CN113631511B - Magnetic refrigeration module and preparation method thereof - Google Patents
Magnetic refrigeration module and preparation method thereof Download PDFInfo
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- CN113631511B CN113631511B CN201980093584.2A CN201980093584A CN113631511B CN 113631511 B CN113631511 B CN 113631511B CN 201980093584 A CN201980093584 A CN 201980093584A CN 113631511 B CN113631511 B CN 113631511B
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- 229910052688 Gadolinium Inorganic materials 0.000 claims description 10
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
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Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
- F25B2321/002—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Abstract
A magnetic refrigeration module, a magnetic refrigeration device comprising the module and a method for preparing the magnetic refrigeration module. The magnetic refrigeration module includes: a film (11) comprising a graphene material and a magnetocaloric material (15), the magnetocaloric material (15) forming nanoparticles attached to the surface of the film (11). The structure can conveniently realize the magnetic refrigeration device with higher heat conductivity and heat exchange rate.
Description
Technical Field
The application relates to the field of magnetocaloric materials, in particular to a magnetic refrigeration module, a magnetic refrigeration device comprising the magnetic refrigeration module and a method for preparing the magnetic refrigeration module.
Background
The refrigeration mode widely adopted at present is a vapor compression refrigeration technology, which repeatedly compresses and expands a gaseous or liquid refrigerant through a compressor, and takes heat away from the environment or equipment by the refrigerant in the circulation process, thereby realizing refrigeration. However, the refrigerating efficiency of the compressor is low, the energy consumption is huge, and the leakage of the refrigerant seriously affects the ecological environment and the physical health, so that the conventional refrigerating technology is being replaced by the emerging refrigerating technology.
Magnetic refrigeration technology based on the "magnetocaloric effect (Magneto Caloric Effect)" is becoming a very potential alternative technology. In a magnetocaloric material with magnetocaloric effect, the application and removal of an externally applied magnetic field may result in a change in the order of the magnetic moments in the material, which may result in a change in the temperature of the material. The magnetic refrigeration technology utilizes the magnetocaloric effect of the bulk magnetocaloric material to refrigerate without using a refrigerant and a compressor, so that the technology has the characteristics of high efficiency, energy saving and environmental friendliness, and has gained more attention and application.
The existing magnetocaloric material mainly adopts metal gadolinium (Gd) and compounds thereof, mnFe-based compounds and La 1-x Ca x MaO 3 Base compound, la (Fe) 1-x Si x ) 13 Series compounds or heusler (heusler) alloys, etc. However, the thermal conductivity of these magnetocaloric materials themselves is low and hardly meets the application requirements, for example, the thermal conductivity of gadolinium metal is only about 10W/m·k. In addition, to increase heat exchange efficiency, it is often necessary to process magnetocaloric materials into various shapes to increase surface area, e.g. to processInto irregular granules or pellets, or into slabs or cut pieces. The problem associated with this is that these magnetocaloric materials have poor machining properties, limit the shapes that can be machined, and do not guarantee uniformity of properties when forming bulk materials. Therefore, the preparation and processing of the magnetocaloric materials also have a great limitation on the application of the magnetocaloric materials.
There has been a method of forming nanoparticles on the surface of a reduced graphene oxide film, which employs ultra-rapid heating and cooling to form stable nanoparticles of Al, si, sn, au or Pd, etc. on the reduced graphene oxide film. However, a similar approach does not occur in the processing of magnetocaloric materials.
Therefore, there is a need for a magnetic refrigeration module having high thermal conductivity, high heat exchange efficiency, and convenient processing, and a method of manufacturing the same.
Disclosure of Invention
The present application aims to overcome at least one of the above-mentioned drawbacks of the prior art and to provide an improved magnetic refrigeration module, a magnetic refrigeration device comprising such a magnetic refrigeration module and a method for manufacturing a magnetic refrigeration module, so as to achieve a higher thermal conductivity and heat exchange efficiency, and to facilitate processing and manufacturing.
To this end, according to a first aspect of the application, there is provided a magnetic refrigeration module comprising:
a film comprising a graphene material; and
a magnetocaloric material forming nanoparticles attached to the surface of the film.
Preferably, the nanoparticles formed from the magnetocaloric material are separated from each other by defects on the surface of the film.
Preferably, the graphene material comprises at least one of graphene, graphene oxide, and reduced graphene oxide.
Preferably, the graphene material has a thermal conductivity of at least 1000W/m.k, preferably at least 1300W/m.k, more preferably at least 1500W/m.k, particularly preferably at least 2000W/m.k.
Preferably, the magnetocaloric material is gadolinium metal.
