Thermoelectric material, manufactering method for thermoelectric material, refrigerator including thermoelectric material

Abstract

A refrigerator according to one embodiment of the present disclosure may include a storage compartment, a main body including the storage compartment, and a cold air supply device configured to supply cold air to the storage compartment and including a thermoelectric module. The thermoelectric module may include a lower substrate, a lower conductive pattern layer disposed on the lower substrate, a plurality of thermoelectric elements disposed on the lower conductive pattern layer, an upper conductive pattern layer disposed on the thermoelectric elements, and an upper substrate formed on the upper conductive pattern layer. The thermoelectric elements may include bismuth, telluride, selenium, and copper iodide, and the crystal grain size may be 5 to 30 μm.

Description

Technology Field

[0001] Various embodiments of the present disclosure relate to a thermoelectric material, a method for manufacturing a thermoelectric material, and a refrigerator comprising a thermoelectric material. Background Technology

[0002] A refrigerator is a home appliance that prevents food spoilage or deterioration and keeps food fresh by cooling or storing food in the storage compartment at a low temperature. The storage compartment includes a refrigerator compartment maintained at approximately 0 to 5 degrees Celsius for refrigerated storage of food, and a freezer compartment maintained at approximately 0 to minus 30 degrees Celsius for frozen storage of food. A door is provided on the front of the main body to open and close the storage compartment. The door is rotatably provided on the front of the main body to open and close the storage compartment. Additionally, the door is provided as a drawer-type door to open and close the storage compartment.

[0003] Meanwhile, a refrigerator may include a storage compartment capable of holding food and a cold air supply device for cooling the storage compartment. By using the cold air supply device to freeze or refrigerate the storage compartment, the refrigerator can keep food stored in the compartment fresh for a long period. Generally, depending on the method of generating cold air, the cold air supply device can be classified into a refrigeration cycle device that uses a refrigeration cycle and a Peltier cooling device that uses a Peltier element.

[0004] For example, a refrigeration cycle device can obtain cold air by circulating refrigerant along a closed circuit consisting of a compressor, a condenser, an expander, and an evaporator.

[0005] For example, a Peltier cooling device can obtain cold air by using a thermoelectric element that generates the Peltier effect. Here, the Peltier effect refers to a phenomenon in which, when a potential difference is applied to both sides of an object, heat flows along with the current, causing one side to be heated and the other side to be cooled.

[0006] The information described above may be provided as related art for the purpose of aiding understanding of the present disclosure. No claim or determination is made as to whether any of the foregoing may be applied as prior art related to the present disclosure. means of solving the problem

[0007] A thermoelectric material according to one embodiment of the present disclosure comprises bismuth (Bi), telluride (Te), selenium (Se), and copper iodide (CuI), and the grain size may be 5 to 30 μm.

[0008] A method for manufacturing a thermoelectric material according to one embodiment of the present disclosure may include a process of forming a thermoelectric material using a powder made using bismuth (Bi), telluride (Te), selenium (Se), and copper iodide (CuI), and a process of heat-treating the thermoelectric material at 400 to 550 degrees Celsius.

[0009] A refrigerator according to one embodiment of the present disclosure may include a storage compartment, a main body including the storage compartment, and a cold air supply device configured to supply cold air to the storage compartment and including a thermoelectric module. The thermoelectric module may include a lower substrate, a lower conductive pattern layer disposed on the lower substrate, a plurality of thermoelectric elements disposed on the lower conductive pattern layer, an upper conductive pattern layer disposed on the thermoelectric elements, and an upper substrate formed on the upper conductive pattern layer. The thermoelectric elements may include bismuth, telluride, selenium, and copper iodide, and the crystal grain size may be 5 to 30 μm.

[0010] The effects obtainable from the exemplary embodiments of the present disclosure are not limited to those mentioned above, and other unmentioned effects can be clearly derived and understood by those skilled in the art to which the exemplary embodiments of the present disclosure belong from the description below. That is, unintended effects resulting from the implementation of the exemplary embodiments of the present disclosure can also be derived by those skilled in the art from the exemplary embodiments of the present disclosure. Brief explanation of the drawing

[0011] FIG. 1 is a drawing illustrating the schematic internal and external appearance of a refrigerator according to one embodiment of the present disclosure. FIG. 2 is a functional block diagram schematically illustrating the configuration of a refrigerator according to one embodiment of the present disclosure in terms of function and control. FIG. 3 is a perspective view of a thermoelectric module according to one embodiment. FIG. 4 is a side cross-sectional view of a thermoelectric module according to one embodiment. FIG. 5 is a diagram illustrating the structure of a refrigerator including a thermoelectric module according to one embodiment. FIG. 6 is an exemplary drawing for explaining the process of heat exchange using a thermoelectric module according to one embodiment. FIG. 7 is a flowchart illustrating a method for manufacturing a thermoelectric module according to one embodiment. FIG. 8 is an experimental example in which the amount of change in performance of a thermoelectric material according to the heat treatment temperature according to one embodiment is measured. FIG. 9 is an experimental example in which the change in performance of a thermoelectric material according to a heat treatment temperature and heat treatment time was measured according to one embodiment. FIG. 10 is an experimental example in which the size of crystal grains was measured according to the heat treatment temperature according to one embodiment. FIG. 11 is a diagram showing a portion of a thermoelectric material according to one embodiment observed with an electron microscope. In the following description, the attached drawings are referenced, and specific examples of implementation are illustrated within the drawings. Additionally, other examples may be used and structural modifications may be made without departing from the scope of the various examples. Specific details for implementing the invention

[0012] The various embodiments used to illustrate the principles of the present disclosure in FIGS. 1 through 11 disclosed below and in this patent document are for illustrative purposes only and should not be construed as limiting the scope of the present disclosure in any way. Those skilled in the art will understand that the principles of the present disclosure may be implemented in any system or device appropriately arranged.

[0013] The various embodiments of the present disclosure and the terms used therein are not intended to limit the technical features described in the present disclosure to specific embodiments, and should be understood to include various modifications, equivalents, or substitutions of said embodiments.

[0014] In relation to the description of the drawings, similar reference numerals may be used for similar or related components.

[0015] The singular form of the noun corresponding to the item may include one or multiple items, unless the relevant context clearly indicates otherwise.

[0016] In the present disclosure, each of the phrases such as “A or B”, “at least one of A and B”, “at least one of A or B”, “A, B or C”, “at least one of A, B and C”, and “at least one of A, B, or C” may include any one of the items listed together in the corresponding phrase, or all possible combinations thereof.

[0017] The term “and / or” includes a combination of multiple related described components or any of the multiple related described components.

[0018] Terms such as "first," "second," or "first" or "second" may be used simply to distinguish a component from another component and do not limit the components in other aspects (e.g., importance or order).

[0019] Additionally, terms such as 'front,' 'rear,' 'top,' 'bottom,' 'side,' 'left,' 'right,' 'top,' and 'bottom' used in this disclosure are defined based on the drawings, and the shape and location of each component are not limited by these terms.

[0020] Terms such as “include” or “have” are intended to specify the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in this disclosure, and do not preclude the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0021] When it is said that a component is "connected," "combined," "supported," or "in contact" with another component, this includes not only cases where the components are directly connected, combined, supported, or in contact, but also cases where they are indirectly connected, combined, supported, or in contact through a third component.

[0022] When it is said that a component is located "on" another component, this includes not only cases where one component is in contact with the other, but also cases where another component exists between the two components.

[0023] A refrigerator according to one embodiment may include a main body.

[0024] The “main body” may include an inner body, an outer body positioned on the outside of the inner body, and an insulating material provided between the inner body and the outer body.

[0025] The “inner body” may include at least one of a case, plate, panel, or liner forming a storage chamber. The inner body may be formed as a single body or may be formed by assembling multiple plates. The “outer body” may form the exterior of the main body and may be coupled to the outer side of the inner body so that an insulating material is disposed between the inner body and the outer body.

[0026] The “insulating material” can insulate the interior and exterior of the storage room so that the temperature inside the storage room is maintained at a set appropriate temperature without being affected by the external environment. According to one embodiment, the insulating material may include a foamed insulating material. The foamed insulating material can be formed by injecting and foaming urethane foam, which is a mixture of polyurethane and a foaming agent, between the inner and outer layers.

[0027] According to one embodiment, the insulation material may additionally include a vacuum insulation material in addition to a foam insulation material, or the insulation material may consist solely of a vacuum insulation material instead of a foam insulation material. The vacuum insulation material may include a core material and an outer shell material that accommodates the core material and seals the interior under vacuum or near-vacuum pressure. However, the insulation material is not limited to the foam insulation material or vacuum insulation material described above and may include various materials that can be used for insulation.

[0028] The "storage room" may include a space defined by an internal structure. The storage room may further include an internal structure defining a space corresponding to the storage room. Various items such as food, medicine, and cosmetics may be stored in the storage room, and the storage room may be formed so that at least one side is open to allow for the retrieval and retrieval of items.

[0029] A refrigerator may include one or more storage compartments. When two or more storage compartments are formed in a refrigerator, each storage compartment may have a different use and may be maintained at a different temperature. To this end, each storage compartment may be partitioned from one another by a partition containing insulation.

[0030] The storage room may be provided to be maintained within an appropriate temperature range according to its intended use and may include a "refrigeration room," "freezing room," or "variable temperature room" distinguished according to its intended use and / or temperature range. The refrigerator room may be maintained at a temperature suitable for refrigerated storage of goods, and the freezer room may be maintained at a temperature suitable for frozen storage of goods. "Refrigeration" may mean cooling goods to a temperature that does not freeze them; for example, the refrigerator room may be maintained within a range of 0°C to 7°C. "Freezing" may mean cooling goods to freeze them or to maintain them in a frozen state; for example, the freezer room may be maintained within a range of -20°C to -1°C. The variable temperature room may be used as either a refrigerator room or a freezer room, with or without the user's choice.

[0031] Storage rooms may be referred to by various names, such as "vegetable room," "fresh room," "cooling room," and "ice-making room," in addition to terms like "refrigeration room," "freezing room," and "variable temperature room." The terms "refrigeration room," "freezing room," and "variable temperature room" used below should be understood as encompassing storage rooms with corresponding uses and temperature ranges.

[0032] According to one embodiment, the refrigerator may include at least one door configured to open and close one side of the storage compartment. The door may be provided to open and close each of one or more storage compartments, or a single door may be provided to open and close multiple storage compartments. The door may be installed to be rotatable or sliding on the front of the main body.

