WO2022153594A1 - 車室暖房用のヒーターエレメント、ヒーターユニット及びヒーターシステム、並びに車室浄化用のヒーターエレメント - Google Patents

車室暖房用のヒーターエレメント、ヒーターユニット及びヒーターシステム、並びに車室浄化用のヒーターエレメント Download PDF

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Publication number
WO2022153594A1
WO2022153594A1 PCT/JP2021/033211 JP2021033211W WO2022153594A1 WO 2022153594 A1 WO2022153594 A1 WO 2022153594A1 JP 2021033211 W JP2021033211 W JP 2021033211W WO 2022153594 A1 WO2022153594 A1 WO 2022153594A1
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WO
WIPO (PCT)
Prior art keywords
heater
heater element
honeycomb structure
outer peripheral
peripheral wall
Prior art date
Application number
PCT/JP2021/033211
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English (en)
French (fr)
Japanese (ja)
Inventor
由紀夫 宮入
昌明 桝田
義文 高木
浩文 山口
徹 早瀬
拓哉 中島
Original Assignee
日本碍子株式会社
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Publication date
Application filed by 日本碍子株式会社 filed Critical 日本碍子株式会社
Priority to JP2022575067A priority Critical patent/JPWO2022153594A1/ja
Priority to CN202180089723.1A priority patent/CN116685484A/zh
Priority to DE112021006821.0T priority patent/DE112021006821T5/de
Publication of WO2022153594A1 publication Critical patent/WO2022153594A1/ja
Priority to US18/349,345 priority patent/US20230354479A1/en

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/02—Details
    • H05B3/03—Electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
    • B60H1/00—Heating, cooling or ventilating [HVAC] devices
    • B60H1/22—Heating, cooling or ventilating [HVAC] devices the heat being derived otherwise than from the propulsion plant
    • B60H1/2215—Heating, cooling or ventilating [HVAC] devices the heat being derived otherwise than from the propulsion plant the heat being derived from electric heaters
    • B60H1/2225—Heating, cooling or ventilating [HVAC] devices the heat being derived otherwise than from the propulsion plant the heat being derived from electric heaters arrangements of electric heaters for heating air
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/141—Conductive ceramics, e.g. metal oxides, metal carbides, barium titanate, ferrites, zirconia, vitrous compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/22—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
    • H05B3/24—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor being self-supporting
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/40—Heating elements having the shape of rods or tubes
    • H05B3/42—Heating elements having the shape of rods or tubes non-flexible
    • H05B3/48—Heating elements having the shape of rods or tubes non-flexible heating conductor embedded in insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/40—Heating elements having the shape of rods or tubes
    • H05B3/42—Heating elements having the shape of rods or tubes non-flexible
    • H05B3/48—Heating elements having the shape of rods or tubes non-flexible heating conductor embedded in insulating material
    • H05B3/50—Heating elements having the shape of rods or tubes non-flexible heating conductor embedded in insulating material heating conductor arranged in metal tubes, the radiating surface having heat-conducting fins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
    • B60H1/00—Heating, cooling or ventilating [HVAC] devices
    • B60H1/22—Heating, cooling or ventilating [HVAC] devices the heat being derived otherwise than from the propulsion plant
    • B60H2001/2268—Constructional features
    • B60H2001/2271—Heat exchangers, burners, ignition devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
    • B60H1/00—Heating, cooling or ventilating [HVAC] devices
    • B60H1/22—Heating, cooling or ventilating [HVAC] devices the heat being derived otherwise than from the propulsion plant
    • B60H2001/2268—Constructional features
    • B60H2001/2287—Integration into a vehicle HVAC system or vehicle dashboard
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/02—Heaters using heating elements having a positive temperature coefficient
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/022—Heaters specially adapted for heating gaseous material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/022—Heaters specially adapted for heating gaseous material
    • H05B2203/023—Heaters of the type used for electrically heating the air blown in a vehicle compartment by the vehicle heating system
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/022—Heaters specially adapted for heating gaseous material
    • H05B2203/024—Heaters using beehive flow through structures

Definitions

  • the present invention relates to a heater element for heating the passenger compartment, a heater unit and a heater system, and a heater element for purifying the passenger compartment.
  • Patent Document 1 proposes a heater element using a honeycomb structure that is compact and can increase the heat transfer area per volume.
  • This heater element has a honeycomb structure having an outer peripheral wall, a partition wall arranged inside the outer peripheral wall and partitioning a plurality of cells forming a flow path from the first end surface to the second end surface, and a first end surface.
  • Patent Document 2 proposes a heater element in which a pair of electrode layers are arranged on the surface of the outer peripheral wall of the honeycomb structure. Since the electrode layer does not face the gas flow path in this heater element, corrosion of the electrode layer can be suppressed.
  • the electrode layer and the outside are connected by an electric wire.
  • the honeycomb structure used for the heater element of Patent Document 2 is made of a material that does not have PTC characteristics, and the electrical resistance due to the temperature rise of the PTC material layer in contact with the outer peripheral wall of the honeycomb structure is increased. The current is controlled by the increase. Therefore, the sensitivity of temperature control is lower than that of the case where the honeycomb structure is made of a material having PTC characteristics.
  • the present invention has been made to solve the above-mentioned problems, and includes a heater element for heating a passenger compartment, which can increase the amount of power supplied from the outside and improve the heat generation performance, and the heater element. It is an object of the present invention to provide a heater unit and a heater system for heating a passenger compartment used. Another object of the present invention is to provide a heater element that can also be used for purifying a vehicle interior.
  • the present invention has an outer peripheral wall and a partition wall that is disposed inside the outer peripheral wall and forms a plurality of cells that form a flow path from the first end surface to the second end surface.
  • the honeycomb structure has a shape having a major axis and a minor axis in a cross section orthogonal to the central axis.
  • the pair of electrode layers are formed in a band shape extending parallel to the central axis, and in a cross section orthogonal to the central axis, the outer periphery thereof is opposed to each other with a long axis passing through the center of gravity of the honeycomb structure. It is placed on the surface of the wall and
  • the heater element is a heater element which is arranged on the end side of each electrode layer and further includes a plate-shaped external connecting member which is in contact with each electrode layer in a plane.
  • the present invention is a heater unit for heating a passenger compartment including two or more of the heater elements.
  • the present invention relates to the heater unit.
  • An inflow pipe that communicates the outside air introduction section or the passenger compartment with the inflow port of the heater unit, It is a heater system for heating a passenger compartment provided with a battery for applying a voltage to the heater unit and an outflow pipe for communicating the outlet of the heater unit with the passenger compartment.
  • the present invention has an outer peripheral wall and a partition wall which is arranged inside the outer peripheral wall and forms a plurality of cells which form a flow path from the first end surface to the second end surface.
  • the honeycomb structure has a shape having a major axis and a minor axis in a cross section orthogonal to the central axis.
  • the pair of electrode layers are formed in a band shape extending parallel to the central axis, and in a cross section orthogonal to the central axis, the outer periphery thereof is opposed to each other with a long axis passing through the center of gravity of the honeycomb structure. It is placed on the surface of the wall and
  • the heater element is a heater element which is arranged on the end side of each electrode layer and further includes a plate-shaped external connecting member which is in contact with each electrode layer in a plane.
  • a heater element for vehicle interior heating capable of increasing the amount of power supplied from the outside and improving heat generation performance, and a heater unit and a heater system for vehicle interior heating using this heater element. can do. Further, according to the present invention, it is possible to provide a heater element that can also be used for purifying a vehicle interior.
  • FIG. 5 is a schematic cross-sectional view of another heater element according to an embodiment of the present invention, orthogonal to the central axis of the honeycomb structure.
  • FIG. 5 is a schematic cross-sectional view of another heater element according to an embodiment of the present invention, orthogonal to the central axis of the honeycomb structure.
