an excessive variation of the exhaust gas temperature of the automobile to be suppressed. The present invention has been created in view of the above circumstances. In an embodiment, an object of the present invention is to provide a latent heat storage body which has a melting point of about 300 to 550° C. and is difficult to cause leakage of a phase changing material, and a product obtained by applying the body (e.g., powder, a heat storage device, etc.). Further, in another embodiment, an object of the present invention is to provide a method for producing such a latent heat storage body. Solution to Problem As a result of intensive studies, the present inventors have found that microcapsules containing a combination of Al and Zn have a suitable melting point and are advantageous in preventing leakage of phase changing materials. The present invention has been completed based on the finding, and is illustrated below: (Invention 1) A microcapsule for latent heat storage materials, the microcapsule comprising a metal core containing Zn and Al and a shell covering the metal