[0033] The “door” may be configured to seal the storage room when the door is closed. The door may include insulation material, similar to the main body, to insulate the storage room when the door is closed.

[0034] According to one embodiment, the door may include a door outer panel forming the front of the door, a door inner panel forming the rear of the door and facing the storage room, an upper cap, a lower cap, and a door insulation material provided inside the same.

[0035] A gasket may be provided on the edge of the door inner panel to seal the storage compartment by adhering to the front of the main body when the door is closed. The door inner panel may include a dyke that protrudes rearward to allow a door basket for storing items to be mounted.

[0036] According to one embodiment, the door may include a door body and a front panel detachably coupled to the front side of the door body and forming the front of the door. The door body may include a door outer panel forming the front of the door body, a door inner panel forming the rear of the door body and facing the storage compartment, an upper cap, a lower cap, and a door insulation material provided inside them.

[0037] Refrigerators can be classified into French Door Type, Side-by-side Type, BMF (Bottom Mounted Freezer), TMF (Top Mounted Freezer), or 1-door refrigerators depending on the arrangement of the door and storage compartment.

[0038] According to one embodiment, the refrigerator may include a cold air supply device arranged to supply cold air to the storage compartment.

[0039] The “cold air supply device” may include a machine, apparatus, electronic device, and / or a system combining these that can generate cold air and guide cold air to cool a storage room.

[0040] According to one embodiment, a cold supply device can generate cold air through a refrigeration cycle that includes the processes of compression, condensation, expansion, and evaporation of a refrigerant. To this end, the cold supply device may include a refrigeration cycle device having a compressor, a condenser, an expansion device, and an evaporator capable of driving the refrigeration cycle. According to one embodiment, the cold supply device may include a semiconductor such as a thermoelectric element. The thermoelectric element can cool a storage chamber through heat generation and cooling action via the Peltier effect.

[0041] According to one embodiment, the refrigerator may include a machine room arranged to accommodate at least some parts belonging to a cold air supply device.

[0042] The “machine room” may be configured to be partitioned and insulated from the storage room to prevent heat generated from components placed in the machine room from being transferred to the storage room. The interior of the machine room may be configured to communicate with the exterior of the main body to dissipate heat from components placed inside the machine room.

[0043] According to one embodiment, the refrigerator may include a dispenser provided on the door to provide water and / or ice. The dispenser may be provided on the door so that it is accessible to a user without opening the door.

[0044] According to one embodiment, the refrigerator may include an ice-making device configured to generate ice. The ice-making device may include an ice-making tray that stores water, an ice-removing device that separates ice from the ice-making tray, and an ice bucket that stores the ice generated from the ice-making tray.

[0045] According to one embodiment, the refrigerator may include a control unit for controlling the refrigerator.

[0046] The “control unit” may include a memory that stores or remembers a program and / or data for controlling a refrigerator, and a processor that outputs a control signal for controlling a cold air supply device, etc., according to the program and / or data stored in the memory.

[0047] The memory stores or records various information, data, commands, programs, etc., necessary for the operation of the refrigerator. The memory can store temporary data generated while generating control signals to control the components included in the refrigerator. The memory may include at least one of volatile memory or non-volatile memory, or a combination thereof.

[0048] The processor controls the overall operation of the refrigerator. The processor can control the components of the refrigerator by executing programs stored in memory. The processor may include a separate NPU that performs the operation of an artificial intelligence model. Additionally, the processor may include a central processing unit, a graphics processing unit (GPU), etc. The processor can generate control signals to control the operation of the cold air supply unit. For example, the processor can receive temperature information of the storage compartment from a temperature sensor and generate a cooling control signal to control the operation of the cold air supply unit based on the temperature information of the storage compartment.

[0049] Additionally, the processor can process user input of the user interface and control the operation of the user interface according to programs and / or data stored in memory. The user interface may be provided using an input interface and an output interface. The processor can receive user input from the user interface. Additionally, the processor can transmit display control signals and image data to the user interface to display an image on the user interface in response to the user input.

[0050] The processor and memory may be provided as a single unit or separately. The processor may include one or more processors. For example, the processor may include a main processor and at least one sub-processor. The memory may include one or more memory units.

[0051] According to one embodiment, the refrigerator may include a processor and memory that control all components included in the refrigerator, and may include a plurality of processors and a plurality of memories that individually control the components of the refrigerator. For example, the refrigerator may include a processor and memory that control the operation of a cold air supply device according to the output of a temperature sensor. Additionally, the refrigerator may separately provide a processor and memory that control the operation of a user interface according to user input.

[0052] The communication module can communicate with external devices, such as servers, mobile devices, and other home appliances, through nearby Access Points (APs). The Access Point (AP) can connect the Local Area Network (LAN) to which the refrigerator or user device is connected to the Wide Area Network (WAN) to which the server is connected. The refrigerator or user device can be connected to the server through the Wide Area Network (WAN).

[0053] The input interface may include keys, touchscreens, microphones, etc. The input interface may receive user input and transmit it to the processor.

[0054] The output interface may include a display, a speaker, etc. The output interface can output various notifications, messages, information, etc. generated by the processor.

[0055] FIG. 1 is a drawing illustrating the schematic internal and external appearance of a refrigerator according to one embodiment of the present disclosure.

[0056] All features, components, and / or arrangement relationships between components illustrated in FIG. 1 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in other figures of this specification. Likewise, all features, components, and / or arrangement relationships between components described in relation to FIG. 2 through 11 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in FIG. 1.

[0057] Referring to FIG. 1, a refrigerator (1) according to one embodiment may include a main body (10). The main body (10) may include an outer body (11) and an inner body (12) disposed inside the outer body (11). The outer body (11) may be provided to form at least a portion of the outer appearance of the main body (10). In one example, the outer body (11) may be configured to include a metal material with excellent durability and aesthetic appeal. The inner body (12) may be provided to define the space of the storage room (20). The inner body (12) may include a case, plate, panel and / or liner forming the storage room (20). The inner body (12) may be formed as a single body or may be formed by assembling a plurality of plates. In one example, the inner body (12) may be integrally injection molded using a plastic material, but the present document is not limited thereto.

[0058] According to one embodiment, a receiving space may be formed between the outer (11) and the inner (12). Insulating material for insulating the storage room (20) may be provided in at least a portion of the receiving space. The insulating material may insulate the inside of the storage room (20) and the outside of the storage room (20) so that the temperature inside the storage room (20) can be maintained at a set appropriate temperature without being affected by the external environment of the storage room (20).

[0059] According to one embodiment, the insulation material may include a foamed insulation material. In one example, after fixing the inner layer (12) and the outer layer (11) with a jig or the like, the foamed insulation material may be formed by injecting and foaming a urethane foam mixed with polyurethane and a foaming agent into the receiving space between the inner layer (12) and the outer layer (11). According to one example, the insulation material may include a vacuum insulation material in addition to the foamed insulation material or in place of the foamed insulation material. The vacuum insulation material may include a core material and an outer shell material that accommodates the core material and seals the interior to a vacuum or near-vacuum pressure. The vacuum insulation material may further include an adsorbent that adsorbs gas and moisture to stably maintain a vacuum state. The insulation material of the refrigerator (1) is not limited to the foamed insulation material or vacuum insulation material described above, but may be constructed using various materials that can be used for insulation.

[0060] According to one embodiment, the refrigerator (1) may include a storage room (20). The storage room (20) may store food. The food includes edible or drinkable food items, specifically, meat, fish, seafood, fruit, vegetables, water, ice, beverages, kimchi, or alcoholic beverages such as wine. In addition to food, medicines or cosmetics may be stored in the storage room (20), and there are no limitations on the items that can be stored in the storage room (20).

[0061] According to one embodiment, the refrigerator (1) may include one or more storage compartments (20). When two or more storage compartments (20) are formed in the refrigerator (1), each storage compartment may have a different use and may be maintained at a different temperature. To this end, each storage compartment (20) may be partitioned from one another by a partition (14) containing an insulating material. In one example, the storage compartments may be referred to as a "refrigeration compartment," a "freezing compartment," or a "variable temperature compartment," respectively, depending on their use and / or temperature range. "Refrigeration" may mean cooling food to a temperature that does not freeze, and for example, the refrigerator compartment may be maintained within a range of 0 degrees Celsius to 7 degrees Celsius. "Freezing" may mean cooling food to freeze or to maintain it in a frozen state, and for example, the freezer compartment may be maintained within a range of -20 degrees Celsius to -1 degree Celsius. A variable temperature room may refer to a storage room that can be maintained at a predetermined variable temperature, either by the user's choice or independently. According to one example, a storage room may be configured such that part of it is used as a refrigerator room and the remaining part is used as a freezer room. In addition to the aforementioned names such as "refrigerator room," "freezer room," and "variable temperature room," the storage room may be referred to by various other names such as "vegetable room," "fresh room," "cooling room," and "ice-making room."

[0062] According to one embodiment, the number, size, and / or shape of the storage room (20) may vary depending on the shape or location of the partition wall (14). According to one example, the partition wall (14) may be formed integrally with the main body (10). According to one example, the partition wall (14) may be a separate partition provided separately from the main body (10) and assembled to the main body (10).

[0063] According to one embodiment, the storage room (20) may be divided into left and right sections by a vertical partition (14v) (a partition extending in the vertical direction). Depending on the position of the vertical partition (14v), the size of the storage room (20) divided into left and right sections may vary. For example, the vertical partition (14v) may be provided in the center so that the storage room (20) divided into left and right sections is arranged in a mirror-symmetric manner. According to one example, there may be multiple vertical partitions. If there are multiple vertical partitions, the storage room may be divided into three or more sections along the left and right directions.

[0064] According to one embodiment, the storage room (20) may be divided vertically by a horizontal partition (14h) (a partition extending in the horizontal direction). Depending on the position of the horizontal partition (14h), the size of the vertically divided storage room (20) may vary. According to one example, there may be multiple horizontal partitions. If there are multiple horizontal partitions, the storage room may be divided into three or more sections along the vertical direction.

[0065] According to one embodiment, the refrigerator may be configured to include a plurality of storage compartments having various sizes and shapes depending on various combinations of vertical and horizontal partitions.

[0066] According to one embodiment, a plurality of shelves (24) and / or a plurality of storage containers (25) may be provided inside the storage room (20). Each of the plurality of shelves (24) and the plurality of storage containers (25) may be separable from the interior space of the storage room (20).