  • FIG. 5 is a schematic cross-sectional view of another heater element according to an embodiment of the present invention, orthogonal to the central axis of the honeycomb structure.
  • FIG. 5 is a schematic cross-sectional view of another heater element according to an embodiment of the present invention, orthogonal to the central axis of the honeycomb structure.
  • FIG. 5 is a schematic cross-sectional view of another heater element according to an embodiment of the present invention, orthogonal to the central axis of the honeycomb structure. It is a partially enlarged view of the honeycomb structure in the heater element of FIG. It is a schematic cross-sectional view orthogonal to the central axis of the honeycomb joint having 5 honeycomb segments.
  • FIG. 5 is a schematic partially enlarged cross-sectional view of another heater element according to an embodiment of the present invention, orthogonal to the central axis of the honeycomb structure. It is a schematic front view of the heater unit which concerns on embodiment of this invention seen from the 1st end surface side of a heater element.
  • FIG. 5 is a schematic cross-sectional view of the heater element produced in Example 1 orthogonal to the central axis of the honeycomb joint. It is the schematic of the evaluation box used in an Example. This is the result of the current density distribution of the heater elements produced in Examples 1 and 2.
  • the heater element according to the embodiment of the present invention can be suitably used as a heater element for heating the passenger compartment of a vehicle.
  • Vehicles are not particularly limited, and examples thereof include automobiles and trains. Examples of automobiles include, but are not limited to, gasoline-powered vehicles, diesel-powered vehicles, gas-fueled vehicles using CNG (compressed natural gas), LNG (liquefied natural gas), fuel cell vehicles, electric vehicles, and plug-in hybrid vehicles.
  • the heater element according to the embodiment of the present invention can be particularly suitably used for a vehicle having no internal combustion engine such as an electric vehicle and a train.
  • FIG. 1 is a schematic perspective view of a heater element according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the heater element of FIG. 1 orthogonal to the central axis of the honeycomb structure.
  • the heater element 100 according to the embodiment of the present invention is arranged inside the outer peripheral wall 11 and the outer peripheral wall 11, and forms a plurality of cells 14 for forming a flow path from the first end surface 13a to the second end surface 13b.
  • a honeycomb structure 10 having a partition wall 12 and a pair of electrode layers 20 arranged on the surface of the outer peripheral wall 11 are provided.
  • the honeycomb structure 10 has a shape having a major axis X2 and a minor axis X3 in a cross section orthogonal to the central axis X1.
  • the pair of electrode layers 20 are formed in a band shape extending parallel to the central axis X1 and have an outer circumference so as to face each other with a long axis X2 passing through the center of gravity of the honeycomb structure 10 in a cross section orthogonal to the central axis X1. It is arranged on the surface of the wall 11.
  • the heater element 100 is further provided with a plate-shaped external connecting member 30 which is arranged on the end side of each electrode layer 20 and is in contact with each electrode layer 20 in a plane.
  • the electrode layer 20 and the external connecting member 30 By disposing the electrode layer 20 and the external connecting member 30 in this way, the electrode layer 20 and the external connecting member 30 come into surface contact with each other, and it becomes easy to increase the amount of power supplied from the outside, so that the heat generation performance can be improved. can.
  • each component of the heater element 100 will be described in detail.
  • the honeycomb structure 10 is not particularly limited as long as it has a cross section orthogonal to the central axis X1 and has a major axis X2 and a minor axis X3.
  • the cross section (outer shape) orthogonal to the central axis X1 is rectangular, oval (oval, elliptical, oval, rounded rectangular, etc.), polygonal (at least facing at least). It can be a hexagon, octagon, etc., where two sides are longer than the other.
  • the cross section has a rectangular shape.
  • the end faces first end face 13a and second end face 13b) have the same shape as the cross section.
  • the cross section When the cross section is rectangular, the cross section has a short side 15 and a long side 16. Then, a pair of electrode layers 20 are arranged on both surfaces of the outer peripheral wall 11 including the long side 16.
  • the ratio of the length of the short side 15 to the length of the long side 16 is not particularly limited, but is preferably 1: 2 to 1:15, more preferably 1: 2 to 1:10, and even more preferably 1: 3 to 1. : 8. By controlling the ratio in such a range, it becomes easy to adapt to the size of the heater element used in the existing heater unit.
  • the length of the long side 16 can be, for example, 30 mm to 250 mm.
  • the length of the short side 15 can be, for example, 5 mm to 200 mm. In particular, by setting the length of the short side 15 to 10 mm or less and reducing the distance between the pair of electrode layers 20, heating can be performed even at a low voltage of about 10 V.
  • the shape of the cell 14 in the cross section orthogonal to the central axis X1 is not particularly limited, but is preferably a quadrangle (rectangle, square), a hexagon, an octagon, or a combination of two or more of these. Among these, a quadrangle and a hexagon are preferable, and a hexagon is more preferable.
  • FIGS. 1 and 2 are examples of a honeycomb structure 10 having a rectangular cross section and a square cell 14 in a cross section orthogonal to the central axis X1.
  • FIGS. 3 to 6 examples of a heater element including the honeycomb structure 10 having another shape are shown in FIGS. 3 to 6.
  • FIG. 3 is an example of a heater element 200 having a honeycomb structure 10 having a rectangular cross section (race track shape) and a square cell 14 in a cross section orthogonal to the central axis X1.
  • FIG. 4 is an example of a heater element 300 including a honeycomb structure 10 having an elliptical cross section and a rectangular cell 14 in a cross section orthogonal to the central axis X1.
  • FIG. 5 is an example of a heater element 400 including a honeycomb structure 10 having a rectangular cross section (race track shape) and a hexagonal cell 14 in a cross section orthogonal to the central axis X1.
  • FIG. 3 is an example of a heater element 200 having a honeycomb structure 10 having a rectangular cross section (race track shape) and a square cell 14 in a cross section orthogonal to the central axis X1.
  • FIG. 4
  • FIG. 6 shows a honeycomb structure in which the cross section orthogonal to the central axis X1 is a hexagon in which two opposite sides provided with the electrode layer 20 are longer than the other sides, and the shape of the cell 14 is rectangular.
  • the heater element 500 including the body 10.
  • a pair of heater elements 200, 300, 400, and 500 are opposed to each other on the surface of the outer peripheral wall 11 so as to face each other with the long axis X2 passing through the center of gravity of the honeycomb structure 10 in a cross section orthogonal to the central axis X1.
  • the electrode layer 20 is arranged, and a plate-shaped external connecting member 30 that is in flat contact with each electrode layer 20 is arranged on the end side of each electrode layer 20.
  • the heater element 100 will be mainly described, but the same applies to the heater elements 200, 300, 400, and 500.
  • the honeycomb structure 10 preferably does not have a partition wall 12 parallel to the long axis X2 in a cross section orthogonal to the central axis X1. With such a configuration, the cell 14 can be uniformly heated during heating and use, and deformation and cracking of the cell 14 can be suppressed.
  • FIG. 7 a partially enlarged view of the honeycomb structure 10 in the heater element 100 of FIG. 2 is shown in FIG.
  • the partition wall 12 has angles ⁇ and ⁇ with respect to the long axis X2.
  • the angles ⁇ and ⁇ are preferably 30 to 60 °.
  • the honeycomb structure 10 may be a honeycomb joint body having a plurality of honeycomb segments and a joint layer for joining the plurality of honeycomb segments.
  • the honeycomb joint By using the honeycomb joint, it is possible to increase the total cross-sectional area of the cell 14, which is important for securing the flow rate of gas, while suppressing the occurrence of cracks.
  • FIG. 8 shows a schematic cross-sectional view orthogonal to the central axis X1 of the honeycomb joint having five honeycomb segments.
  • the honeycomb joint 17 has five honeycomb segments 18 and a bonding layer 19 for joining between the honeycomb segments 18.
