WO2014049692A1 - 二次電池用電極の製造方法および熱風乾燥炉 - Google Patents
二次電池用電極の製造方法および熱風乾燥炉 Download PDFInfo
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- WO2014049692A1 WO2014049692A1 PCT/JP2012/074584 JP2012074584W WO2014049692A1 WO 2014049692 A1 WO2014049692 A1 WO 2014049692A1 JP 2012074584 W JP2012074584 W JP 2012074584W WO 2014049692 A1 WO2014049692 A1 WO 2014049692A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B13/00—Machines and apparatus for drying fabrics, fibres, yarns, or other materials in long lengths, with progressive movement
- F26B13/10—Arrangements for feeding, heating or supporting materials; Controlling movement, tension or position of materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B13/00—Machines and apparatus for drying fabrics, fibres, yarns, or other materials in long lengths, with progressive movement
- F26B13/10—Arrangements for feeding, heating or supporting materials; Controlling movement, tension or position of materials
- F26B13/108—Arrangements for feeding, heating or supporting materials; Controlling movement, tension or position of materials using one or more blowing devices, e.g. nozzle bar, the effective area of which is adjustable to the width of the material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
- F26B21/004—Nozzle assemblies; Air knives; Air distributors; Blow boxes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
- F26B21/06—Controlling, e.g. regulating, parameters of gas supply
- F26B21/10—Temperature; Pressure
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B3/00—Drying solid materials or objects by processes involving the application of heat
- F26B3/02—Drying solid materials or objects by processes involving the application of heat by convection, i.e. heat being conveyed from a heat source to the materials or objects to be dried by a gas or vapour, e.g. air
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for manufacturing a secondary battery electrode and a hot air drying furnace used in the method.
- the process of manufacturing the electrode constituting the secondary battery includes a process of applying the electrode paste on the surface of the electrode foil, a process of drying the electrode paste (that is, removing the solvent), and the like.
- a hot air drying furnace is generally used for drying the electrode paste.
- the outline of the process of drying the electrode paste using a hot air drying furnace is that the electrode foil coated with the electrode paste on the surface is transported to the inside of the hot air drying furnace, and inside the hot air drying furnace, Hot air is blown from the nozzle to the upper electrode paste to evaporate the solvent (NMP (N-methylpyrrolidone), water, etc.) contained in the electrode paste, thereby removing the solvent.
- “removal” is a concept including making the residual amount of the solvent not more than a predetermined standard value, and does not mean that the solvent is completely removed.
- the temperature of the hot air is lowered by the latent heat of evaporation generated when the solvent evaporates.
- the standard value for the residual amount of solvent after drying is set for the secondary battery electrode, it has been found that the residual amount of solvent increases when the temperature of the hot air decreases.
- the conventional hot air drying furnace is configured to increase the amount of hot air so as to suppress the effect of temperature drop due to latent heat of vaporization and to ensure a drying condition in which the residual amount of solvent is not more than a standard value.
- the amount of hot air in the hot air drying furnace that is, the amount of outside air introduced
- the increase in the amount of outside air introduced directly leads to an increase in the air conditioning load in the area where the hot air drying furnace is installed. It was.
- Patent Document 1 Japanese Patent Document 1
- Patent Document 1 Japanese Patent Document 1
- the temperature of the hot air is set to a temperature that takes into account the temperature decrease due to latent heat of evaporation, and the temperature decreases due to latent heat of evaporation.
- the air volume of hot air is reduced without exceeding the allowable upper limit temperature of the workpiece.
- the binder contained in the electrode material such as a lithium ion secondary battery is a resin component, it has a property of solidifying when the hot air temperature exceeds a predetermined temperature, and the solidification of the binder is the battery resistance of the secondary battery. It will cause a rise.
- Patent Document 1 since the heat capacity of the electrode paste is small, the temperature decrease due to the latent heat of evaporation becomes small at the timing when the amount of solvent evaporation is small as in the beginning of the drying process. In some cases, the temperature of the hot air exceeds the temperature at which the binder solidifies.