Preferably, the particle size of the nanoparticles is less than 30nm, preferably less than 20nm, more preferably less than 10nm.
Preferably, the magnetic refrigeration module comprises a construction formed from a plurality of layers of films stacked together or wound or folded from a single layer of film such that the nanoparticles are located between adjacent two layers of film.
According to another aspect of the present application, there is provided a magnetic refrigeration apparatus comprising:
the magnetic refrigeration module; and
a magnet configured to provide a magnetic field for the magnetic refrigeration module.
Preferably, the magnetic refrigeration device further comprises a heat sink capable of absorbing heat from the magnetic refrigeration module.
Preferably, the magnetic refrigeration device further comprises a thermal interface material disposed between the heat sink and the magnetic refrigeration module.
According to another aspect of the present application, there is provided a method of preparing a magnetic refrigeration module, the method comprising the steps of:
providing a film comprising a graphene material;
distributing a magnetocaloric material on the surface of the film;
heating the magnetocaloric material to a molten state; and
the magnetocaloric material and the film are cooled such that the magnetocaloric material forms nanoparticles on the surface of the film.
Preferably, the nanoparticles formed from the magnetocaloric material are separated from each other by defects on the surface of the film.
The magnetic refrigeration module and the magnetic refrigeration device fully utilize the characteristics of the magnetic thermal material and the graphene material, can greatly improve the heat conductivity of the magnetic refrigeration module and obviously improve the heat exchange efficiency. The preparation method of the magnetic refrigeration module can quickly form ultrafine nano particles and avoid reducing the performance of the nano particles.
Drawings
Exemplary embodiments of the present application will be described in detail below with reference to the attached drawings, and it should be understood that the embodiments described below are only for explaining the present application, not limiting the scope of the present application. Features that are structurally identical or functionally similar are denoted by the same reference numerals in the various figures of the application. It should be understood that the dimensions, proportions, and number of parts of the figures are not intended to limit the application. In the drawings:
fig. 1A and 1B are schematic perspective views showing a pre-production state and a post-production state of a magnetic refrigeration module according to an embodiment of the present application, respectively;
FIG. 2 is a schematic diagram illustrating a magnetic refrigeration apparatus according to an embodiment of the present application; and
fig. 3 is a flowchart illustrating a method of manufacturing a magnetic refrigeration module according to an embodiment of the present application.
Detailed Description
Preferred embodiments of the present application will be described in detail below with reference to examples. Those skilled in the art will appreciate that these exemplary embodiments are not meant to impose any limitations on the present application. Furthermore, features in embodiments of the application may be combined with each other without conflict. In the drawings, other components are omitted for brevity, but this does not indicate that the magnetic refrigeration module and the magnetic refrigeration apparatus of the present application may not include other components, nor that the manufacturing method of the present application may not include other steps.
In the present application, "magnetocaloric material" refers generally to a magnetic material having a magnetocaloric effect, for example, the aforementioned metal gadolinium (Gd), a compound thereof, and the like. The magnetic refrigeration can be realized by the magnetic heat material, but the existing magnetic heat material has low common heat conductivity and is difficult to meet the heat dissipation requirement in actual operation. It is known that, in general, the thermal conductivity of metals is substantially lower than 500W/m·k, whereas graphene theoretically has a thermal conductivity as high as 5300W/m·k, and graphene films having a thermal conductivity as high as 3200W/m·k have been realized in the laboratory. Therefore, based on the characteristics of the graphene material and the magnetocaloric material, the application creatively provides an improved magnetic refrigeration module, and the module combines the graphene material and the magnetocaloric material together, so that the module has remarkable advantages in the aspect of magnetic refrigeration. The magnetic refrigeration module of the present application is described in detail below with reference to fig. 1A and 1B.
Fig. 1A and 1B schematically illustrate a pre-fabrication state and a post-fabrication state, respectively, of a magnetic refrigeration module 10 according to an embodiment of the present application. As shown in fig. 1A and 1B, the magnetic refrigeration module of the present application includes a film 11 and a magnetocaloric material 15, wherein the film 11 includes a graphene material. In the present application, "graphene material" refers generally to layered carbon materials having a hexagonal lattice, which may include graphene, graphene Oxide (GO), reduced Graphene Oxide (RGO), and doped graphene films, or other graphene compounds, and the like. As graphene materials generally have various defects, these defects may present areas on the surface of the thin film-like graphene material separated by adjacent defects. For example, as can be seen in fig. 1A and 1B, there are generally hexagonal areas 12 and defects 13 on the surface of the film 11. In the magnetic refrigeration module 10 after the preparation, the magnetic material 15 forms nanoparticles attached to the surface of the film 11. Since graphene materials have very high thermal conductivities, as previously described, the magnetic refrigeration module 10 of the present application can achieve much higher thermal conductivities than the magnetocaloric material 15 itself. In addition, the magnetocaloric material 15 forms nanoparticles, which significantly increases the surface area, and thus also greatly improves the heat exchange efficiency.