[0067] According to one embodiment, each storage room (20) may be formed so that at least one side is open for storing food. According to one example, the refrigerator (1) may include a door (30) for opening and closing each storage room (20). In one example, the door (30) may be positioned at the front of the main body (10) and the storage room (20) to open and close the storage room (20). The door (30) may be configured to seal the storage room (20) while the door is closed. The door (30) may include an insulating material, similar to the main body (10), to insulate the storage room (20) from the external environment while the door (30) is closed.

[0068] According to one embodiment, the door (30) may be configured to open and close by rotating around a hinge (16), but the present disclosure is not limited thereto. In one example, the door may be configured to open and close in a sliding manner.

[0069] According to one embodiment, the door (30) may include a door panel (30a) and / or a door body (30b). The door panel (30a) and the door body (30b) may be joined so as to be separable. The door body (30b) may, for example, have one side fixed to the main body (10) by a hinge (16). The door panel (30a) may form part of the front exterior appearance of the refrigerator (1). Thus, the door panel (30a) may be an important aesthetic element when the refrigerator (1) is placed indoors. The door panel (30a) may be configured to be replaceable and have various colors and / or various designs so that the user can decorate the front exterior appearance of the refrigerator (1) according to their taste. According to one example, the door panel (30a) and the door body (30b) may be formed as a single unit.

[0070] According to one embodiment, the door (30) may include a door handle (not shown), a door shelf (313), a shelf support (314), and / or a gasket (315). A user may open and close the door (30) using the door handle. The door handle may be formed as a recess on the bottom or top surface of the door (30) or as a protrusion on the front surface of the door (30), and is not limited to a specific shape.

[0071] According to one embodiment, the door shelf (313) may be provided to store food. On both the left and right sides of the door shelf (313), shelf support members (314) may be provided to support the door shelf (313). The shelf support members (314) may be formed to extend vertically from the door (30), for example. For example, the shelf support members (314) may be provided to extend vertically and protrude from the back surface (inner surface facing the storage room (20)) of the door (30) toward the storage room (20). The shelf support members (314) may be provided as a separate component that is detachable from the door (30), or alternatively, may be formed integrally with the door (30).

[0072] According to one embodiment, the gasket (315) may be provided to wrap around the edge of the door body (30b). The gasket (315) may be provided to seal the gap between the main body (10) and the door (30) when the door (30) is closed.

[0073] According to one embodiment, the refrigerator (1) may include a cooling device. The cooling device may include a machine, apparatus, electronic device, and / or a system combining these, capable of generating cold air and guiding the generated cold air to the storage room to cool the storage room. Multiple cooling devices may be provided, and different types of cooling devices may be included. In one example, the cooling device may include at least some of a compressor or a Peltier. For example, the refrigerator (1) may include only a compressor, only a Peltier, or a compressor and a Peltier together in a hybrid form.

[0074] In one example, a cooling device may be provided inside the main body (10) to supply cold air to each storage room (20), for example.

[0075] FIG. 2 is a functional block diagram schematically illustrating the configuration of a refrigerator according to one embodiment of the present disclosure in terms of function and control.

[0076] All features, components, and / or arrangement relationships between components illustrated in FIG. 2 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in other figures of this specification. Likewise, all features, components, and / or arrangement relationships between components described in relation to FIG. 1 and FIG. 3 through 11 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in FIG. 2.

[0077] Referring to FIG. 2, a refrigerator (1) according to one embodiment may include at least one input / output device (40), at least one communication device (50), at least one sensor device (60), at least one cooling device (70), at least one display (80), at least one processor (100), and / or at least one memory (101).

[0078] According to one embodiment, the input / output device (40) may include any type of user input means for obtaining setting information from a user for controlling the operation of the refrigerator (1). Various user inputs obtained through the input / output device (40) may be transmitted to a processor (100) described later. In one example, various user inputs obtained through the input / output device (40) may be transmitted externally through a communication device (50) described later, and this document is not limited thereto.

[0079] According to one embodiment, the input device of the input / output device (40) may be installed on a door (e.g., the door (30) of FIG. 1) for the convenience of the user. The input device may include any type of user input means including one or more buttons or switches. Setting data by the user (e.g., desired storage room temperature, etc.) may be input through the input device. For example, the input device may include a touch panel that receives the user's touch input and generates an electrical signal corresponding to the received touch input, and the present document is not limited to a specific type of input unit. In one example, the touch panel constituting the input device may be formed of a transparent material that does not distort the image displayed on the display panel, located on the front of a separate display panel provided in the refrigerator (1). In one example, the input device may include an infrared signal receiver. The user may input setting data remotely via a remote control, and the input setting data may be received by the input device as an infrared signal. In one example, the input device may include a microphone, and setting data by the user's voice may be obtained through the microphone.

[0080] According to one embodiment, setting data (e.g., desired storage room temperature, etc.) obtained through an input device may be transmitted to a processor (100) described below. In one example, the setting data obtained through the input device may be transmitted externally through a communication device (50) described below, and this document is not limited thereto.

[0081] According to one embodiment, the refrigerator (1) may include a communication device (50) that supports the transmission and reception of signals with the outside. In one example, the communication device (50) includes a communication circuit and can receive and / or transmit wired / wireless signals between an external wired / wireless communication system, an external server, and / or other devices according to a predetermined wired / wireless communication protocol. In one example, the communication device (50) may include one or more modules that connect the refrigerator (1) to one or more networks. In one example, the communication device (50) may include at least one of a mobile communication module, a wired / wireless internet module, a short-range communication module, and / or a location information module.

[0082] According to one embodiment, a mobile communication module may transmit and receive wireless signals with at least one of an external base station, an external terminal, and an external server through a mobile communication network according to any of the various communication protocols for mobile communication. The wireless signals may include data signals of various forms. In one example, the wireless signals may include voice call signals, video call call signals, and text / multimedia message signals, but the present document is not limited thereto.

[0083] According to one embodiment, the wired / wireless internet module may support, for example, WLAN (wireless LAN), Wi-Fi (wireless-fidelity), Wi-Fi Direct, DLNA (digital living network alliance), WiBro (wireless broadband), WiMAX (world interoperability for microwave access), HSDPA (high speed downlink packet access), HSUPA (high speed uplink packet access), LTE (long term evolution), or LTE-A (long term evolution-advanced), but is not limited thereto. In one example, the wired / wireless internet module of the communication device (50) may transmit and receive data according to at least one wired / wireless internet technology among the internet technologies not listed above.

[0084] According to one embodiment, the short-range communication module may support short-range communication using at least one of the following technologies, for example, Bluetooth, RFID (radio frequency identification), infrared data association (IrDA), UWB (ultra-wide band), ZigBee, NFC (near field communication), Wi-Fi, Wi-Fi Direct, and Wireless USB (universal serial bus). The short-range communication module may support wireless communication between the refrigerator (1) and a wireless communication system, between the refrigerator (1) and another device, or between the refrigerator (1) and a network where another device is located, for example, through a short-range wireless communication network.

[0085] According to one embodiment, the location information module may be a GPS (global positioning system) module or a Wi-Fi module, for example, as a module for obtaining the location of the refrigerator (1). If the refrigerator (1) utilizes a GPS module, it can receive information regarding the location of the refrigerator (1) by using signals sent from GPS satellites. If the refrigerator (1) utilizes a Wi-Fi module, it can receive information regarding the location of the refrigerator (1) based on information from a wireless access point (AP) that transmits and receives wireless signals to and from the Wi-Fi module.

[0086] According to one embodiment, the communication device (50) can receive a setting data signal input by a user from a user's mobile terminal in the form of a wireless signal according to a predetermined wireless communication protocol. In one example, the communication device (50) can receive information and / or commands for controlling the operation of the refrigerator (1) from an external server in the form of a signal according to a predetermined wired / wireless communication protocol. The communication device (50) can transmit the received various signals to a processor (100) described later. In one example, the communication device (50) can transmit various data generated or acquired on the refrigerator (1) in the form of a wired / wireless signal according to a predetermined wired / wireless communication protocol, for example, to a user's mobile terminal or an external server.

[0087] According to one embodiment, the refrigerator (1) may include a sensor device (60). In one example, the sensor device (60) may include a temperature sensor, a proximity sensor, a distance sensor and / or a camera. However, the types of sensors listed herein are merely exemplary and are not limited thereto.

[0088] According to one embodiment, the temperature sensor may include a plurality of temperature sensors that are provided inside each storage room (20) to detect the temperature inside the storage room (e.g., storage room (20) of FIG. 1). A plurality of temperature sensors may be installed in each of the plurality of storage rooms (20) to detect the temperature of each storage room (20). An electrical signal corresponding to the detected temperature may be transmitted to a processor (100). The processor (100) may control the operation or shutdown of a cooling device (70) to maintain the temperature of the storage room constant according to the received current temperature. Each of the plurality of temperature sensors may include a thermistor whose electrical resistance changes according to the temperature. In one example, the temperature sensor may include an external temperature sensor that is provided outside the refrigerator (1) (e.g., at a location on the outside (11) of FIG. 1) to detect the external temperature around the refrigerator (1).

[0089] According to one embodiment, the distance sensor can measure the distance to an object located around the refrigerator (1), for example, to a user. The distance sensor may be, for example, an ultrasonic sensor or an infrared sensor, but is not limited thereto. The distance sensor (62) can detect an object or user around the refrigerator (1) and transmit the detected electrical signal to the processor (100).

[0090] According to one embodiment, a proximity sensor may be provided to detect the opening and closing of the door (30). The proximity sensor (63) may detect whether the door (30) is in contact with the main body (e.g., the main body (10) of FIG. 1) and is closing the storage room (20). A plurality of proximity sensors (63) may be installed on each of the plurality of doors (30). The proximity sensor (63) may transmit an electrical signal regarding the detected opening and closing state of the door (30) to the processor (100).

[0091] According to one embodiment, a camera may be installed inside each storage room (20) to acquire an internal image of each storage room (20). In one example, the camera may be provided outside the refrigerator (1) (e.g., at a location on the outside (11) of FIG. 1) to acquire an external image of the refrigerator (1). The camera may include image sensors that capture an image and convert it into an electrical signal. The image sensors may include, for example, a charge-coupled device (CCD) image sensor or a complementary metal oxide semiconductor (CMOS) image sensor. The electrical signal regarding the image captured by the camera may be transmitted to a processor (100). The camera installed inside the storage room (20) may detect the opening and closing of the door. For example, the camera may be an infrared camera to detect a person's body temperature or the external temperature.