- the temperature of the hot air is lowered in order to prevent the binder from solidifying, it takes time (that is, the drying efficiency is lowered) to reduce the residual amount of the solvent to a predetermined standard value or less. That is, conventionally, when reducing the air volume in the hot air drying furnace, it has been difficult to ensure the drying efficiency while reliably adjusting the temperature of the hot air to a predetermined temperature or lower.
- the present invention has been made in view of such a problem of the present situation, and a secondary battery capable of appropriately maintaining the temperature of the hot air while having a lower air volume than the conventional one in order to reduce the cost of the secondary battery.
- An object of the present invention is to provide a method for producing an electrode for use and a hot air drying furnace used in the method.
- the first invention comprises a transport roller for transporting an electrode foil coated with an electrode paste, a nozzle for blowing hot air, which is a gas heated to the electrode paste, and hot air to the nozzle.
- a manufacturing method of an electrode for a secondary battery by a hot air drying furnace provided with an exhaust fan and an exhaust duct for exhausting hot air after being sprayed on the electrode paste The temperature of the hot air at a certain first position is measured by a first temperature sensor, and is located downstream of the first position in the flow direction of the hot air blown from the nozzle.
- the temperature of the hot air at the second position which is the flow field of the hot air blown from the nozzle, is measured by a second temperature sensor, and in the flow direction of the hot air blown from the nozzle, from the second position
- the temperature of the hot air at the third position which is the flow field of the hot air blown out from the nozzle, is also measured on the downstream side by the third temperature sensor, and measured by the second temperature sensor by the control device
- the temperature decrease amount of the hot air at the first position due to the latent heat of vaporization of the electrode paste is calculated
- the corrected temperature of the hot air at the first position is calculated by adding the calculated temperature drop amount to the set temperature of the hot air at the first position to calculate the corrected temperature of the hot air at the first position.
- the corrected temperature of the hot air at the first position is calculated by adding the calculated temperature drop amount to the set temperature of the hot air at the first position to calculate the corrected temperature of the hot air at the first position.
- the control device includes a temperature drop amount of the hot air at the first position due to the latent heat of vaporization of the electrode paste, a temperature of the hot air at the second position, and the third position.
- Map information which is information obtained in advance with a correlation with the temperature of the hot air at the position, the measured temperature of the hot air at the second position by the second temperature sensor, and the temperature by the third temperature sensor Based on the measured temperature of the hot air at the third position, the amount of temperature drop of the hot air at the first position is calculated using the map information.
- the third invention is a transport roller for web transporting the electrode foil in a state where the electrode paste is applied, and a nozzle for discharging hot air which is a heated gas sprayed on the electrode paste.
- a hot-air drying furnace comprising a control device for adjusting, an exhaust fan and an exhaust duct for exhausting hot air discharged from the nozzle, wherein the control device has a first blowing position of the nozzle.
- a first temperature sensor for detecting the temperature of the hot air at one position, and a downstream side of the first position in the flow direction of the hot air discharged from the nozzle;
- a second temperature sensor for detecting a temperature of the hot air at a second position, which is a flow field of the hot air discharged from the nozzle, and a flow direction of the hot air discharged from the nozzle, from the second position.
- a third temperature sensor for detecting the temperature of the hot air at a third position, which is a flow field of the hot air discharged from the nozzle, which is located on the downstream side, and connected to the electrode paste This is information obtained in advance by correlating the amount of decrease in hot air temperature at the first position due to latent heat of vaporization, the temperature of hot air at the second position, and the temperature of hot air at the third position.
- Map information is stored, and the control device, based on the hot air temperature measured by the second temperature sensor and the hot air temperature measured by the third temperature sensor, Using the information, calculate the temperature drop amount of the hot air at the first position, and add the calculated temperature drop amount of the hot air at the first position to the set temperature of the hot air at the first position, The corrected set temperature of the hot air at the first position is calculated, and the output of the heater is calculated based on the difference between the corrected set temperature of the hot air and the temperature of the hot air measured by the first temperature sensor. It adjusts and controls the temperature of the hot air in said 1st position.