As shown in fig. 1B, the nanoparticles formed of the magnetocaloric material 15 are separated from each other on the surface of the film 11. It is known that defects (e.g., vacancies, grain boundaries, and slits) are inevitably formed on the surface of a film formed of a graphene material. These defects block the migration of the nanoparticles, allowing the nanoparticles to be effectively confined within the area divided by adjacent defects. This phenomenon is evident in the Reduction of Graphene Oxide (RGO). As a result, the nanoparticles formed of the magnetocaloric material 15 remain isolated from each other and do not undergo significant aggregation and coalescence, separating the defects 13 on the surface of the nanoparticle coating 11 from each other. Thus, the formed nano particles are finer, have larger surface area and are distributed more uniformly, and the heat exchange efficiency is further improved.
According to an embodiment of the present application, the graphene material of the film 11 is Reduced Graphene Oxide (RGO), because the surface of the reduced graphene oxide in the form of a film has defects 13 forming a grid that are dispersed more uniformly, facilitating the formation of nanoparticles. Different types of graphene materials obtained in different ways or of different types may have different thermal conductivities and surface defects, and therefore other types of graphene materials may also be selected according to different application requirements. Of course, when other graphene materials are employed, additional preparation steps may be employed to process the graphene materials.
To significantly increase the overall thermal conductivity of the magnetic refrigeration module of the present application, in one embodiment, the graphene material of the film 11 may have a thermal conductivity of at least 1000W/m·k, preferably at least 1300W/m·k, more preferably at least 1500W/m·k, and particularly preferably at least 2000W/m·k. With the development of technology, it is conceivable that the magnetic refrigeration module of the present application can apply graphene materials having higher thermal conductivity.
Gadolinium metal is used as a conventional magnetocaloric material, usually in the form of granules or plates. In an embodiment of the application, gadolinium metal is used as the magnetocaloric material, wherein the gadolinium metal is in the form of nanoparticles, wherein the particle size of the nanoparticles may be less than 30nm, preferably less than 20nm, more preferably less than 10nm, such as 1nm, 3nm, 5nm, etc. In addition, gadolinium-based alloy, ni-Mn-Sn-based alloy or Mn-Fe-based alloy can be adopted as the magnetocaloric material of the application. It should be noted, however, that since structural phase transformation, magnetic phase transformation, or composition segregation, etc. may occur in the alloy during the formation of the nanoparticles, the process parameters need to be adjusted accordingly.
As shown in fig. 1B, the magnetic refrigeration module 10 of the present application is shown to include only one layer of film 11, however, in actual products, the magnetic refrigeration module 10 may include a configuration formed of multiple layers of film 11, such a configuration may be stacked of multiple individual films 11, for example, with the film 11 having a size comparable to that of the finally formed magnetic refrigeration module 10 selected, or may be wound from a single layer of film 11 into a solid or hollow cylindrical magnetic refrigeration module, or may be folded from a single layer of film 11 such that nanoparticles are located between adjacent two layers of film 11. By forming the multilayer structure, the film 11 can be made to act as an oxidation barrier layer, preventing oxidation of the nanoparticles, thereby making it possible to fully exert the properties of the nanoparticles and avoiding accidental ignition of the magnetocaloric material (for example, gadolinium metal has flammability). During formation of the multilayer film structure, a certain pressure may be applied to compact the formed stack or roll.
Referring to fig. 2, there is shown a magnetic refrigeration apparatus 100 according to an embodiment of the present application, the magnetic refrigeration apparatus 100 including a magnetic refrigeration module 10 as described above, and a magnet. In fig. 2, the N pole 20 and S pole 30 of the magnet are shown at each end of the magnetic refrigeration module 10. The magnet generates a magnetic field passing through the magnetic refrigeration module 10 from the N pole 20 to the S pole 30 to generate a magnetocaloric effect within the magnetic refrigeration module 10. In addition, the magnetic refrigeration apparatus 100 further includes a heat sink 40, the heat sink 40 being capable of absorbing heat from the magnetic refrigeration module 10 and dissipating the heat to the external environment by conduction, convection or radiation. To reduce the thermal contact resistance between the heat sink 40 and the magnetic refrigeration module 10, a thermal interface material 60 may also be provided between the heat sink 40 and the magnetic refrigeration module 10. The thermal interface material 60 is a material commonly used in the art and will not be described in detail herein. Also shown in fig. 2 is a heat source 50, such as a heat-generating device or space that requires cooling, and another thermal interface material 70 may also be provided between the heat source 50 and the magnetic refrigeration module 10. The principle of operation of the magnetic refrigeration device 100 is known and will not be described in detail herein.