  • Each honeycomb segment 18 has an outer peripheral wall 11 and a partition wall 12 that is arranged inside the outer peripheral wall 11 and partitions a plurality of cells 14 that form a flow path from the first end surface 13a to the second end surface 13b.
  • the joining layer 19 can be formed by using a joining material.
  • the joining material is not particularly limited, but a ceramic material to which a solvent such as water is added to form a paste can be used.
  • the joining material may contain ceramics having PTC characteristics, or may contain the same ceramics as the outer peripheral wall 11 and the partition wall 12.
  • the joining material can also be used as an outer peripheral coating material after joining the honeycomb segments 18.
  • the area of each end face of the honeycomb structure 10 is not particularly limited, but may be, for example, 20 to 500 cm 2 .
  • the length of the honeycomb structure 10 (the length of the flow path of each cell 14) is not particularly limited, but may be, for example, 3 to 40 mm.
  • the outer peripheral wall 11 and the partition wall 12 of the honeycomb structure 10 are made of a material capable of generating heat by energization. Therefore, from the time when a gas such as outside air or vehicle interior air flows in from the first end surface 13a, until it passes through the plurality of cells 14 and flows out from the second end surface 13b, the gas generates heat in the outer peripheral wall 11 and It can be heated by heat transfer from the partition wall 12.
  • the outer peripheral wall 11 and the partition wall 12 are made of a material having PTC (Positive Temperature Coefficient) characteristics. That is, the outer peripheral wall 11 and the partition wall 12 have a characteristic that when the temperature rises and exceeds the Curie point, the resistance value rapidly rises and it becomes difficult for electricity to flow. Since the outer peripheral wall 11 and the partition wall 12 have PTC characteristics, when the heater element 100 becomes hot, the current flowing through them is limited, so that excessive heat generation of the heater element 100 is suppressed.
  • PTC Pressure Temperature Coefficient
  • the outer peripheral wall 11 and the partition wall 12 are made of a material mainly composed of barium titanate (BaTIO 3 ) -based crystal particles in which a part of Ba is replaced with a rare earth element. It is preferably composed of ceramics.
  • a "main component” means a component which accounts for more than 50% by mass in the whole component.
  • the content of BaTiO 3 crystal particles can be determined by, for example, fluorescence X-ray analysis, EDAX (energy dispersive X-ray) analysis, or the like. Other crystal particles can be measured in the same manner as this method.
  • the composition formula of the BaTiO 3 crystal particles in which a part of Ba is replaced with a rare earth element can be represented by (Ba 1-x A x ) TiO 3 .
  • A represents one or more rare earth elements, and 0.0001 ⁇ x ⁇ 0.010.
  • A is not particularly limited as long as it is a rare earth element, but is preferably one or more selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Eu, Gd, Dy, Ho, Er and Yb. , More preferably La. x is preferably 0.001 or more, more preferably 0.0015 or more, still more preferably 0.002 or more, from the viewpoint of suppressing the electric resistance from becoming too high at room temperature.
  • x is preferably 0.010 or less, more preferably 0.009 or less, still more preferably 0.008 or less, from the viewpoint of suppressing insufficient sintering and excessively high electrical resistance at room temperature. ..
  • the BaTIO 3 -based crystal particles in which a part of Ba is replaced with a rare earth element has a (Ba + rare earth element) / Ti ratio, preferably 1.005 to 1.050.
  • the element ratios of Ba, rare earth elements and Ti can be determined by, for example, fluorescent X-ray analysis, ICP-MS (inductively coupled plasma mass spectrometry) and the like.
  • the BaTIO 3 crystal particles in which a part of Ba is replaced with a rare earth element has an average crystal grain size of preferably 5 to 200 ⁇ m, more preferably 5 to 180 ⁇ m, and further preferably 5 to 160 ⁇ m. By controlling the average crystal grain size within such a range, the electrical resistance at room temperature can be stably reduced.
  • the average crystal grain size of the BaTiO 3 crystal particles can be measured as follows. A 5 mm ⁇ 5 mm ⁇ 5 mm square sample is cut out from the ceramics and embedded in resin. The embedded sample is mirror-polished by mechanical polishing and observed by SEM.
  • the average crystal grain size is the average of four or more SEM observation images obtained by dividing the length of the straight line by the number of BaTiO 3 crystal particles.
  • the content of the BaTiO 3 crystal particles in which a part of Ba is replaced with a rare earth element in the ceramics is not particularly limited as long as it is the main component, but is preferably 90% by mass or more, more preferably 92% by mass or more. , More preferably 94% by mass or more.
  • the upper limit of the content of the BaTiO 3 crystal particles is not particularly limited, but is generally 99% by mass, preferably 98% by mass.
  • the content of the BaTiO 3 crystal particles can be measured by, for example, fluorescent X-ray analysis or EDAX (energy dispersive X-ray) analysis. Other crystal particles can be measured in the same manner as this method.
  • the ceramics used for the outer peripheral wall 11 and the partition wall 12 preferably contain Ba 6 Ti 17 O 40 crystal particles.
  • the presence of Ba 6 Ti 17 O 40 crystal particles in ceramics can reduce the electrical resistance at room temperature.
  • Ba 6 Ti 17 O 40 crystal particles are liquid phased during the firing process to promote rearrangement, grain growth and densification of BaTIO 3 crystal particles. Therefore, it is considered that the electrical resistance at room temperature decreases.
  • the content of Ba 6 Ti 17 O 40 crystal particles in the ceramics is 1.0 to 10.0% by mass, preferably 1.2 to 8.0% by mass, and more preferably 1.5 to 6.0% by mass. be.
  • the content of Ba 6 Ti 17 O 40 crystal particles in the ceramics is 1.0 to 10.0% by mass, preferably 1.2 to 8.0% by mass, and more preferably 1.5 to 6.0% by mass. be.
  • the ceramics used for the outer peripheral wall 11 and the partition wall 12 can further contain BaCO 3 crystal particles.
  • BaCO 3 crystal particles are crystal particles derived from BaCO 3 powder, which is a raw material for ceramics. BaCO 3 crystal particles do not have to be contained in the ceramic because they have almost no effect on the electrical resistance of the ceramic at room temperature. However, if the content of BaCO 3 crystal particles in the ceramics is too large, it may affect the electrical resistance at room temperature, and the number of other crystal particles may decrease, so that the desired characteristics may not be obtained. Therefore, the content of BaCO 3 crystal particles is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, and further preferably 1.5% by mass or less. The lower limit of the content of BaCO 3 crystal particles is not particularly limited, but is generally 0.1% by mass, preferably 0.2% by mass.
  • the ceramics used for the outer peripheral wall 11 and the partition wall 12 may further contain components conventionally added to the PTC material in addition to the above crystal particles.
  • Such components include additives such as shifters, property improvers, metal oxides and conductor powders, as well as unavoidable impurities.
  • the ceramics used for the outer peripheral wall 11 and the partition wall 12 substantially do not contain lead (Pb) from the viewpoint of reducing the environmental load.
  • the ceramics have a Pb content of preferably 0.01% by mass or less, more preferably 0.001% by mass or less, and further preferably 0% by mass. Due to the low Pb content, for example, warmed air can be safely applied to organisms such as humans by contacting them with ceramics.
  • the Pb content is preferably less than 0.03% by mass, more preferably less than 0.01% by mass, and further preferably 0% by mass when converted to PbO.
  • the lead content can be determined by, for example, fluorescent X-ray analysis, ICP-MS (inductively coupled plasma mass spectrometry), or the like.
  • the ceramics used for the outer peripheral wall 11 and the partition wall 12 substantially do not contain an alkali metal which may affect the electric resistance at room temperature.
  • the ceramics have an alkali metal content of preferably 0.01% by mass or less, more preferably 0.001% by mass or less, and further preferably 0% by mass.
  • the alkali metal content can be determined by, for example, fluorescent X-ray analysis, ICP-MS (inductively coupled plasma mass spectrometry), or the like.