[0092] According to one embodiment, the refrigerator (1) may include a cooling device (70). In one example, the cooling device (70) may include a compressor (71) and / or a thermoelectric module (72). A plurality of cooling devices (70) may be included depending on the implementation mode of the main body (10). For example, a plurality of cooling devices (70) may be included depending on the implementation mode of the storage room (20) of the main body (10). For example, as many cooling devices (70) as there are storage rooms (20), the number of cooling devices (70) may be provided. Alternatively, different types of cooling devices may be included in the storage rooms (20). For example, the refrigerator (1) may include a compressor (71) and a thermoelectric module (72) together in a hybrid form.

[0093] The compressor (71) may include a compressor, a condenser, an expander, and an evaporator, and may include refrigerant pipes connecting them. The refrigerant may circulate between the compressor, the condenser, the expander, and the evaporator through the refrigerant pipes.

[0094] The compressor can compress the refrigerant to a high-temperature, high-pressure state. For example, the compressor can compress gaseous refrigerant to a high temperature, high pressure, by receiving electrical energy from an external source and utilizing rotational force such as that of an electric motor. The compressor is a variable-capacity compressor, and its capacity can be varied by changing the frequency according to drive control commands. The compressed refrigerant can be moved to the condenser via refrigerant pipes. The condenser can condense the compressed refrigerant received from the compressor. The condenser can dissipate the heat generated while condensing the refrigerant to the outside of the condenser. The refrigerant condensed while passing through the condenser can be moved to the expansion valve. The condensed refrigerant can be converted into a low-temperature, low-pressure liquid state while passing through the expansion valve. In one example, the expansion valve can be implemented as an electronic expansion valve capable of controlling the opening ratio (an electronic expansion valve capable of controlling the ratio of the cross-sectional area of ​​the valve's flow path in the partially open state to the cross-sectional area of ​​the valve's flow path in the fully open state). In such a case, the amount of refrigerant passing through the expansion valve can be controlled depending on the opening ratio of the electronic expansion valve. In one example, the expansion device can be implemented as a capillary device. Liquid refrigerant can pass through the expansion device and move to the evaporator. In the evaporator, heat exchange with the surrounding gas can take place as the liquid refrigerant evaporates. As the liquid refrigerant evaporates through the evaporator, it absorbs the latent heat of the surroundings, and as a result, the gas surrounding the evaporator is cooled, thereby generating cold air. The generated cold air can be moved to the storage room (20) through a flow path provided between the outer layer (e.g., outer layer (12) in FIG. 1) and the inner layer (e.g., inner layer (11) in FIG. 1). The refrigerant vaporized in the evaporator can be moved back to the compressor and circulated.

[0095] The thermoelectric module (72) includes a thermoelectric element, thereby enabling the storage room (20) to be cooled by heat generation and cooling action through the Peltier effect. In the thermoelectric element of the thermoelectric module (72), thermal energy is released / absorbed when electrons move due to the difference in energy levels between the metal and the PN semiconductor, thereby generating a cooling effect. For example, the thermoelectric module (72) has a P-type semiconductor and an N-type semiconductor located between the first surface and the second surface. When electrons move from metal A on the first surface to metal B on the second surface, where the energy level of the P-type semiconductor is low and the energy level of the P-type semiconductor is high, heat is released while losing energy. Metal B on the second plane has a high energy level, so it absorbs heat while gaining energy during electron transfer. Since the energy level of the N-type semiconductor of metal B is high, it absorbs heat while gaining heat when electrons move to metal A on the first plane. Since the energy level of N-type metal A is low, it loses energy and releases heat again when electrons move. In this way, the first plane becomes a heating state due to the operation, and the second plane becomes a cooling state due to the operation.

[0096] The thermoelectric module (72) may be manufactured in the form of a module including one or more individual Peltier elements, and one individual Peltier element may be composed of multiple semiconductor elements. The thermoelectric module (72) may include multiple Peltiers. A driving circuit for operating the thermoelectric module (72) may be equipped with a voltage source, and one or more Peltiers may be connected in series. By controlling the voltage source through a DC / DC converter, duty cycle, or frequency variation, the magnitude of the voltage and current applied to the Peltiers may be adjusted to enable heating or cooling functions.

[0097] According to one embodiment, the refrigerator (1) may include a machine room in which at least some parts of a cooling device (70) are placed. The machine room may be configured to be partitioned and insulated from the storage room (20) so as to prevent heat generated from the parts placed in the machine room from being transferred to the storage room (20). The interior of the machine room may be configured to communicate with the exterior of the main body (10) so as to dissipate heat from the parts placed inside the machine room.

[0098] According to one embodiment, the refrigerator (1) may include a display (80). In one example, the display (80) may be installed on the door (30). In one example, the display (80) may display various setting data (e.g., desired storage room temperature, etc.) obtained from a user or from the outside through an input / output device (40) and / or a communication device (50) or operation control information of the refrigerator (1). In one example, the display (80) may display various sensing information obtained from a sensor device (60) (e.g., one or more temperature information measured by a temperature sensor), the current operating status of the refrigerator (1), and / or various warning / error messages. For example, the display (80) may display a message regarding the performance degradation of the refrigerator (1) along with instructions for applying for service. The display (80) may be one of various visual display means capable of displaying images, characters, numbers, etc., including a liquid crystal display (LCD) panel, a light emitting diode (LED) panel, an organic light emitting diode (OLED) panel, a micro light emitting diode (uLED) panel, and a plasma display panel (PDP), and is not limited to a specific type of display part. In one example, the display (80) may include a speaker and may provide each of the aforementioned information in the form of voice through the speaker.

[0099] According to one embodiment, the refrigerator (1) may include a memory (101) for storing or remembering a program and / or data for controlling each component of the refrigerator (1), and a processor (100) for generating a control signal for controlling each component of the refrigerator (1) according to the program and / or data stored in the memory (101) and information obtained from each of the other components.

[0100] According to one embodiment, the processor (100) includes a processing circuit and can execute instructions (or instructions) included in a program (or application) stored in memory (101). The processor (110) may include, for example, a microcontroller unit (MCU), a central processing unit (CPU), a graphic processing unit (GPU), a neural processing unit (NPU), a tensor processing unit (TPU), a digital signal processor (DSP), an application-specific integrated circuit (ASIC), a field programmable gate array (FPGA), and / or a programmable logic device, but is not limited to any means capable of executing a program (or instructions or commands). The processor (100) includes a main processor and may include one or more sub-processors. In one embodiment, the MCU may serve as a sub-processor to drive the cooling device (70).

[0101] According to one embodiment, the memory (101) may include volatile memory and / or non-volatile memory, and may include, for example, a hard disk storage device, RAM, ROM, and / or flash memory, but is exemplary and not limited thereto.

[0102] According to one embodiment, the memory (101) includes one or more storage media and can store various data that can be used to control the operation of each component of the refrigerator (1). The memory (101) can store, for example, a number of applications used in the refrigerator (1), data for controlling the operation of the refrigerator (1), and commands. At least some of the applications stored in the memory (101) can be downloaded from an external server via wireless communication. At least some of the applications stored in the memory (101) may be stored in the memory (101) from the time of shipment for the basic functions of the refrigerator (1).

[0103] According to one embodiment, the memory (101) can store information regarding the occurrence of abnormal operation (failure) of a plurality of Peltier elements included in the thermoelectric module (72). The failure information regarding the plurality of Peltier elements can be stored and referenced in the form of an index. The memory (101) can store information regarding temperature control and operating time when the thermoelectric module (72) is in operation. The refrigerator (1) may include a plurality of thermoelectric modules (72), and information regarding each of the plurality of thermoelectric modules (72) can be stored separately in the memory (101).

[0104] According to one embodiment, the processor (100) may receive various input / setting information, such as desired storage room temperature information, from an input / output device (40) and / or a communication device (50). The processor (100) may obtain detection information from a sensor device (60), such as one or more temperature information detected by a temperature sensor, a detection signal detected by a distance sensor, door opening / closing information detected by a proximity sensor, and / or image information detected by a camera. In one example, the processor (100) may receive image information obtained from a camera and obtain information regarding the state inside or outside the storage room (20) of the refrigerator (1) by analyzing the received image information.

[0105] According to one embodiment, the processor (100) can generate operation control commands for each component of the refrigerator (1) based on various information received from an input / output device (40), a communication device (50), and / or a sensor device (60). In one example, the processor (100) can control the operation of a cooling device (70), such as a compressor (71) and / or a thermoelectric module (72), to control the temperature inside the storage room (20). In one example, the processor (100) can control the operation of each component of the cooling device (70) using information regarding the temperature of each storage room (20) received from a temperature sensor. For example, if the temperature inside the storage room (20) is higher than a preset temperature, the processor (100) can operate the compressor (71) of the cooling device (70) to lower the temperature of the storage room (20). When the proximity sensor of the sensor device (60) detects the opening or closing of the door, the thermoelectric module (72) can be operated to prevent a change in the temperature of the storage room (20).

[0106] In one example, the processor (100) may generate a command to control whether and how information is displayed through the display (80). In one example, the processor (100) may generate a command to control turning on the lighting of the open storage room (20) based on information regarding the opening of the door (30) from the proximity sensor. For example, the processor (100) may generate a command to control the operating status of each of the input / output device (40), the communication device (50), the sensor device (60), and / or the lighting device.

[0107] In the present disclosure, the processor (100) is disclosed as a single comprehensive component that controls all components included in the refrigerator (1), but the present document is not limited thereto. In one example, the refrigerator (1) may be configured to include a plurality of processor components that individually control some of the components of the refrigerator (1). In one example, the refrigerator (1) may separately include a processor and memory for controlling the operation of the cold air supply device (70) according to the output of the temperature sensor. In one example, the refrigerator (1) may separately include a processor and memory for controlling the operation of the user interface according to user input. The processor (100) may include a plurality of processors, and the memory (101) may include a plurality of memory devices.

[0108] A refrigerator (1) according to one embodiment comprises: a main body (10) including a receiving space; a cooling device (72) installed in the main body and supplying cold air to the receiving space (20); one or more temperature sensors (60) disposed in the main body; a memory (101); and a processor (100) for controlling the cooling device (72). The cooling device (72) comprises: a power source; a plurality of Peltier elements connected in series from the power source; a plurality of switching elements connected in parallel to each of the plurality of Peltier elements; and at least one sensor. The processor can operate the cooling device by applying power to the power source according to a temperature change detected by the one or more temperature sensors, and while the current supplied from the power source flows through the plurality of Peltier elements, in response to detecting an abnormal operation of the first Peltier element among the plurality of Peltier elements using the at least one sensor, the processor can control the first switching element connected in parallel to the first Peltier element so that the current flows excluding the first Peltier element.