- the first to third inventions can reliably prevent the temperature of the hot air from exceeding the allowable upper limit temperature of the workpiece while reducing the amount of hot air for drying the electrode paste. Thereby, reduction of an air-conditioning load can be aimed at and the reduction of the manufacturing cost of a secondary battery is realizable.
- the flowchart which shows the flow of the manufacturing method of the secondary battery which concerns on one Embodiment of this invention.
- the schematic diagram which shows the whole structure of the manufacturing apparatus (hot air drying furnace) of the electrode for secondary batteries which concerns on 1st embodiment of this invention.
- the schematic diagram which shows the flow of the hot air in the hot air drying furnace which concerns on 1st embodiment in this invention, (a) A schematic perspective view, (b) The partial expansion schematic diagram around a nozzle.
- Control flow diagram of hot air drying furnace (a) In the case of a hot air drying furnace according to an embodiment of the present invention, (b) In the case of a conventional hot air drying furnace.
- the schematic diagram which shows the whole structure of the manufacturing apparatus (hot air drying furnace) of the electrode for secondary batteries which concerns on 2nd embodiment of this invention.
- the schematic diagram which shows the flow of the hot air in the hot air drying furnace which concerns on 2nd embodiment to this invention, (a) A schematic perspective view, (b) The partial expansion schematic diagram around a nozzle. The figure which shows the experimental result for confirming the application effect of the hot air drying furnace which concerns on one Embodiment of this invention.
- the secondary battery includes an electrode paste preparation step (Step-1), a coating step (Step-2), a drying step (Step-3), a slitting step (Step-4), and a pressing step (Step-5).
- the electrode body manufacturing process (Step-6), the assembly process (Step-7), the initial charge and the aging process (Step-8), etc. are shipped (Step-9).
- the electrode paste production step (Step-1) is a step for producing a paste for producing a positive electrode or a negative electrode (referred to as electrode paste).
- the positive electrode paste is produced by, for example, kneading nickel manganese cobaltate as a positive electrode active material, acetylene black as a conductive material, PVDF as a binder with a solvent (for example, NMP), further diluting, and the like.
- the electrode paste for the negative electrode is produced, for example, by kneading graphite as a negative electrode active material, CMC as a thickener, and SBR as a binder together with a solvent (for example, water), and further diluting.
- the coating step (Step-2) is a step of applying the positive electrode or negative electrode electrode paste generated in the electrode paste preparation step (Step-1) to the surface of the electrode foil, such as a die coater. Using the equipment, the electrode paste is applied to the surface of the electrode foil with a predetermined basis weight.
- the drying step (Step-3) is a step of drying the electrode paste coated on the surface of the electrode foil to form a composite layer, and more specifically, a solvent (NMP) contained in the electrode paste by heating. Or the like is evaporated to evaporate the residual amount of the solvent in the mixture layer to a predetermined standard value or less.
- the drying step (STEP-3) is performed using a hot air drying furnace.
- the pressing step (Step-4) is a step for pressing the composite material layer formed through the drying step (Step-3) together with the electrode foil to increase the density of the composite material layer to a predetermined density.
- the slitting step (Step-5) is a step of cutting the electrode foil and the composite material layer continuous in the length direction with a predetermined length and a predetermined width suitable for constituting the electrode body.
- Each of the above steps (Step-1) to (Step-5) is a step (electrode manufacturing step) for manufacturing an electrode (positive electrode and negative electrode) for a secondary battery.
- a negative electrode and a separately manufactured separator are laminated, and the laminated body is wound to produce an electrode body (Step-6).
- Step-7 a terminal is attached to the manufactured electrode body, and the electrode body is sealed in a case together with an electrolytic solution to assemble a secondary battery (Step-7). Then, the assembled secondary battery is initially charged and subjected to a predetermined aging process (Step-8), and then the secondary battery is shipped (Step-9).
- the manufacturing process of the secondary battery includes various processes such as a process for manufacturing a separator and a process for manufacturing a case. However, for convenience of explanation, those explanations are omitted here.