  • the Curie point of the material constituting the outer peripheral wall 11 and the partition wall 12 is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and further preferably 125 ° C. or higher from the viewpoint of efficiently heating air for heating.
  • the upper limit of the Curie point is preferably 250 ° C., more preferably 225 ° C., still more preferably 200 ° C., still more preferably 150 ° C. from the viewpoint of safety as a part placed in or near the vehicle interior. °C.
  • the Curie points of the materials constituting the outer peripheral wall 11 and the partition wall 12 can be adjusted by the type of shifter and the amount of addition.
  • the Curie point of barium titanate (BaTIO 3 ) is about 120 ° C., but the Curie point is shifted to the low temperature side by substituting a part of Ba and Ti with one or more of Sr, Sn and Zr. Can be done.
  • the Curie point is measured by the following method.
  • the sample is attached to a sample holder for measurement, mounted in a measuring tank (example: MINI-SUBZERO MC-810P, manufactured by Tabai Espec), and the change in electrical resistance of the sample with respect to the temperature change when the temperature rises from 10 ° C. , Measured using a DC resistance meter (eg, multimeter 3478A, manufactured by YHP).
  • a DC resistance meter eg, multimeter 3478A, manufactured by YHP
  • the thickness of the partition wall 12 in the honeycomb structure 10 is preferably 0.3 mm or less, more preferably 0.25 mm or less, still more preferably 0.2 mm or less.
  • the thickness of the partition wall 12 is preferably 0.02 mm or more, more preferably 0.04 mm or more, still more preferably 0.06 mm or more.
  • the thickness of the partition wall 12 refers to the length at which the line segment crosses the partition wall 12 when the centers of gravity of adjacent cells 14 are connected by a line segment in a cross section orthogonal to the flow path direction of the cell 14.
  • the thickness of the partition wall 12 refers to the average value of the thicknesses of all the partition walls 12.
  • the thickness of the outer peripheral wall 11 is preferably 0.05 mm or more, more preferably 0.06 mm or more, still more preferably 0.08 mm or more.
  • the thickness of the outer peripheral wall 11 is preferably 1.0 mm or less, more preferably 0.5 mm or less. It is more preferably 0.4 mm or less, and even more preferably 0.3 mm or less.
  • the thickness of the outer peripheral wall 11 is the normal of the side surface from the boundary between the outer peripheral wall 11 and the outermost cell 14 or the partition wall 12 to the side surface of the honeycomb structure 10 in the cross section orthogonal to the flow path of the cell 14. Refers to the length in the direction.
  • the cell density of the honeycomb structure 10 is preferably 93 cells / cm 2 or less, more preferably 62 cells / cm 2 or less.
  • the cell pitch of the honeycomb structure 10 is preferably 1.0 mm or more, more preferably 1.3 mm or more. By controlling the cell density or cell pitch within such a range, the ventilation resistance can be suppressed and the output of the blower can be suppressed.
  • the lower limit of the cell density of the honeycomb structure 10 is not particularly limited, but is preferably 10 cells / cm 2 and more preferably 20 cells / cm 2 .
  • the upper limit of the cell pitch of the honeycomb structure 10 is also not particularly limited, but is preferably 3.0 mm, more preferably 2.0 mm.
  • the cell density of the honeycomb structure 10 is a value obtained by dividing the number of cells by the area of each end face of the honeycomb structure 10.
  • the cell pitch of the honeycomb structure 10 refers to the length of a line segment connecting the centers of gravity of two adjacent cells 14 on each end surface of the honeycomb structure 10.
  • the volume resistivity of the honeycomb structure 10 (outer peripheral wall 11 and partition wall 12) at room temperature (25 ° C.) is preferably 0.5 to 1000 ⁇ ⁇ cm. If the volume resistivity is in such a range, it can be said that the electrical resistance at room temperature is low. Then, by lowering the electric resistance at room temperature, it is possible to secure the heat generation performance required for heating and to suppress the increase in power consumption.
  • the pair of electrode layers 20 are provided on the surface of the outer peripheral wall 11 of the honeycomb structure 10, compared with the case where the pair of electrode layers 20 are provided on the end faces (first end face 13a, second end face 13b) of the honeycomb structure 10.
  • the distance between the electrodes becomes large, but by setting the volume resistivity in such a range, the heat generation performance required for heating can be obtained.
  • the volume resistivity of the honeycomb structure at room temperature is preferably 10 to 1000 ⁇ ⁇ cm.
  • the volume resistivity of the honeycomb structure at room temperature is preferably 0.5 to 100 ⁇ ⁇ cm.
  • the volume resistivity of the honeycomb structure 10 is measured as follows. Two or more test pieces having dimensions of 30 mm ⁇ 30 mm ⁇ 15 mm are randomly cut and collected from the honeycomb structure 10. Then, the electrical resistance at the measurement temperature is measured by the two-terminal method, and the volume resistivity is calculated from the shape of the test piece. The average value of the volume resistivity of all the test pieces is taken as the measured value at the measured temperature.
  • the aperture ratio of the honeycomb structure 10 is preferably 80% or more, more preferably 85% or more. By controlling the aperture ratio within this range, it is possible to suppress the pressure loss when the gas passes.
  • the upper limit of the aperture ratio of the honeycomb structure 10 is not particularly limited, but is preferably 95%, more preferably 90%. By controlling the aperture ratio within this range, the strength of the honeycomb structure 10 can be maintained.
  • the aperture ratio of the honeycomb structure 10 is obtained by dividing the area of the cell 14 by the area of the entire cross section (total area of the outer peripheral wall 11, the partition wall 12 and the cell 14) in the cross section orthogonal to the central axis X1 of the honeycomb structure 10. It is a value expressed as a percentage of the value obtained in the above.
  • the heater element 100 includes a pair of electrode layers 20 arranged on the surface of the outer peripheral wall 11.
  • the pair of electrode layers 20 are formed in a band shape extending parallel to the central axis X1 of the honeycomb structure 10. Further, the pair of electrode layers 20 are arranged on the surface of the outer peripheral wall 11 so as to face each other with the long axis X2 passing through the center of gravity of the honeycomb structure 10 in a cross section orthogonal to the central axis X1 of the honeycomb structure 10. Orthogonal.
  • the electrode layer 20 is not particularly limited, but for example, a metal or alloy containing at least one selected from Cu, Ag, Al, Ni and Si can be used. It is also possible to use an ohmic electrode layer capable of ohmic contact with the outer peripheral wall 11 and / or the partition wall 12 having PTC characteristics.
  • the ohmic electrode layer contains, for example, at least one selected from Au, Ag and In as the base metal, and at least one selected from Ni, Si, Ge, Sn, Se and Te for n-type semiconductors as the dopant.
  • the contained ohmic electrode layer can be used.
  • the electrode layer 20 may be one layer or two or more layers. When the electrode layers 20 are two or more layers, the materials of the respective layers may be the same type or different types.
  • the thickness of the electrode layer 20 is not particularly limited and can be appropriately set according to the method of forming the electrode layer 20.
  • the method for forming the electrode layer 20 include metal precipitation methods such as sputtering, vapor deposition, electrolytic precipitation, and chemical precipitation.
  • the electrode layer 20 can be formed by applying the electrode paste and then baking it. Further, the electrode layer 20 can also be formed by thermal spraying.
  • the thickness of the electrode layer 20 is about 5 to 30 ⁇ m for baking of the electrode paste, about 100 to 1000 nm for dry plating such as sputtering and vapor deposition, about 10 to 100 ⁇ m for thermal spraying, and for wet plating such as electrolytic precipitation and chemical precipitation. It is preferably about 5 to 30 ⁇ m.
  • the heater element 100 includes a plate-shaped external connecting member 30 that is arranged on the end side of each electrode layer 20 and is in contact with each electrode layer 20 in a plane.