[0109] According to one embodiment, the one or more sensors are a plurality of voltage sensing sensors corresponding to each of the plurality of Peltier elements, and the processor monitors whether the real-time sensing voltage for each of the plurality of Peltier elements falls within a predetermined normal range using the plurality of voltage sensing sensors while the cooling device is operating, and if the sensing voltage of the first Peltier element exceeds the normal range, the processor can identify a failure of the first Peltier element.

[0110] According to one embodiment, the processor can confirm that the cooling device is in a normal operating state by controlling the first switching element and then using the voltage sensing sensor to confirm that the voltage of the first Peltier element is below the normal range.

[0111] According to one embodiment, the first switching element may be arranged to be serially connected between the previous Peltier element of the first Peltier element and the next Peltier element of the first Peltier element according to the serial connection order of the plurality of Peltier elements, such that current flows in the on state.

[0112] According to one embodiment, the processor can allow current to be transferred from the previous Peltier element of the first Peltier element to the next Peltier element of the first Peltier element through the first switching element while the first switching element is in the on state.

[0113] According to one embodiment, while the sensing voltage of at least some of the plurality of Peltier elements is included in the normal range, at least some of the switching elements corresponding to at least some of the Peltier elements can maintain an off state in which no current flows.

[0114] According to one embodiment, the processor stores the occurrence of abnormal operation of the first Peltier element in the memory, and when the cooling device is restarted, the processor can control the first switching element connected in parallel with the first Peltier element by referring to the memory.

[0115] According to one embodiment, the one or more sensors are a plurality of current sensing sensors corresponding to each of the plurality of Peltier elements, and the processor monitors whether the real-time sensing current for each of the plurality of Peltier elements is within a normal range using the plurality of current sensing sensors while the cooling device is operating, and if the sensing current of the first Peltier element deviates from the normal range, the processor can identify a failure of the first Peltier element.

[0116] According to one embodiment, the cooling device includes one or more current cutoff switches disposed between the plurality of switches and the plurality of Peltier elements, and the processor can control the first switching element and the first current cutoff switch connected to the first Peltier element together in response to detecting abnormal operation of the first Peltier element.

[0117] According to one embodiment, the processor operates the cooling device by applying power to the power source according to a temperature change detected by one or more temperature sensors, monitors a first cooling time required until the temperature detected by one or more temperature sensors is included within a normal range, and can detect a failure of the refrigerator in response to determining that the first cooling time is greater than the expected time according to temperature control.

[0118] FIG. 3 is a perspective view of a thermoelectric module according to one embodiment.

[0119] FIG. 4 is a side cross-sectional view of a thermoelectric module according to one embodiment.

[0120] All features, components, and / or arrangement relationships between components illustrated in FIGS. 3 and 4 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in other figures of this specification. Likewise, all features, components, and / or arrangement relationships between components described in relation to FIGS. 1 and 2 and FIGS. 5 through 11 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in FIGS. 3 and 4.

[0121] Referring to FIGS. 3 and 4, a thermoelectric module (400) according to one embodiment (e.g., the thermoelectric module (72) of FIG. 2) may include at least one of a lower substrate (410), a lower conductive pattern layer (420), a plurality of thermoelectric elements (430), an upper conductive pattern layer (440), or an upper substrate (450). The lower conductive pattern layer (420) may be disposed on the lower substrate (410). A plurality of thermoelectric elements (430) may be disposed on the lower conductive pattern layer (420). The upper conductive pattern layer (440) may be disposed on the plurality of thermoelectric elements (430). The upper substrate (450) may be disposed on the upper conductive pattern layer (440). The thermoelectric module (400) may further include at least one Surface Mount Device (SMD) connector electrically connected to the lower conductive pattern layer (420).

[0122] According to one embodiment, the lower substrate (410) may be positioned to support the lower conductive pattern layer (420) and a plurality of thermoelectric elements (430). The lower substrate (410) may be at least one of the cooling surface and the heat dissipation surface of the thermoelectric module (400). For example, the lower substrate (410) may be a ceramic substrate comprising at least one of alumina, aluminum nitride (AlN), beryllia (BeO), and silicon nitride (Si3N4). For example, the lower substrate (410) may be a metal substrate comprising at least one of aluminum, copper, stainless steel, and nickel. However, the material of the lower plate (410) of the present disclosure is not limited thereto, and for example, the lower substrate (410) may be made of various materials including at least one of sapphire, silicon, silicon carbide (SiC), aluminum silicon carbide composite (AlSiC), and quartz.

[0123] According to one embodiment, the lower conductive pattern layer (420) may include at least one lower electrode pattern. The at least one lower electrode pattern may be electrically in contact with at least one thermoelectric element. For example, the at least one lower electrode pattern may be electrically in contact with at least one of an n-type thermoelectric element (430a) and a p-type thermoelectric element (430b).

[0124] According to one embodiment, a plurality of thermoelectric elements (430) may include n-type thermoelectric elements (430a) and p-type thermoelectric elements (430b). For example, the plurality of thermoelectric elements (430) may include n-type thermoelectric elements (430a) and p-type thermoelectric elements (430b) arranged alternately.

[0125] According to one embodiment, at least one of the n-type thermoelectric element (430a) and the p-type thermoelectric element (430b) may include a thermoelectric material (431). For example, the thermoelectric material (431) may include at least one of bismuth telluride (Bi2Te3), lead telluride (PbTe), silicon Germanium (SiGe), skutterudite, metal halide compounds, and hafnium hydride (HfH2), but is not limited thereto.

[0126] According to one embodiment, the upper conductive pattern layer (440) may include at least one upper electrode pattern. The at least one upper electrode pattern may be electrically in contact with at least one thermoelectric element. For example, the at least one upper electrode pattern may be electrically in contact with at least one of an n-type thermoelectric element (430a) and a p-type thermoelectric element (430b).

[0127] According to one embodiment, the upper substrate (450) may be positioned to support the upper conductive pattern layer (440). The upper substrate (450) may be at least one of the cooling surface and the heat dissipation surface of the thermoelectric module (400). For example, the upper substrate (450) may be a ceramic substrate comprising at least one of alumina (Al2O3), aluminum nitride (AlN), beryllia (BeO), and silicon nitride (Si3N4). For example, the upper substrate (450) may be a metal substrate comprising at least one of aluminum, copper, stainless steel, and nickel. However, the material of the upper substrate (450) of the present disclosure is not limited thereto, and for example, the upper substrate (450) may be implemented in various materials including at least one of sapphire, silicon, silicon carbide (SiC), aluminum silicon carbide composite (AlSiC), and quartz.

[0128] In one embodiment, when power is supplied to the thermoelectric module (400), power can be transferred to the thermoelectric module (400). For example, when power is supplied to the thermoelectric module (400), current can flow from the positive terminal to the n-type thermoelectric element (430a). For example, when power is supplied to the thermoelectric module (400), current can flow from the negative terminal to the p-type thermoelectric element (430b). For example, when a DC voltage is applied to the thermoelectric module (400) from an external power source, heat generation and heat absorption can occur at both ends of the plurality of thermoelectric elements (430).

[0129] According to one embodiment, a plurality of thermoelectric elements (430) may include at least one of an n-type thermoelectric element (430a) and a p-type thermoelectric element (430b). A plurality of thermoelectric elements (430) may include n-type thermoelectric elements (430a) and p-type thermoelectric elements (430b) arranged alternately.

[0130] According to one embodiment, the thermoelectric element (430) may include a thermoelectric material (431) and a multilayer diffusion prevention layer (432). The multilayer diffusion prevention layer (432) may be composed of at least three layers. Although the drawing describes the multilayer diffusion prevention layer (432) as being composed of four layers as an example, this is for convenience of explanation and the scope of the present disclosure is not limited to the number of diffusion prevention layers shown. According to one embodiment, the multilayer diffusion prevention layer may include at least one metal among Co, Ni, Cr, and W.

[0131] According to one embodiment, the thermoelectric material (431) may be composed of at least two of bismuth (Bi), tellurium (Te), cobalt (Co), samarium (Sb), indium (In), and cerium (Ce). Non-limiting examples include Bi-Te systems, Co-Sb systems, Pb-Te systems, Ge-Tb systems, Si-Ge systems, Sb-Te systems, Sm-Co systems, transition metal silicide systems, skuttrudite systems, silicide systems, Half-Whistler systems, or combinations thereof.

[0132] However, it is not limited thereto, and the thermoelectric material (431) may include at least one element selected from the group consisting of transition metals, rare earth elements, group 13 elements, group 14 elements, group 15 elements, and group 16 elements. Here, examples of rare earth elements include Y, Ce, La, etc., examples of transition metals may include one or more of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Ag, and Re, examples of group 13 elements may include one or more of B, Al, Ga, and In, examples of group 14 elements may include one or more of C, Si, Ge, Sn, and Pb, examples of group 15 elements may include one or more of P, As, Sb, and Bi, and examples of group 16 elements may include one or more of S, Se, and Te.

[0133] If the thickness of the thermoelectric material (431) is too thin and the distance between the heat dissipation section and the cooling section is too close, the region where a temperature difference occurs due to interference may be too small. On the other hand, if the thickness of the thermoelectric material (431) is too thick and the distance between the heat dissipation section and the cooling section is too far, the thermoelectric element region exhibiting a temperature distribution with a high thermoelectric performance index may be relatively small, and the efficiency may be lowered.

[0134] According to one embodiment, the multilayer diffusion prevention layer (432) may include a first diffusion prevention layer (432a), a second diffusion prevention layer (432b), a third diffusion prevention layer (432c), and a fourth diffusion prevention layer (432d). The first diffusion prevention layer (432a), the second diffusion prevention layer (432b), the third diffusion prevention layer (432c), and the fourth diffusion prevention layer (432d) may be sequentially stacked from a thermoelectric material (431).