- a method for manufacturing a secondary battery electrode according to an embodiment of the present invention is a manufacturing method related to the drying step (Step-3) of the electrode manufacturing steps described above, and hot air according to an embodiment of the present invention.
- the drying furnace is used for realizing the manufacturing method in the drying step (Step-3).
- the hot air drying furnace 1 according to the first embodiment of the present invention is an apparatus used in the drying step (see FIG. 1) among the steps of manufacturing the secondary battery electrode, .., A plurality of nozzles 4..., A control device 5, a plurality of temperature sensors 7, 8, 9, and the like.
- an electrode paste having a predetermined width is provided on the surface of the electrode foil 6 which is a work introduced into the hot air drying furnace 1 so as to be continuous in the length direction of the electrode foil 6. 6a is coated.
- the nozzle 4 has a structure capable of discharging hot air in two directions, upstream and downstream with respect to the conveying direction of the electrode foil 6 in the hot air drying furnace 1. Yes.
- the control device 5 is discharged from the nozzle 4 in order to adjust the drying state of the electrode paste 6 a (see FIG. 3A) on the electrode foil 6 introduced into the hot air drying furnace 1.
- This is a device for controlling the temperature of hot air.
- the control device 5 is connected to a plurality (three systems) of temperature sensors 7, 8, and 9, and is configured to receive the temperature measurement results from the temperature sensors 7, 8, and 9.
- the hot air drying furnace 1 includes an air supply facility 11 for supplying gas to the nozzles 4, 4... And an exhaust facility for exhausting the gas supplied by the air supply facility 11 from the hot air drying furnace 1. 12 is provided. And in this embodiment, it is set as the structure which uses air (outside air) as "gas” supplied to each nozzle 4 * 4 ....
- the “gas” supplied to the nozzles 4, 4... Is not limited to air, and for example, a “gas” other than air such as an inert gas should be adopted. Is also possible.
- the air supply facility 11 includes an air supply fan 11a and an air supply duct 11b, and a heater for heating a gas (air in this embodiment) supplied to the hot air drying furnace 1 in the middle of the air supply duct 11b. 10 is provided.
- a gas (air in this embodiment) heated by the heater 10 supplied by the air supply facility 11 is referred to as “hot air”.
- the air supply duct 11 b of the air supply facility 11 is connected to a branch duct 13 provided inside the furnace body 2, and the hot air supplied from the air supply facility 11 is supplied to each nozzle 4. It is set as the structure distributed to 4 ....
- the exhaust facility 12 includes an exhaust fan 12a and an exhaust duct 12b, and is connected to the furnace body 2 and exhausts hot air supplied to the furnace body 2 to the outside of the furnace body 2 through the exhaust duct 12b. It is configured to do.
- the heater 10 is connected to the control device 5 and can adjust the output of the heater 10 in accordance with a signal output from the control device 5. Further, the air supply fan 11a and the exhaust fan 12a are connected to the control device 5, and in accordance with a signal output from the control device 5, the fan rotation speed of each fan 11a and 12a (more specifically, each fan 11a The setting frequency of each inverter included in 12a) can be changed to adjust the air volume of each fan 11a and 12a.
- the electrode paste 6a is coated on the surface of the electrode foil 6 conveyed by the plurality of conveying rollers 3 ⁇ in the coating step (Step-2). Are transported by the transport rollers 3, 3..., And hot air discharged from the plurality of nozzles 4, 4... Is sprayed onto the electrode paste 6a on the electrode foil 6.
- a plurality (three in the present embodiment) of temperature sensors 7, 8, 9 are arranged at positions along the flow of hot air blown out from the nozzle 4.
- the hot air discharged from the nozzle 4 flows along the surface of the electrode foil 6 (that is, the electrode paste 6a). It flows so that it may wrap around to the back side, and it is comprised so that it may flow toward the connection direction of the exhaust duct 12b after that.
- the other part of the hot air that flows along the surface of the electrode foil 6 that is, the electrode paste 6a
- the hot air is distributed to the plurality of nozzles 4, 4... By the branch duct 13 inside the furnace body 1.
- the nozzle 4 having a shorter flow path length higher-temperature hot air is emitted.