  • the plate-shaped external connecting member 30 By disposing the plate-shaped external connecting member 30 on each electrode layer 20 in this way, it becomes easy to increase the amount of power supplied from the outside to the electrode layer 20, so that the heat generation performance can be improved.
  • the end side of each electrode layer 20 means the total length of each electrode layer 20 from the end of each electrode layer 20 in the long axis X2 direction passing through the center of gravity of the honeycomb structure 10. Means the area up to 30% of.
  • the external connecting member 30 may be arranged on the end side of each electrode layer 20, and may not necessarily be in contact with the end of each electrode layer 20.
  • a bent portion may be formed in the external connecting member 30, and the bent portion may be connected to each electrode layer 20.
  • the external connecting member 30 preferably has a width substantially the same as the width of the end portion of the electrode layer 20 on the side where the external connecting member 30 is arranged. With such a configuration, the contact area between the electrode layer 20 and the external connecting member 30 is increased, so that the effect of improving the heat generation performance is enhanced.
  • the width substantially the same as the width of the end portion of the electrode layer 20 means within ⁇ 20% of the width of the end portion of the electrode layer 20.
  • Each of the external connecting members 30 is arranged on one end side of the electrode layer 20 parallel to the central axis X1.
  • One end side on which the external connecting member 30 is arranged may be the same side (for example, FIGS. 1 to 5) or different in the direction of the major axis X2 of the honeycomb structure 10 (for example, FIGS. 1 to 5). For example, FIG. 6).
  • the one end side is more preferably the same side.
  • each of the external connecting members 30 extends in the same direction from the end side thereof toward the outside. With such a configuration, when applied to the heater element 100, it becomes possible to make it compact.
  • the material of the external connecting member 30 is not particularly limited, but may be, for example, metal.
  • the metal a single metal, an alloy, or the like can be adopted, but from the viewpoint of corrosion resistance, electrical resistance, and linear expansion rate, for example, it is selected from the group consisting of Cr, Fe, Co, Ni, Cu, and Ti. It is preferable to use an alloy containing at least one kind, and stainless steel, Fe—Ni alloy, and phosphorus bronze are more preferable.
  • the shape and size of the external connecting member 30 are not particularly limited, and may be appropriately adjusted according to the structure of the heater unit to be manufactured.
  • the method of connecting the external connecting member 30 and the electrode layer 20 is not particularly limited as long as they are electrically connected, and can be connected by, for example, diffusion joining, a mechanical pressurizing mechanism, welding, or the like.
  • the method for manufacturing the honeycomb structure 10 includes a molding step and a firing step.
  • clay containing a ceramic raw material containing BaCO 3 powder, TiO 2 powder, and rare earth nitrate or hydroxide powder is molded to prepare a honeycomb molded body having a relative density of 60% or more.
  • the ceramic raw material can be obtained by dry-mixing each powder so as to have a desired composition.
  • the sol can be obtained by adding a dispersion medium, a binder, a plasticizer and a dispersant to a ceramic raw material and kneading them.
  • the clay may contain additives such as shifters, metal oxides, property improvers, and conductor powders, if necessary.
  • the blending amount of the components other than the ceramic raw material is not particularly limited as long as the relative density of the honeycomb molded product is 60%.
  • dispersion medium examples include water or a mixed solvent of water and an organic solvent such as alcohol, and water can be particularly preferably used.
  • binder examples include organic binders such as methyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol. In particular, it is preferable to use methyl cellulose and hydroxypropoxyl cellulose in combination.
  • organic binders such as methyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol.
  • methyl cellulose and hydroxypropoxyl cellulose in combination.
  • One type of binder may be used alone, or two or more types may be used in combination, but it is preferable that the binder does not contain an alkali metal element.
  • plasticizer examples include polyoxyalkylene alkyl ethers, polycarboxylic acid-based polymers, and alkyl phosphoric acid esters.
  • a surfactant such as polyoxyalkylene alkyl ether, ethylene glycol, dextrin, fatty acid soap, or polyalcohol can be used.
  • the dispersant may be used alone or in combination of two or more.
  • the honeycomb molded body can be produced by extrusion molding the clay.
  • a mouthpiece having a desired overall shape, cell shape, partition wall thickness, cell density and the like can be used.
  • the relative density of the honeycomb molded product obtained by extrusion molding is 60% or more, preferably 61% or more. By controlling the relative density of the honeycomb molded body within such a range, the honeycomb molded body can be densified and the electric resistance at room temperature can be reduced.
  • the upper limit of the relative density of the honeycomb molded product is not particularly limited, but is generally 80%, preferably 75%.
  • the honeycomb molded body can be dried before the firing step.
  • the drying method is not particularly limited, and for example, conventionally known drying methods such as hot air drying, microwave drying, dielectric drying, vacuum drying, vacuum drying, and freeze drying can be used. Among these, a drying method that combines hot air drying and microwave drying or dielectric drying is preferable in that the entire molded product can be dried quickly and uniformly.
  • the firing step includes holding at 1150 to 1250 ° C., then raising the temperature to a maximum temperature of 1360 to 1430 ° C. at a heating rate of 20 to 500 ° C./hour, and holding the temperature for 0.5 to 10 hours.
  • a honeycomb structure 10 containing a BaTIO 3 crystal particle in which a part of Ba is replaced with a rare earth element is obtained. be able to.
  • the Ba 2 TiO 4 crystal particles generated in the firing process can be easily removed, so that the honeycomb structure 10 can be densified.
  • the holding time at 1150 to 1250 ° C. is not particularly limited, but is preferably 0.5 to 10 hours. With such a holding time, Ba 2 TiO 4 crystal particles generated in the firing process can be stably removed easily.
  • the firing step preferably comprises holding at 900 to 950 ° C. for 0.5 to 5 hours.
  • the mixture By holding the mixture at 900 to 950 ° C. for 0.5 to 5 hours, BaCO 3 is efficiently decomposed, and a honeycomb structure 10 having a predetermined composition can be easily obtained.
  • a degreasing step for removing the binder may be performed before the firing step.
  • the atmosphere of the degreasing step is preferably an air atmosphere in order to completely decompose the organic components. Further, the atmosphere of the firing process is preferably an atmospheric atmosphere from the viewpoint of controlling electrical characteristics and manufacturing cost.
  • the firing furnace used in the firing step and the degreasing step is not particularly limited, but an electric furnace, a gas furnace, or the like can be used.
  • the electrode layer 20 is formed on a predetermined surface of the outer peripheral wall 11 of the honeycomb structure 10 thus obtained.
  • the electrode layer 20 can be formed by the method described above.
  • the electrode layer 20 may be a single layer, but may be a plurality of layers having different compositions.
  • the external connecting member 30 is connected to the electrode layer 20.
  • the above method can be used.
  • the heater element 100 can generate heat of the honeycomb structure 10 by applying a voltage from the external connecting member 30 via the pair of electrode layers 20.
  • a voltage from the external connecting member 30 via the pair of electrode layers 20 As the applied voltage, from the viewpoint of rapid heating, it is preferable to apply a voltage of 200 V or more, and more preferably a voltage of 250 V or more is applied.
  • the gas can be heated by flowing the gas through the cell 14.
  • the temperature of the gas flowing into the cell 14 can be, for example, ⁇ 60 ° C. to 20 ° C., and typically ⁇ 10 ° C. to 20 ° C.
  • the heater element 100 according to the embodiment of the present invention by disposing the electrode layer 20 and the external connecting member 30 as described above, it becomes easy to increase the amount of power supplied from the outside to the electrode layer 20, and thus the heat generation performance is improved. Can be made to. Further, the heater element 100 according to the embodiment of the present invention has a simpler structure than an existing heater element in which a PTC element and an aluminum fin are integrated via an insulating ceramic plate, and the heater unit becomes larger. It is possible to suppress that. Further, in the existing heater element, the heating rate (heating time) of the gas is not sufficient because the PTC element does not come into direct contact with the gas. However, the heater element 100 according to the embodiment of the present invention has the outer peripheral wall 11 and the partition wall. Since the honeycomb structure 10 in which 12 is made of a material having PTC characteristics is in direct contact with the gas, the rate of temperature rise of the gas can be increased.