[0135] According to one embodiment, the first diffusion prevention layer (432a) may be disposed on the upper and lower surfaces of the thermoelectric material (431). The first diffusion prevention layer (432a) may include at least one metal among Co, Ni, Cr, and W, but is not limited thereto and may further include a metal or metal alloy having a diffusion prevention effect in the art. For example, the first diffusion prevention layer (432a) may include nickel (Ni). The first diffusion prevention layer (432a) containing nickel may be a layer that assists in bonding strength. The first diffusion prevention layer (432a) may improve the bonding strength between adjacent layers when manufacturing the thermoelectric element (430).

[0136] According to one embodiment, the thickness of the first diffusion prevention layer (432a) may be 0.1 μm to 2.0 μm. If the first diffusion prevention layer (432a) exceeds 2.0 μm, voids may be formed due to mutual diffusion between the thermoelectric element (430) and the first diffusion prevention layer (432a) when operating in a high-temperature region (e.g., 200 degrees Celsius or higher), thereby reducing the thermoelectric properties.

[0137] According to one embodiment, the second diffusion prevention layer (432b) may be disposed on the first diffusion prevention layer (432a). The second diffusion prevention layer (432b) may be disposed between the first diffusion prevention layer (432a) and the third diffusion prevention layer (432c). The second diffusion prevention layer (432b) can stably maintain the thermoelectric properties of the thermoelectric element (430) by suppressing compound diffusion and vacancy formation.

[0138] According to one embodiment, the second diffusion barrier layer (432b) may include a nickel (Ni)-based alloy. The second diffusion barrier layer (432b) may have a nickel-based alloy composition different from the third diffusion barrier layer (432c) described later. For example, the second diffusion barrier layer (432b) may include a nickel-phosphorus (Ni-P) alloy. Here, the phosphorus content may be 1 wt% to 8 wt%. If the phosphorus content exceeds 8 wt%, internal stress increases, which may reduce adhesion. However, it is not limited thereto, and the second diffusion barrier layer (432b) may be a Ni-M-based alloy. Here, M may be at least one metal among Al, Co, W, Sn, An, and Pb.

[0139] According to one embodiment, the thickness of the second diffusion barrier layer (432b) may be 0.5 μm to 3.0 μm. If the thickness of the second diffusion barrier layer is excessively thick, the thermoelectric properties may be reduced.

[0140] According to one embodiment, the third diffusion prevention layer (432c) may be disposed on the second diffusion prevention layer (432b). The third diffusion prevention layer (432c) may be disposed between the second diffusion prevention layer (432b) and the fourth diffusion prevention layer (432d). The third diffusion prevention layer (432c) may contribute to stabilization by increasing adhesion with the fourth diffusion prevention layer (432d).

[0141] According to one embodiment, the third diffusion barrier layer (432c) may include a nickel-based alloy. For example, the third diffusion barrier layer (432c) may include a nickel-phosphorus (Ni-P) alloy. Here, the phosphorus content may be 1 wt% to 8 wt%. If the phosphorus content exceeds 8 wt%, internal stress increases and adhesion may decrease.

[0142] According to one embodiment, the thickness of the third diffusion barrier layer (432c) may be 3.0 μm to 15.0 μm. If the thickness of the third diffusion barrier layer (432c) is excessively thick, the thermoelectric properties may be reduced.

[0143] According to one embodiment, the fourth diffusion prevention layer (432d) may be disposed on the third diffusion prevention layer (432c). The fourth diffusion prevention layer (432d) can increase the bonding strength between the electrode and the thermoelectric element (430), thereby increasing durability against thermal stress such as thermal expansion.

[0144] According to one embodiment, the fourth diffusion barrier layer (432d) may be composed of at least one type of metal. For example, the use of nickel may be excluded in the fourth diffusion barrier layer (432d). For example, the fourth diffusion barrier layer (432d) may be a non-nickel (Ni-free) metal or alloy comprising one or more selected from the group consisting of Au, Mo, Ag, Al, and Zn. The thickness of the fourth diffusion barrier layer (432d) may be 0.03 μm to 0.5 μm.

[0145] According to one embodiment, the first diffusion prevention layer (432a), the second diffusion prevention layer (432b), and the third diffusion prevention layer (432c) may each be composed of a nickel (Ni) containing layer or a Ni alloy layer. The fourth diffusion prevention layer (432d) may be composed of a non-nickel metal or alloy layer.

[0146] According to one embodiment, the total thickness of the first diffusion prevention layer (432a), the second diffusion prevention layer (432b), and the third diffusion prevention layer (432c) may be 3.0 μm to 20.0 μm.

[0147] FIG. 5 is an exemplary drawing for explaining a refrigerator that cools a storage room using a thermoelectric module according to one embodiment.

[0148] FIG. 6 is an enlarged view of part A of FIG. 5 according to one embodiment.

[0149] All features, components, and / or arrangement relationships between components illustrated in FIGS. 5 and 6 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in other figures of this specification. Likewise, all features, components, and / or arrangement relationships between components described in relation to FIGS. 1 through 4 and FIGS. 7 through 11 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in FIGS. 5 and 6.

[0150] FIGS. 5 and 6 are schematic drawings for explaining a structure for cooling a refrigerator (500) (e.g., refrigerator (1) of FIG. 1) using a thermoelectric module (400) (e.g., thermoelectric module (400) of FIG. 4). The illustrated structure does not limit the scope of the present disclosure.

[0151] Referring to FIGS. 5 and 6, a refrigerator (500) according to one embodiment may include at least one of a main body (510), a door (520), a storage compartment (510a), or a thermoelectric cooler (530). Here, the thermoelectric cooler (530) may be referred to as a Peltier cooler.

[0152] According to one embodiment, the main body (510) may be configured to form or define at least one storage room (510a). The main body (510) may include an insulating material. One side of the main body (510) may be formed open.

[0153] According to one embodiment, the door (520) may be positioned to open and close an open portion of the main body (510). The door (520) may be positioned at the front of the main body (510) and configured to seal the storage room (510a). The door (520) may include an insulating material.

[0154] According to one embodiment, the thermoelectric cooler (530) may include at least one of a thermoelectric module (400) (e.g., the thermoelectric module (400) of FIG. 4), a first heat diffusion member (532), a second heat diffusion member (533), an air cooling fin (534), a heat sink (535), a first fan (536), or a second fan (537). The thermoelectric cooler structure illustrated in FIG. 5 and FIG. 6 can likewise be applied to the refrigerator of FIG. 1 (e.g., the refrigerator (1) of FIG. 1).

[0155] According to one embodiment, the thermoelectric cooler (530) may be positioned to penetrate the main body (510). The thermoelectric cooler (530) may protrude a portion toward the inside of the main body (510). The thermoelectric cooler (530) may protrude a portion toward the outside of the main body (510). The thermoelectric cooler (530) may be positioned to supply cold air to the inside of the main body (510) and release heat to the outside of the main body (510).

[0156] According to one embodiment, the thermoelectric module (400) may be placed inside the main body (510). The thermoelectric module (400) can generate a cooling effect by using the voltage supplied from the refrigerator (500) to release / absorb thermal energy when electrons move due to the energy level difference between PN semiconductors.

[0157] According to one embodiment, the first heat diffusion member (532) may be disposed on one side of the thermoelectric module (400). The first heat diffusion member (532) may be disposed in contact with one surface of the thermoelectric module (400). The first heat diffusion member (532) may be disposed in the direction of the storage chamber (510a) of the thermoelectric module (400). The first heat diffusion member (532) may perform a cooling function.

[0158] According to one embodiment, the first heat diffusion member (532) can improve heat exchange efficiency by making the temperature of the heat-generating surface uniform. The first heat diffusion member (532) may include at least one of copper, aluminum, an aluminum-copper composite, a graphite sheet, or a ceramic composite.

[0159] According to one embodiment, the second heat diffusion member (533) may be disposed on the other side of the thermoelectric module (400). The second heat diffusion member (533) may be disposed in contact with the other surface of the thermoelectric module (400). The second heat diffusion member (533) may be disposed in the outer direction of the thermoelectric module (400). The second heat diffusion member (533) may perform a heat generation function. The second heat diffusion member (533) may function as a heat radiator.

[0160] According to one embodiment, the second heat diffusion member (533) can improve heat exchange efficiency by making the temperature of the cooling surface uniform. The second heat diffusion member (533) may include at least one of copper, aluminum, an aluminum-copper composite, a graphite sheet, or a ceramic composite.

[0161] The first heat diffusion member (532) and the second heat diffusion member (533) may be arranged to exchange heat with the thermoelectric module (400) with the thermoelectric module (400) in between. The surroundings of the first heat diffusion member (532) and the second heat diffusion member (533) may be composed of an insulating material so that direct heat exchange between them is not possible.

[0162] According to one embodiment, the air cooling fin (534) may be positioned to be in contact with the first heat diffusion member (532). The air cooling fin (534) may be positioned to face the storage chamber (510a). The air cooling fin (534) may absorb heat inside the storage chamber (510a) and transfer it to the first heat diffusion member (532). The air cooling fin (534) may have, for example, an aluminum fin structure, but is not limited thereto.

[0163] According to one embodiment, the heat sink (535) may be positioned to be in contact with the second heat diffusion member (533). The heat sink (535) may be positioned to face the outside of the main body (510). The heat sink (535) may dissipate heat received from the second heat diffusion member (533) to the outside. The heat sink (535) may include, for example, aluminum or copper, but is not limited thereto.

[0164] According to one embodiment, the first fan (536) may be positioned to generate airflow around the air cooling fins (534). The first fan (536) may be positioned inside the main body (510). The first fan (536) may be omitted.

[0165] According to one embodiment, the second fan (537) may be positioned to effectively dissipate heat generated from the heat sink (535) to the outside. The second fan (537) may be positioned on the outside of the main body (510).

[0166] FIG. 7 is a flowchart showing the manufacturing process of a thermoelectric module according to one embodiment.

[0167] All features, components, and / or arrangement relationships between components illustrated in FIG. 7 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in other figures of this specification. Likewise, all features, components, and / or arrangement relationships between components described in relation to FIG. 1 through 6 and FIG. 8 through 11 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in FIG. 7.

[0168] Referring to FIG. 7, a method for manufacturing a thermoelectric material according to one embodiment may include a raw material preparation process (710), a powder production process (720), a material molding process (730), a heat treatment process (740), a material inspection process (750), or a thermoelectric module manufacturing process (760). In FIG. 7, processes 710 to 750 may be a method for manufacturing a thermoelectric material (431). The thermoelectric material (431) manufactured in the process of FIG. 7 may be substantially the same as the thermoelectric material of FIG. 4 (e.g., the thermoelectric material (431) of FIG. 4).