Having generally described the structure of the magnetic refrigeration module 10 and the magnetic refrigeration apparatus 100 of the present application, a method of manufacturing the magnetic refrigeration module 10 of the present application is described below with reference to fig. 3.
As shown in fig. 2, the preparation method of the magnetic refrigeration module of the present application generally includes the following steps:
at step S1, a film 11 comprising graphene material is provided. The film 11 may be formed by various methods such as mechanical peeling, redox, vapor deposition, and the like.
At step S2, the magnetocaloric material 15 is distributed on the surface of the film 11. The magnetocaloric material 15 is generally spread substantially uniformly in the form of ultrafine particles on the surface of the membrane 11. The particle size of the magnetocaloric material 15 may be in the order of micrometers, e.g. 2 μm, 4 μm, etc. Of course, sizes less than 1 μm may also be used.
At step S3, the magnetocaloric material 15 is heated to a molten state. The heating magnetocaloric material 15 may be laser heating, infrared heating, electric heating, or the like. To reduce heat loss and avoid adverse effects such as oxidation of the magnetocaloric material 15, the heating time should be as short as possible, for example, in the range of 1 to 10 milliseconds. Of course heating times of less than 1 millisecond, for example 900 microseconds, may also be used. The heating temperature should be above the melting point of the magnetocaloric material 15, but the temperature should be avoided from being too high, for example in the range 1700K to 2500K. It is conceivable that the heating temperature and the heating time may be calibrated according to the kind of the magnetocaloric material.
At step S4, the magnetocaloric material 15 and the film 11 are cooled, so that the magnetocaloric material 15 forms nanoparticles on the surface of the film 11. The cooling time to room temperature should also be as short as possible, and in view of the limitation of rapid cooling, the cooling time will generally be longer than the heating time, in the range of approximately 10 to 20 milliseconds. Of course, cooling times of less than 10 milliseconds may also be employed where the device is viable.
By such ultra-rapid heating, the magnetocaloric material 15 can be rapidly melted and dispersed on the entire surface of the film 11 at a high temperature. With rapid cooling, the magnetocaloric material 15 nucleates around the defects 13 on the surface of the film 11 and forms ultrafine nanoparticles. Preferably, during the formation of the nanoparticles, the defects 13 on the surface of the film 11 limit the movement of the nanoparticles so that the nanoparticles are distributed in the areas 12 separated by adjacent defects 13. Therefore, the defects 13 on the surface of the nanoparticle coating film 11 formed of the magnetocaloric material 15 are separated from each other without aggregation and merging.
The method for preparing the magnetic refrigeration module can be used for rapidly and conveniently manufacturing the magnetic refrigeration module with ultrahigh heat conductivity and heat exchange efficiency, and breaks through the bottleneck of the application of the existing magnetic heat material.
The application has been described in detail with reference to specific embodiments thereof. It will be apparent that the embodiments described above and shown in the drawings are to be understood as illustrative and not limiting of the application. It will be apparent to those skilled in the art that various modifications or variations can be made in the present application without departing from the spirit thereof, and that such modifications or variations do not depart from the scope of the application.
Claims (17)
1. A magnetic refrigeration module (10), comprising:
-a membrane (11) comprising graphene material; and
-a magnetocaloric material (15) forming nanoparticles attached on the surface of the membrane (11).
2. The magnetic refrigeration module (10) of claim 1, wherein nanoparticles formed from the magnetocaloric material (15) are separated from each other by defects (13) on the surface of the film (11).
3. The magnetic refrigeration module (10) of claim 1 or 2, wherein the graphene material is reduced graphene oxide.
4. The magnetic refrigeration module (10) of claim 1 or 2, wherein the graphene material has a thermal conductivity of at least 1000W/m-K.
5. The magnetic refrigeration module (10) of claim 4, wherein the graphene material has a thermal conductivity of at least 1300W/m-K.
6. The magnetic refrigeration module (10) of claim 5, wherein the graphene material has a thermal conductivity of at least 1500W/m-K.
7. The magnetic refrigeration module (10) of claim 6, wherein the graphene material has a thermal conductivity of at least 2000W/m-K.
8. The magnetic refrigeration module (10) of claim 1 or 2, wherein the magnetocaloric material (15) is gadolinium metal.
9. The magnetic refrigeration module (10) of claim 1 or 2, wherein the nanoparticles have a particle size of less than 30nm.