  • the heater element according to the embodiment of the present invention can also be suitably used as a heater element for purifying the passenger compartment of a vehicle.
  • FIG. 9 shows a schematic partially enlarged cross-sectional view orthogonal to the central axis of the honeycomb structure 10 of the heater element used in this embodiment.
  • the heater element used in this embodiment further includes a functional material-containing layer 40 provided on the surface of the partition wall 12 of the honeycomb structure 10.
  • a functional material-containing layer 40 provided on the surface of the partition wall 12 of the honeycomb structure 10.
  • a pair of electrode layers 20 are formed in a band shape extending parallel to the central axis X1 and pass through the center of gravity of the honeycomb structure 10 in a cross section orthogonal to the central axis X1. It is arranged on the surface of the outer peripheral wall 11 so as to face each other with the long axis X2 interposed therebetween. Therefore, as compared with the form in which the pair of electrode layers 20 are provided on both end faces (first end face 13a, second end face 13b) of the honeycomb structure 10, the honeycomb structure 10 can be heated uniformly, so that the functional material can be heated.
  • the content layer 40 can be uniformly heated so that the function of the functional material can be effectively exhibited.
  • the honeycomb structure 10 on the cold inlet (for example, the first end surface 13a) side is low when a voltage is applied. While the current concentrates due to the resistance, the relatively warm outlet (for example, the second end surface 13b) side becomes a high resistance and the current is throttled. It is considered that this makes it easier to uniformly heat the entire honeycomb structure 10 and effectively expresses the function of the functional material.
  • the functional material contained in the functional material-containing layer 40 is not particularly limited, but an adsorbent, a catalyst, or the like can be used.
  • the functional material-containing layer 40 preferably contains, for example, an adsorbent. By containing the adsorbent, it is possible to capture the component to be removed in the air of the vehicle interior.
  • the functional material-containing layer 40 can contain a catalyst. By using a catalyst, the component to be removed can be purified. Further, the adsorbent and the catalyst may be used in combination for the purpose of enhancing the capture function of the component to be removed by the adsorbent.
  • the adsorbent preferably has a function of adsorbing components to be removed (for example, water vapor, carbon dioxide, odor components), adsorbs the components to be removed at -20 to 40 ° C, and desorbs them at a high temperature of 60 ° C or higher. It is more preferable to have a function capable of performing. Examples of the adsorbent having such a function include zeolite, silica gel, activated carbon, alumina, silica, low crystalline clay, and amorphous aluminum silicate complex. The type of the adsorbent may be appropriately selected according to the type of the component to be removed.
  • the catalyst preferably has a function capable of promoting a redox reaction. Examples of the catalyst having such a function include metal catalysts such as Pt, Pd and Ag, and oxide catalysts such as CeO 2 and ZrO 2 .
  • the components to be removed in the air of the passenger compartment are, for example, water vapor, carbon dioxide, and odor components.
  • odor components include ammonia, acetic acid, isovaleric acid, nonenal, formaldehyde, toluene, xylene, paradichlorobenzene, ethylbenzene, styrene, chlorpyriphos, di-n-butyl phthalate, tetradecane, and di-2-ethylhexyl phthalate.
  • Diadinone acetaldehyde, N-methylcarbamic acid-2- (1-methylpropyl) phenyl and the like.
  • the honeycomb structure 10 of the heater element used in this embodiment has a partition wall 12 having a thickness of preferably 0.125 mm or less, more preferably 0., from the viewpoint of supporting a sufficient amount of functional material on the honeycomb structure 10. It is 10 mm or less, more preferably 0.08 mm or less. From the same viewpoint, the cell density is preferably 100 cells / cm 2 or less, more preferably 70 cells / cm 2 or less, further preferably 65 cells / cm 2 or less, and the cell pitch is preferably 1.0 mm or more. , More preferably 1.2 mm or more, still more preferably 1.3 mm or more.
  • the heater unit according to the embodiment of the present invention can be suitably used as a heater unit for heating the passenger compartment of a vehicle.
  • the heater unit according to the embodiment of the present invention uses the heater element 100 having high heat generation performance, the heat generation performance of the heater unit can be improved. Further, since the heater element 100 can be made compact, it is possible to prevent the heater unit from becoming large.
  • FIG. 10 is a schematic front view of the heater unit according to the embodiment of the present invention as viewed from the first end surface side of the heater element.
  • the heater unit 600 according to the embodiment of the present invention includes two or more heater elements 100. Further, in the heater unit 600, the heater elements 100 are laminated and arranged so that the surfaces of the outer peripheral walls 11 of the honeycomb structure 10 including the long sides 16 of the first end surface 13a and the second end surface 13b face each other. With such a configuration, a compact heater unit 600 can be manufactured.
  • the heater unit 600 may further include a housing (housing member) 610.
  • the material of the housing 610 is not particularly limited, and examples thereof include metal and resin. Among them, the material of the housing 610 is preferably resin. By using the resin housing 610, electric shock can be suppressed without grounding.
  • the shape and size of the housing 610 are not particularly limited, and can be the same as the existing heater unit.
  • the heater unit 600 may further include an insulating material 620 arranged between the heater elements 100 which are laminated and arranged. With such a configuration, it is possible to suppress an electrical short circuit between the plurality of heater elements 100.
  • an insulating material 620 a plate material, a mat, a cloth, or the like formed from an insulating material such as alumina or ceramics can be used.
  • the heater unit 600 according to the embodiment of the present invention has a wiring structure capable of controlling the heater element 100.
  • the heater unit 600 according to the embodiment of the present invention can further include a wiring 630 connected to the external connection member 30 of the heater element 100.
  • the wiring structure is not particularly limited, but as shown in FIG. 10, each of the heater elements 100 can be independently controllable.
  • the wiring 630 can be connected to each of the external connection members 30 of the heater element 100.
  • the wiring 630 is connected to an external power source (not shown). With such a wiring structure, each of the heater elements 100 can be controlled independently, so that fine temperature adjustment is possible.
  • the wiring structure may be a parallel wiring structure capable of collectively controlling two or more heater elements 100.
  • the parallel wiring 640a may be connected to one of the external connection members 30 of each heater element 100, and one parallel wiring 640b may be connected to the other external connection member 30.
  • the power consumption of the heater unit 700 can be suppressed.
  • the electrode layer 20 between the heater elements 100 arranged in a laminated manner is set as one electrode layer 20 common to the heater elements 100 arranged in a laminated manner, and two or more heater elements 100 are used.
  • a parallel wiring structure that can be controlled collectively may be used.
  • the external connection member 30 is arranged at the end of the electrode layer 20, the parallel wiring 640a is connected to one external connection member 30 of each heater element 100, and one parallel to the other external connection member 30. Wiring 640b may be connected.
  • the heater system according to the embodiment of the present invention can be suitably used as a heater system for heating the passenger compartment of a vehicle.
  • the heater unit 600 having high heat generation performance is used, the heat generation performance of the heater system can be improved.
  • the heater unit 600 can be made compact, it is possible to prevent the heater system from becoming large.
  • the heater units 700 and 800 may be used instead of the heater unit 600.
  • FIG. 13 is a schematic view showing a configuration example of the heater system according to the embodiment of the present invention.
  • the heater system 900 according to the embodiment of the present invention communicates the heater unit 600, the outside air introduction unit or the vehicle interior 910 according to the embodiment of the present invention with the inflow port 650 of the heater unit 600. It includes inflow pipes 920a and 920b, a battery 940 for applying a voltage to the heater unit 600, and an outflow pipe 930 that communicates the outlet 660 of the heater unit 600 with the passenger compartment 910.
  • the heater unit 600 can be configured to energize and generate heat by connecting to the battery 940 with an electric wire 950 and turning on the power switch in the middle, for example.