[0169] According to one embodiment, a method for manufacturing a thermoelectric material may include a raw material preparation process (710). A quaternary material may be prepared for manufacturing the thermoelectric material. The quaternary material may be bismuth (Bi), telluride (Te), selenium (Se), and copper iodide (CuI).

[0170] According to one embodiment, a method for manufacturing a thermoelectric material may include a powder manufacturing process (720). Powder may be manufactured using the quaternary material prepared in process 710. For example, powder may be manufactured by placing the quaternary material into a ball mill device and rotating it through impact and friction. For example, powder may be manufactured by an atomizer process in which the quaternary material is melted and then rapidly cooled. For example, powder may be manufactured by a melt spinning method in which the quaternary material is melted and then sprayed onto a rotating cooling drum. The method of manufacturing powder is not limited to the foregoing.

[0171] According to one embodiment, a method for manufacturing a thermoelectric material may include a material forming process (730). For example, the molded body may be manufactured by an extrusion process in which powder is heated to a state where it can be plastically deformed and then formed through a mold. For example, the molded body may be manufactured by a Spark Plasma Sintering (SPS) method in which powder is placed into a mold, pressure is applied, and then a high current is passed through the powder for a short period of time to cause sintering between powder particles. For example, the molded body may be manufactured by a Hot Isostatic Pressing (HIP) method in which powder is placed into a chamber containing an inert gas under high temperature and high pressure conditions and isotropic pressure is applied. For example, the molded body may be manufactured by a hot press method in which unidirectional pressure is applied to the powder at a high temperature and simultaneously to cause sintering. The method of manufacturing the molded body is not limited to the foregoing.

[0172] According to one embodiment, a method for manufacturing a thermoelectric material may include a heat treatment process (740). The heat treatment process (740) may be carried out between 400 degrees Celsius and 550 degrees Celsius. As the temperature increases during the heat treatment process (740), the rate of increase in the performance index (ZT) before and after heat treatment may increase (see FIG. 9). For example, the heat treatment process (740) may be carried out between 450 degrees Celsius and 550 degrees Celsius.

[0173] According to one embodiment, the heat treatment process (740) can be performed in a vacuum chamber. During the process of placing a molded body into the vacuum chamber and performing heat treatment, Te may be evaporated by the negative pressure environment of the vacuum chamber. A plurality of pores may be formed by the evaporated Te (see FIG. 11). The pressure inside the vacuum chamber may be maintained at 0.1 MPa.

[0174] If the temperature exceeds 550 degrees during the heat treatment, the surface of the molded body may melt. If the surface of the molded body melts, it inhibits the volatilization of Te during the heat treatment process, and as a result, the formation of multiple pores can be suppressed. Therefore, the temperature of the heat treatment process may be 550 degrees or lower.

[0175] According to one embodiment, the volume of the vacuum chamber may be 10 to 100 times the volume of the molded body (or thermoelectric material) contained within the vacuum chamber. The amount of Te volatilization may vary depending on the volume of the vacuum chamber, and the volume ratio between the vacuum chamber and the molded body (or thermoelectric material) may be adjusted to volatilize an appropriate amount of Te.

[0176] According to one embodiment, during the process of heat treatment being carried out in a vacuum chamber, a process of adding a mixture of Bi (bismuth) or Te (telluride) into the vacuum chamber may be further included. For example, at least one of a Bi-Te alloy, Bi2Te3, Bi4Te3, or Te gas may be added into the vacuum chamber.

[0177] According to one embodiment, a method for manufacturing a thermoelectric material may include a material inspection process (750). In the material inspection process (750), at least one of electrical conductivity, Seebeck coefficient, or Z-value may be measured. In the material inspection process (750), whether the performance index measured using electrical conductivity and Seebeck coefficient is greater than or equal to a predetermined reference value may be inspected.

[0178] According to one embodiment, a process (760) for manufacturing a thermoelectric module using a manufactured thermoelectric material may be performed. A thermoelectric material that has passed through a material inspection process (750) may be used to manufacture a thermoelectric module (760). In the process of manufacturing the thermoelectric module, a process of depositing at least one diffusion barrier layer on the upper and lower surfaces of the thermoelectric material may be performed. After at least one diffusion barrier layer is deposited, a substrate may be attached to the upper and lower surfaces.

[0179] FIG. 8 is an experimental example in which the amount of change in performance of a thermoelectric material according to the heat treatment temperature according to one embodiment is measured.

[0180] The experimental example of FIG. 8 is a graph showing the change in performance index before and after heat treatment of a thermoelectric material (e.g., the thermoelectric material (431) of FIG. 4) manufactured through processes 710 to 750 of FIG. 7.

[0181] The performance index (ZT) can be used as an indicator to measure the performance of thermoelectric materials.

[0182]

[0183] In the above mathematical formula 1, ZT represents the dimensionless performance index, S represents the Seebeck coefficient, σ represents the electrical conductivity, T represents the absolute temperature, and k represents the thermal conductivity.

[0184] The Seebeck coefficient can be an indicator representing the ratio of thermoelectric electromotive force to the temperature difference. It is a coefficient that determines how high a voltage a thermoelectric material can generate due to a temperature difference. For example, the higher the Seebeck coefficient, the higher the voltage a thermoelectric material can generate at the same temperature difference.

[0185] To increase the dimensionless performance index (ZT), the Seebeck coefficient and electrical conductivity, i.e., the power factor (S 2 Materials with high σ) and low thermal conductivity may be required. The dimensionless performance index (ZT) can be determined by electrical conductivity and thermal conductivity in addition to the Seebeck coefficient. To assess the overall performance improvement of thermoelectric materials, the dimensionless performance index (ZT), which reflects the correlation with electrical conductivity and thermal conductivity rather than just the Seebeck coefficient, can be used.

[0186] As the value of the dimensionless performance index (ZT) increases, the amount of heat absorbed and the amount of heat generated increase, indicating that the cooling performance of the thermoelectric material is improved. As the value of the dimensionless performance index (ZT) increases, the energy conversion efficiency of the thermoelectric material may increase. For example, as the value of the dimensionless performance index (ZT) increases, the thermoelectric material can convert electrical energy into thermal energy more efficiently. A thermoelectric material (431) according to one embodiment of the present disclosure is characterized by having an improved performance index.

[0187] The thermoelectric material (431), which had a performance index of 2.40 before heat treatment, was heat-treated at a temperature of 475 degrees Celsius in the heat treatment process (740), and its performance index increased by about 13% to 2.76.

[0188] The thermoelectric material (431), which had a performance index of 2.29 before heat treatment, was heat-treated at a temperature of 500 degrees Celsius in a heat treatment process (740), and its performance index increased by about 15% to 2.70.

[0189] The performance index of the thermoelectric material (431), which was 2.27 before heat treatment, increased by about 17% to 2.73 after undergoing heat treatment at a temperature of 525 degrees Celsius in the heat treatment process (740).

[0190] Based on the experimental values ​​shown in Fig. 8, it can be confirmed that the performance increase rate increases as the heat treatment temperature increases. However, if the heat treatment temperature exceeds 550 degrees, the surface of the thermoelectric material (431) melts, which suppresses the volatilization of Te within the vacuum chamber, so it may be desirable not to exceed 550 degrees for the heat treatment temperature.

[0191] FIG. 9 is an experimental example in which the change in performance of a thermoelectric material according to a heat treatment temperature and heat treatment time was measured according to one embodiment.

[0192] In FIG. 9, a first thermoelectric material (910) (e.g., the thermoelectric material (431) of FIG. 4) was subjected to a heat treatment process (740) at 500 degrees Celsius for 20 minutes and 1 hour, respectively. In FIG. 9, a second thermoelectric material (920) (e.g., the thermoelectric material (431) of FIG. 4) was subjected to a heat treatment process (740) at 500 degrees Celsius for 1 hour twice, at 500 degrees Celsius for 2 hours, at 500 degrees Celsius for 4 hours, and at 525 degrees Celsius for 1 hour.

[0193] Referring to FIG. 9, it can be seen that the electrical conductivity increases as a result of heat-treating the first thermoelectric material (910) and the second thermoelectric material (920) at 500 degrees Celsius or higher. Here, the first thermoelectric material (910) and the second thermoelectric material (920) are each any thermoelectric material manufactured by the manufacturing method shown in FIG. 7, and the characteristics of the illustrated first thermoelectric material (910) and the second thermoelectric material (920) do not limit the scope of the rights of the present disclosure.

[0194] For example, based on the data obtained by heat-treating the first thermoelectric material (910) and the second thermoelectric material (920), it was confirmed that the Seebeck coefficient can increase as the heat treatment time increases.

[0195] As shown in FIG. 9, the performance index measured using the changed Seebeck coefficient and electrical conductivity after heat-treating the first thermoelectric material (910) twice in different environments is 2.95 and 2.80. The performance index measured using the changed Seebeck coefficient and electrical conductivity after heat-treating the second thermoelectric material (920) four times in different environments is 2.95, 3.02, 3.05, 3.04, and 3.07. Thus, it can be confirmed that when heat treatment is performed based on the heat treatment process (740) according to one embodiment of the present disclosure, the performance index of the thermoelectric material is at least greater than 2.7 and furthermore greater than 2.9.

[0196] As shown in Fig. 9, it can be confirmed that the performance index can be improved by performing heat treatment at a temperature of 500 degrees Celsius for more than 1 hour.

[0197] FIG. 10 is an experimental example in which the size of crystal grains was measured according to the heat treatment temperature according to one embodiment.

[0198] All features, components, and / or arrangement relationships between components illustrated in FIG. 10 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in other figures of this specification. Likewise, all features, components, and / or arrangement relationships between components described in relation to FIG. 1 through 9 and FIG. 11 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in FIG. 10.

[0199] Figures 10(a) and 10(b) each show arbitrary support points of a thermoelectric material (e.g., the thermoelectric material (431) of Figure 4) after heat treatment. In Figure 10(a), the average grain size is 16.71 μm, and in Figure 10(b), the average grain size is 12.47 μm.

[0200] According to one embodiment, the size of the crystal grains of the thermoelectric material (431) may be 5 μm to 30 μm. Here, the size of the crystal grains may refer to an average size. If the size of the crystal grains becomes smaller than 5 μm, the electrical conductivity decreases, which may lower the performance index. If the size of the crystal grains becomes larger than 30 μm, the thermal conductivity increases, which may lower the performance index. Therefore, to improve the performance index, it is necessary to form crystal grains within an appropriate size range as described in the present disclosure.