10. The magnetic refrigeration module (10) of claim 9, wherein the nanoparticle has a particle size of less than 20nm.
11. The magnetic refrigeration module (10) of claim 10, wherein the nanoparticle has a particle size of less than 10nm.
12. The magnetic refrigeration module (10) of claim 1 or 2, wherein the magnetic refrigeration module (10) comprises a construction formed of multiple layers of films (11), the construction being stacked of multiple individual films (11) or being rolled or folded from a single layer of films (11) such that the nanoparticles are located between adjacent two layers of films (11).
13. A magnetic refrigeration device (100), comprising:
the magnetic refrigeration module (10) of any of claims 1 to 12; and
a magnet configured to provide a magnetic field for the magnetic refrigeration module (10).
14. The magnetic refrigeration apparatus (100) of claim 13, wherein the magnetic refrigeration apparatus (100) further comprises a heat sink (40) capable of absorbing heat from the magnetic refrigeration module (10).
15. The magnetic refrigeration apparatus (100) of claim 13 or 14, wherein the magnetic refrigeration apparatus (100) further comprises a thermal interface material (60) disposed between the heat sink (40) and the magnetic refrigeration module (10).
16. A method of preparing a magnetic refrigeration module (10), the method comprising the steps of:
providing a membrane (11), the membrane comprising a graphene material;
-distributing a magnetocaloric material (15) on the surface of the membrane (11);
heating the magnetocaloric material (15) to a molten state; and
-cooling the magnetocaloric material (15) and the membrane (11) such that the magnetocaloric material (15) forms nanoparticles on the surface of the membrane (11).
17. A method as claimed in claim 16, wherein the nanoparticles formed from the magnetocaloric material (15) are separated from each other by defects (13) on the surface of the film (11).
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2019/077126 WO2020177093A1 (en) | 2019-03-06 | 2019-03-06 | Magnetic refrigeration module and preparation method therefor |
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| Publication Number | Publication Date |
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| CN113631511A CN113631511A (en) | 2021-11-09 |
| CN113631511B true CN113631511B (en) | 2023-11-24 |
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| CN201980093584.2A Active CN113631511B (en) | 2019-03-06 | 2019-03-06 | Magnetic refrigeration module and preparation method thereof |
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| KR (1) | KR20210136013A (en) |
| CN (1) | CN113631511B (en) |
| DE (1) | DE112019006977T5 (en) |
| WO (1) | WO2020177093A1 (en) |
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| US20120019342A1 (en) * | 2010-07-21 | 2012-01-26 | Alexander Gabay | Magnets made from nanoflake precursors |
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| CN206003836U (en) * | 2016-08-31 | 2017-03-08 | 鸿之微科技（上海）有限公司 | Magneto-thermoelectric device |
| CN206695450U (en) * | 2017-03-14 | 2017-12-01 | 华南理工大学 | A kind of infinitesimal heat regenerative system in parallel for room temperature magnetic refrigerating |
| CN109099616A (en) * | 2018-08-09 | 2018-12-28 | 宁夏欣达节能技术有限公司 | Graphene film type refrigerant evaporation tube and its device |
-
2019
- 2019-03-06 DE DE112019006977.2T patent/DE112019006977T5/en active Pending
- 2019-03-06 CN CN201980093584.2A patent/CN113631511B/en active Active
- 2019-03-06 KR KR1020217028361A patent/KR20210136013A/en not_active Application Discontinuation
- 2019-03-06 WO PCT/CN2019/077126 patent/WO2020177093A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389536A (en) * | 2002-07-15 | 2003-01-08 | 南京大学 | Composite room temperature magnetic refrigerating material and its prepn. |
| CN103801686A (en) * | 2013-12-31 | 2014-05-21 | 深圳市国创新能源研究院 | Graphene nanocomposite and preparation method thereof |
| CN103938012A (en) * | 2014-04-23 | 2014-07-23 | 中国科学院理化技术研究所 | Carbon-based room-temperature magnetic refrigeration composite and preparation method thereof |
| CN106554006A (en) * | 2015-09-25 | 2017-04-05 | 国家纳米科学中心 | A kind of material with carbon element, preparation method and applications |
| WO2018090329A1 (en) * | 2016-11-18 | 2018-05-24 | 深圳先进技术研究院 | Functionalized flexible electrode and fabrication method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112019006977T5 (en) | 2021-11-25 |
| CN113631511A (en) | 2021-11-09 |
| WO2020177093A1 (en) | 2020-09-10 |
| KR20210136013A (en) | 2021-11-16 |
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