  • a steam compression heat pump 960 can be installed on the upstream side of the heater unit 600.
  • the steam compression heat pump 960 is configured as the main heating device, and the heater unit 600 is configured as the auxiliary heater.
  • the steam compression heat pump 960 includes heat including an evaporator 961 that absorbs heat from the outside during cooling and evaporates the refrigerant, and a condenser 962 that liquefies the refrigerant gas and releases heat to the outside during heating. It can be equipped with a exchanger.
  • the steam compression heat pump 960 is not particularly limited, and a steam compression heat pump 960 known in the art can be used.
  • a blower 970 can be installed on the upstream side and / or the downstream side of the heater unit 600. From the viewpoint of ensuring safety by arranging high-voltage parts as far as possible from the passenger compartment 910, it is preferable to install the blower 970 on the upstream side of the heater unit 600.
  • the blower 970 When the blower 970 is driven, air flows into the heater unit 600 from inside the passenger compartment 910 or outside the passenger compartment 910 through the inflow pipes 920a and 920b. The air is heated while passing through the heating unit 600 that is generating heat. The heated air flows out from the heater unit 600 and is sent into the passenger compartment 910 through the outflow pipe 930.
  • the outlet of the outflow pipe 930 may be arranged near the feet of the occupant so that the heating effect is particularly high even in the passenger compartment 910, or the pipe outlet may be arranged in the seat to warm the seat from the inside. Alternatively, it may be arranged near the window to have an effect of suppressing fogging of the window.
  • Valves 921a and 921b can be installed in the inflow pipe 920a and the inflow pipe 920b on the upstream side of the confluence, respectively.
  • By controlling the opening and closing of the valves 921a and 921b it is possible to switch between the mode in which the outside air is introduced into the heater unit 600 and the mode in which the air in the passenger compartment 910 is introduced into the heater unit 600. For example, when the valve 921a is opened and the valve 921b is closed, the mode is set to introduce the outside air into the heater unit 600. It is also possible to open both the valve 921a and the valve 921b to introduce the outside air and the air in the passenger compartment 910 into the heater unit 600 at the same time.
  • Example 1 A heater element A1 having a shape as shown in FIG. 14 having a cross section orthogonal to the central axis of the honeycomb joint was produced. Specifically, the heater element A1 was manufactured as follows. BaCO 3 powder, TiO 2 powder and La (NO 3 ) 3.6H 2 O powder were prepared as ceramic raw materials. These powders were weighed to have a predetermined composition after firing and dry-mixed to obtain a mixed powder. Dry mixing was carried out for 30 minutes. Next, with respect to 100 parts by mass of the obtained mixed powder, a total of 3 to 30 weights of water, a binder, a plasticizer and a dispersant were added so that a ceramic molded body having a relative density of 64.8% could be obtained after extrusion molding.
  • BaCO 3 powder, TiO 2 powder and La (NO 3 ) 3.6H 2 O powder were prepared as ceramic raw materials. These powders were weighed to have a predetermined composition after firing and dry-mixed to obtain a mixed powder. Dry mixing was carried out for 30
  • the obtained honeycomb molded body was dielectric-dried and hot-air dried, degreased in an air atmosphere (450 ° C. ⁇ 4 hours) in a firing furnace, and then calcined in an air atmosphere to obtain a honeycomb segment.
  • Got The firing was carried out by holding at 950 ° C. for 1 hour, raising the temperature to 1200 ° C. for 1 hour, raising the temperature to 1400 ° C. (maximum temperature) at 200 ° C./hour, and holding at 1400 ° C. for 2 hours.
  • the details of the obtained honeycomb segment are as follows. Content of BaTiO 3 crystal particles: 95.0% by mass Ba 6 Ti 17 O 40 Crystal particle content: 4.0% by mass The content of BaCO 3 crystal particles is 1.0% by mass, and the La atomic ratio (x value) of BaTiO 3 crystal particles: 0.001. (Ba + La) / Ti ratio of BaTiO 3 crystal particles: 1.030 Average crystal grain size of BaTiO 3 crystal particles: 20 ⁇ m
  • the content of each crystal particle was identified using an X-ray diffractometer.
  • a multifunctional powder X-ray diffractometer (D8Avance, manufactured by Bruker) was used.
  • the crystal particles were identified by analyzing the obtained X-ray diffraction data by the Rietveld method using the analysis software TOPAS (manufactured by BrukerAXS).
  • the content of each crystal particle was measured using an X-ray diffractometer.
  • the same equipment and analysis software as described above were used, and the content of each crystal particle was determined by the Rietveld method.
  • the chemical composition of the ceramics was analyzed by ICP emission spectroscopy to determine the atomic ratios of elements such as La, Ba and Ti.
  • the average crystal grain size of the ceramics was measured according to the above method.
  • the SEM observation was performed using a model S-3400N manufactured by Hitachi High-Technologies Corporation at an acceleration voltage of 15 kV and a magnification of 3000. The above measurement conditions were the same in the following examples.
  • honeycomb segments were prepared, and a bonding material was applied to the side surfaces of the honeycomb segments to join them to obtain a honeycomb bonded body.
  • a bonding material a ceramic material was used as a paste by adding a solvent such as water.
  • honeycomb joint The details of the obtained honeycomb joint are as follows. The physical property values were measured by the method described above. Shape of honeycomb joint in cross section orthogonal to the central axis: rectangular shape Cell shape in cross section orthogonal to the central axis: Square Partition thickness: 0.10 mm Cell density: 64 cells / cm 2 Cell pitch: 1.27 mm Cross section orthogonal to the direction in which the cell extends: 32 mm x 180 mm Length in the direction of cell extension: 14 mm End face area: 57.6 cm 2 Angle of bulkhead with respect to major axis: 0 ° and 90 ° Volume resistivity at room temperature (25 ° C): 14 ⁇ ⁇ cm Aperture ratio: 85% Curie point: 120 ° C
  • electrode layers were formed on both sides of the outer peripheral wall including the long side of the rectangular cross section of the honeycomb joint.
  • the Al—Ni electrode paste was applied to both sides of the outer peripheral wall, then the silver electrode paste was applied and baked at 700 ° C. to form the Al—Ni electrode layer and the silver electrode layer. ..
  • a plate-shaped external connecting member made of phosphorus bronze was connected to one end side of each electrode layer to obtain a heater element A1.
  • Example 2 The heater element A2 was produced in the same manner as in Example 1 except that the honeycomb joint having the shape shown in FIG. 8 was used as the honeycomb joint. Specifically, the heater element A2 was manufactured as follows. BaCO 3 powder, TiO 2 powder and La (NO 3 ) 3.6H 2 O powder were prepared as ceramic raw materials. These powders were weighed to have a predetermined composition after firing and dry-mixed to obtain a mixed powder. Dry mixing was carried out for 30 minutes. Next, with respect to 100 parts by mass of the obtained mixed powder, a total of 3 to 30 weights of water, binder, plasticizer and dispersant were added so that a ceramic molded body having a relative density of 63.6% could be obtained after extrusion molding.
  • BaCO 3 powder, TiO 2 powder and La (NO 3 ) 3.6H 2 O powder were prepared as ceramic raw materials. These powders were weighed to have a predetermined composition after firing and dry-mixed to obtain a mixed powder. Dry mixing was carried out for 30 minutes. Next, with
  • the obtained honeycomb molded body was dielectric-dried and hot-air dried, degreased in an air atmosphere (450 ° C. ⁇ 4 hours) in a firing furnace, and then calcined in an air atmosphere to obtain a honeycomb segment.
  • Got The firing was carried out by holding at 950 ° C. for 1 hour, raising the temperature to 1200 ° C. for 1 hour, raising the temperature to 1400 ° C. (maximum temperature) at 50 ° C./hour, and holding at 1400 ° C. for 2 hours.