[0201] According to one embodiment, crystal grains of 5 μm to 30 μm can be formed through the heat treatment process (740) of FIG. 7. For example, crystal grains of 5 μm to 30 μm can be formed by heat treatment in a vacuum chamber at a temperature between 400°C and 550°C.

[0202] FIG. 11 is a diagram showing a portion of a thermoelectric material according to one embodiment observed with an electron microscope.

[0203] All features, components, and / or arrangement relationships between components illustrated in FIG. 11 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in other figures of this specification. Likewise, all features, components, and / or arrangement relationships between components described in relation to FIG. 1 through 10 may be included, either alone or in combination with, the features, components, and arrangement relationships between components described in FIG. 11.

[0204] Referring to FIG. 11, a thermoelectric material (431) according to one embodiment may include a plurality of pores (431b). The plurality of pores (431b) may be empty spaces formed when Te volatilizes during a heat treatment process (740) performed in a vacuum chamber.

[0205] According to one embodiment, a plurality of pores (431b) may be formed adjacent to the side (431a) of the thermoelectric material (431). Here, the side (431a) of the thermoelectric material (431) may refer to a surface where a diffusion barrier is not deposited during the thermoelectric module manufacturing process. The side (431a) of the thermoelectric material (431) may be a curved surface. Since the plurality of pores (431b) are generated by the volatilization of Te during the heat treatment process (740), they may be formed adjacent to the side (431a). However, this is not limited thereto, and some of the plurality of pores (431b) may be positioned closer to the center than to the side (431a).

[0206] According to one embodiment, the total volume of the plurality of pores (431b) may be 1 vol% to 10 vol% of the total volume of the thermoelectric material (431). The plurality of pores (431b) may have the role of reducing the thermal conductivity of the thermoelectric material (431) to increase the performance index. If the total volume of the plurality of pores (431b) exceeds 10 vol% of the total volume of the thermoelectric material (431), the durability may be weakened due to a decrease in the strength of the thermoelectric material (431). If the plurality of pores (431b) exceed 10 vol% of the total volume of the thermoelectric material (431), the electrical conductivity may be excessively reduced, and consequently, the performance index may be reduced.

[0207] According to one embodiment, a plurality of pores (431b) may be formed by heat-treating a thermoelectric material (431) within a vacuum chamber. To control the volume of the plurality of pores (431b) during the manufacturing process of the thermoelectric material (431), the heat treatment time may be experimentally adjusted, or at least one of a Bi-Te alloy, Bi2Te3, Bi4Te3, or Te gas may be added to the vacuum chamber.

[0208] A thermoelectric material (431) according to one embodiment may include bismuth (Bi), telluride (Te), selenium (Se), and copper iodide (CuI), and the grain size may be 5 to 30 μm.

[0209] According to one embodiment, the thermoelectric material (431) may include a plurality of pores (431b) formed in a portion adjacent to the side of the thermoelectric material (431).

[0210] According to one embodiment, the total volume of the plurality of pores (431b) may be 1 vol% to 10 vol% of the total volume of the thermoelectric material (431).

[0211] According to one embodiment, the plurality of pores (431b) may be formed by the volatilization of the telluride during a heat treatment process.

[0212] According to one embodiment, the performance index of the thermoelectric material (431) may be 2.7 or higher.

[0213] A method for manufacturing a thermoelectric material (431) according to one embodiment may include a process of forming the thermoelectric material (431) using a powder made using bismuth (Bi), telluride (Te), selenium (Se), and copper iodide (CuI), and a process of heat-treating the thermoelectric material (431) at 400 degrees to 550 degrees.

[0214] According to one embodiment, the heat treatment process may be carried out in a vacuum chamber.

[0215] According to one embodiment, the volume of the vacuum chamber may be 10 to 100 times the volume of the thermoelectric material (431) contained within the vacuum chamber.

[0216] According to one embodiment, the method for manufacturing the thermoelectric material (431) may further include a process of adding a mixture of the bismuth and the telluride into the vacuum chamber to control the amount of volatilization of the telluride during the heat treatment process.

[0217] According to one embodiment, the process of forming the thermoelectric material (431) may be one of extrusion, hot press, Spark Plasma Sintering (SPS), or Hot Isostatic Pressing (HIP).

[0218] A refrigerator according to one embodiment may include a storage room (20), a main body (10) including the storage room (20), and a cold air supply device (70) configured to supply cold air to the storage room (20) and including a thermoelectric module (400). The thermoelectric module (400) may include a lower substrate (410), a lower conductive pattern layer (420) disposed on the lower substrate (410), a plurality of thermoelectric elements (430) disposed on the lower conductive pattern layer (420), an upper conductive pattern layer (440) disposed on the thermoelectric elements (430), and an upper substrate (450) formed on the upper conductive pattern layer (440). The thermoelectric element (430) may include a thermoelectric material (431) comprising bismuth (Bi), telluride (Te), selenium (Se), and copper iodide (CuI), with a grain size of 5 to 30 μm.

[0219] According to one embodiment, the thermoelectric material (431) may include a plurality of pores (431b) formed in a portion adjacent to the lateral side of the thermoelectric material (431).

[0220] According to one embodiment, the total volume of the plurality of pores (431b) may be 1 vol% to 10 vol% of the total volume of the thermoelectric material (431).

[0221] According to one embodiment, the plurality of pores (431b) may be formed by the volatilization of the telluride during a heat treatment process.

[0222] According to one embodiment, the performance index of the thermoelectric material (431) may be 2.7 or higher.

[0223] The terms used in this disclosure are used merely to describe specific embodiments and are not intended to limit this disclosure. For example, a component expressed in the singular should be understood as a concept including a plural component unless the context clearly implies only the singular. Each of the phrases used in this disclosure, such as “A or B,” “at least one of A and B,” “at least one of A or B,” “A, B or C,” “at least one of A, B and C,” and “at least one of A, B, or C,” may include any one of the items listed together in the corresponding phrase, or any possible combination thereof. It should be understood that the term “and / or” used in this disclosure encompasses any possible combination of one or more of the listed items. Terms such as “comprising,” “having,” and “consisting of” used in this disclosure are intended merely to specify the existence of the features, components, parts, or combinations thereof described in this disclosure, and the use of such terms is not intended to exclude the existence or addition of one or more other features, components, parts, or combinations thereof. Expressions such as “first,” “second,” used in this disclosure may modify various components regardless of order and / or importance, and are used only to distinguish one component from another and do not limit said components.

[0224] The expression “configured to” as used in this disclosure may be appropriately substituted depending on the context, for example, with “suitable for,” “capable of,” “designed to,” “modified to,” “made to,” or “capable of.” The term “configured to” may not necessarily mean only that which is “specially designed” in hardware. Instead, in some situations, the expression “device configured to” may mean that the device is “capable of” together with other devices or components. For example, the phrase “device configured (or set) to perform A, B, and C” may mean a device dedicated to performing the said operation, or a general-purpose device capable of performing various operations including said operation.

[0225] Meanwhile, terms such as “upper side,” “lower side,” and “front-rear direction” used in this disclosure are defined based on the drawings, and the shape and position of each component are not limited by these terms.

[0226] Although the foregoing description in this disclosure has focused on specific embodiments, this disclosure is not limited to such specific embodiments and should be understood to encompass all various modifications, equivalents, and / or substitutions of various embodiments.

Claims

Claim 1 A thermoelectric material (431) comprising bismuth (Bi), telluride (Te), selenium (Se), and copper iodide (CuI), wherein the grain size is 5 to 30 μm. Claim 2 In claim 1, the thermoelectric material (431) comprises a plurality of pores (431b) formed in a portion adjacent to the side of the thermoelectric material (431). Claim 3 In paragraph 2, the total volume of the plurality of pores (431b) is 1 vol% to 10 vol% of the total volume of the thermoelectric material (431). Claim 4 In paragraph 2 or 3, the plurality of pores (431b) are a thermoelectric material (431) formed by the volatilization of the telluride during a heat treatment process. Claim 5 In any one of claims 1 to 4, the thermoelectric material (431) has a performance index of 2.7 or higher. Claim 6 A method for manufacturing a thermoelectric material (431), comprising: a process of forming the thermoelectric material (431) using powder made using bismuth (Bi), telluride (Te), selenium (Se), and copper iodide (CuI); and a process of heat-treating the thermoelectric material (431) at 400 degrees to 550 degrees Celsius. Claim 7 In claim 6, the method wherein the heat treatment process is carried out in a vacuum chamber. Claim 8 In claim 7, the method wherein the volume of the vacuum chamber is 10 to 100 times the volume of the thermoelectric material (431) contained within the vacuum chamber. Claim 9 A method according to claim 7 or 8, further comprising a process of adding a mixture of bismuth and telluride into the vacuum chamber to control the amount of volatilization of the telluride in the heat treatment process. Claim 10 In claim 6, the process of forming the thermoelectric material (431) is one of the processes of extrusion, hot press, SPS (Spark Plasma Sintering), or HIP (Hot Isostatic Pressing). Claim 11 A refrigerator comprises: a storage chamber (20); a main body (10) including the storage chamber (20); and a cold air supply device (70) configured to supply cold air to the storage chamber (20) and including a thermoelectric module (400), wherein the thermoelectric module (400) comprises: a lower substrate (410); a lower conductive pattern layer (420) disposed on the lower substrate (410); a plurality of thermoelectric elements (430) disposed on the lower conductive pattern layer (420); and an upper conductive pattern layer (440) disposed on the thermoelectric elements (430). A refrigerator comprising an upper substrate (450) formed on the upper conductive pattern layer (440), wherein the thermoelectric element (430) comprises a thermoelectric material (431) comprising bismuth (Bi), telluride (Te), selenium (Se), and copper iodide (CuI), and having a crystal grain size of 5 to 30 μm. Claim 12 In claim 11, the thermoelectric material (431) comprises a plurality of pores (431b) formed in a portion adjacent to the lateral side of the thermoelectric material (431). Claim 13 A refrigerator according to claim 12, wherein the total volume of the plurality of pores (431b) is 1 vol% to 10 vol% of the total volume of the thermoelectric material (431). Claim 14 In paragraph 13, the plurality of pores (431b) are formed by the volatilization of the telluride during the heat treatment process, in a refrigerator. Claim 15 A refrigerator in which, in any one of claims 11 to 14, the performance index of the thermoelectric material (431) is 2.7 or higher.

Images