  • the details of the obtained honeycomb segment are as follows. Content of BaTiO 3 crystal particles: 97.3% by mass Ba 6 Ti 17 O 40 Crystal particle content: 3.9% by mass The content of BaCO 3 crystal particles is 1.0% by mass, and the La atomic ratio (x value) of BaTiO 3 crystal particles: 0.002. (Ba + La) Ti ratio of BaTIO 3 crystal particles: 1.010 Average crystal grain size of BaTiO 3 crystal particles: 8 ⁇ m
  • a bonding material was applied to the side surfaces of the honeycomb segments to join them to obtain a honeycomb bonded body as shown in FIG.
  • a ceramic material was used as a paste by adding a solvent such as water.
  • honeycomb joint The details of the obtained honeycomb joint are as follows. The physical property values were measured by the method described above. Shape of honeycomb joint in cross section orthogonal to the central axis: rectangular shape Cell shape in cross section orthogonal to the central axis: Square Partition thickness: 0.10 mm Cell density: 64 cells / cm 2 Cell pitch: 1.27 mm Cross section orthogonal to the direction in which the cell extends: 32 mm x 180 mm Length in the direction of cell extension: 14 mm End face area: 57.6 cm 2 Angle of bulkhead with respect to major axis: 45 ° Volume resistivity at room temperature (25 ° C): 30 ⁇ ⁇ cm Aperture ratio: 85% Curie point: 120 ° C
  • electrode layers were formed on both sides of the outer peripheral wall including the long side of the rectangular cross section of the honeycomb joint.
  • an Al—Ni electrode paste was applied to both sides of the outer peripheral wall, then a silver electrode paste was applied and baked at 700 ° C. to form an Al—Ni electrode layer and a silver electrode layer. ..
  • a plate-shaped external connecting member made of phosphorus bronze was connected to one end side of each electrode layer to obtain a heater element A2.
  • Example 3 Using the same clay as in Example 1, a heater element A3 having a shape whose cross section orthogonal to the central axis of the honeycomb structure is shown in FIG. 2 was produced. Specifically, the heater element A3 was manufactured as follows. A honeycomb structure was obtained under the same conditions as in Example 1 except that extrusion molding was performed so that the cross section orthogonal to the central axis became a honeycomb structure having a shape as shown in FIG.
  • honeycomb structure shape in cross section orthogonal to the central axis rectangular Cell shape in cross section orthogonal to the central axis: Square partition wall thickness: 0.13 mm Cell density: 64 cells / cm 2 Cell pitch: 1.30 mm Cross section orthogonal to the direction in which the cell extends: 32 mm x 175 mm Length in the direction of cell extension: 14 mm End face area: 57.6 cm 2 Angle of bulkhead with respect to major axis: 45 ° Volume resistivity at room temperature (25 ° C): 14 ⁇ ⁇ cm Aperture ratio: 85% Curie point: 120 ° C
  • electrode layers were formed on both sides of the outer peripheral wall including the long side of the rectangular cross section of the honeycomb structure.
  • an Al—Ni electrode paste was applied to both sides of the outer peripheral wall, then a silver electrode paste was applied and baked at 700 ° C. to form an Al—Ni electrode layer and a silver electrode layer. ..
  • a plate-shaped external connecting member made of phosphorus bronze was connected to one end side of each electrode layer to obtain a heater element A3.
  • the heater elements A1 and A2 obtained above were placed in an evaluation box having a gas inlet and outlet as shown in FIG.
  • An energization heating test was conducted by applying 200 V to the heater elements A1 and A2 while flowing the gas into the evaluation box at 400 L / min from the gas inlet.
  • the temperature of the gas at the gas outlet was measured.
  • the measurement point was a position where the distance L to the ends of the heater elements A1 and A2 was 100 mm.
  • the heater element A1 reached 60 ° C. in 10 seconds.
  • the heater element A2 reached 80 ° C. in 10 seconds.
  • the temperature reached 80 ° C. in 10 seconds.
  • the heater element A2 can uniformly heat the honeycomb joint as compared with the heater element A1. Further, as a result of continuing to apply electric power in the energization heating test, the heater element A1 had deformation and cracks in the partition wall near the electrode layer, whereas the heater element A2 did not have such deformation and cracks. .. Therefore, it is considered that the heater element A2 can further suppress deformation and cracking of the partition wall of the honeycomb structure.
  • a heater element for heating the passenger compartment which can increase the amount of power supplied from the outside and improve the heat generation performance, and a heater element for heating the passenger compartment using this heater element.
  • Heater units and heater systems can be provided. Further, according to the present invention, it is possible to provide a heater element that can also be used for purifying a vehicle interior.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Resistance Heating (AREA)
PCT/JP2021/033211 2021-01-15 2021-09-09 車室暖房用のヒーターエレメント、ヒーターユニット及びヒーターシステム、並びに車室浄化用のヒーターエレメント WO2022153594A1 (ja)

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JP2022575067A JPWO2022153594A1 (US20100012521A1-20100121-C00001.png) 2021-01-15 2021-09-09
CN202180089723.1A CN116685484A (zh) 2021-01-15 2021-09-09 车厢供暖用加热器构件、加热器单元及加热器系统、以及车厢净化用加热器构件
DE112021006821.0T DE112021006821T5 (de) 2021-01-15 2021-09-09 Heizelement zum erwärmen einer fahrzeugkabine, heizeinheit, heizsystem und heizelement zum reinigen einer fahrzeugkabine
US18/349,345 US20230354479A1 (en) 2021-01-15 2023-07-10 Heater element for heating vehicle cabin, heater unit, heater system, and heater element for purifying vehicle cabin

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JP2021-005358 2021-01-15

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55102795U (US20100012521A1-20100121-C00001.png) * 1979-01-13 1980-07-17
JPS5692036U (US20100012521A1-20100121-C00001.png) * 1979-12-18 1981-07-22
JPH0227697U (US20100012521A1-20100121-C00001.png) * 1988-08-11 1990-02-22
JPH0446389U (US20100012521A1-20100121-C00001.png) * 1990-08-20 1992-04-20
JPH04341787A (ja) * 1991-05-17 1992-11-27 Sharp Corp 暖房機を兼ねる空気清浄機
JPH08150323A (ja) * 1994-11-30 1996-06-11 Matsushita Electric Ind Co Ltd 脱臭装置
JP2013020936A (ja) * 2011-03-24 2013-01-31 Ngk Insulators Ltd ヒーター
JP2014054934A (ja) * 2012-09-13 2014-03-27 Ngk Insulators Ltd ヒーター
WO2020036067A1 (ja) * 2018-08-13 2020-02-20 日本碍子株式会社 車室暖房用ヒーターエレメント及びその使用方法、並びに車室暖房用ヒーター

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55102795U (US20100012521A1-20100121-C00001.png) * 1979-01-13 1980-07-17
JPS5692036U (US20100012521A1-20100121-C00001.png) * 1979-12-18 1981-07-22
JPH0227697U (US20100012521A1-20100121-C00001.png) * 1988-08-11 1990-02-22
JPH0446389U (US20100012521A1-20100121-C00001.png) * 1990-08-20 1992-04-20
JPH04341787A (ja) * 1991-05-17 1992-11-27 Sharp Corp 暖房機を兼ねる空気清浄機
JPH08150323A (ja) * 1994-11-30 1996-06-11 Matsushita Electric Ind Co Ltd 脱臭装置
JP2013020936A (ja) * 2011-03-24 2013-01-31 Ngk Insulators Ltd ヒーター
JP2014054934A (ja) * 2012-09-13 2014-03-27 Ngk Insulators Ltd ヒーター
WO2020036067A1 (ja) * 2018-08-13 2020-02-20 日本碍子株式会社 車室暖房用ヒーターエレメント及びその使用方法、並びに車室暖房用ヒーター

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DE112021006821T5 (de) 2024-01-18
CN116685484A (zh) 2023-09-01

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