- the nozzle 4 having the shortest flow path length from the heater 10 is selected, and the temperature sensors 7, 8, 9 are arranged along the flow of hot air blown from the nozzle 4. It is configured.
- the temperature of the hot air blown out from the nozzle 4 having the shortest flow path length from the heater 10 is adjusted to a predetermined temperature or lower so that the temperature of the hot air in the entire hot air drying furnace 1 is cured.
- the temperature is adjusted to a temperature that does not occur.
- the temperature of the hot air discharged from the nozzles 4,... Other than the nozzle 4 to be detected by the temperature sensor 7 is the same.
- the first temperature sensor 7 is disposed at a point A located immediately below the nozzle 4, that is, at the outlet of the nozzle 4. It is set as the structure which measures the temperature TA of the hot air in A.
- the target temperature of the hot air at this point A is defined as a set temperature T S, and the temperature of the hot air blown from the nozzle 4 is matched with the set temperature T S at the point A (see FIG. 2).
- the output to the heater 10 is adjusted.
- Temperature T A of the hot air in the point A is influenced by the latent heat of vaporization of the electrode paste 6a, it is lower than the temperature of the immediately preceding speech balloon.
- the point A in the hot air drying furnace 1 is a position 5 mm above the electrode foil 6, and the hot air setting temperature T S at the point A is 150 ° C. That is, the height of the blowing position on the lower surface of the nozzle 4 is 5 mm above the electrode foil 6.
- the second temperature sensor 8 is disposed at a point B located downstream of the point A where the first temperature sensor 7 is disposed in the flow direction of the hot air discharged from the nozzle 4. by 8, it has a configuration for measuring the temperature T B of the hot air at the point B. Further, point B avoids a portion where the flow of hot air is turbulent due to the influence of hot air emitted from other nozzles 4, and more than a portion where hot air emitted from each nozzle 4, 4 collides with each other. The position where the hot air on the upstream side in the flow direction of the hot air flows in a laminar flow is selected. The temperature T B of the hot air at the point B is lower than the temperature T A because the hot air flows along the electrode foil 6 and is further influenced by the latent heat of vaporization of the electrode paste 6a than the point A. .
- the point B in the hot air drying furnace 1 is a position where the length of the hot air flow path becomes 200 mm from the point A toward the downstream side in the hot air flow direction, and 10 mm above the electrode foil 6. And position.
- the third temperature sensor 9 is disposed at a point C located downstream of the point B where the second temperature sensor 8 is disposed in the flow direction of the hot air discharged from the nozzle 4. by 9, it is configured to measure the temperature T C of the hot air at the point C. Further, the point C avoids a portion where the flow of hot air is turbulent due to the influence of hot air emitted from the other nozzles 4 and is hotter than a portion where hot air emitted from the nozzles 4 and 4 joins. The position where the upstream hot air in the flow direction is flowing in a laminar flow is selected. The temperature T C of the hot air at the point C is lower than the temperature T B because it is further influenced by the latent heat of vaporization of the electrode paste 6 a than the point B while the hot air flows along the electrode foil 6. .
- the point C in the hot air drying furnace 1 is a position where the length of the hot air flow path is 500 mm from the point A toward the downstream side in the hot air flow direction, and 30 mm below the electrode foil 6. And position.
- the hot air temperature is lowered due to the influence of the latent heat of vaporization of the electrode paste 6 a, but this temperature drop is very small, so the temperature sensor 7 arranged at the point A It is difficult to accurately detect this minute temperature drop.
- the points B ⁇ C to measure the temperature T B and the temperature T C is the flow passage cross-sectional area than the point A has been enlarged, because the velocity of the hot air is low, a small temperature change it is capable of stably performing a measurement of the temperature than the temperature T a with, and, since the temperature variation is large, it is possible to easily secure the detection accuracy of the temperature.
- the hot air the temperature T B and the detected downstream of the position (point B and point C) in the flow direction of the hot air than the point A
- the detection accuracy of the temperature drop amount dT can be improved.
- the temperature decrease dT each temperature of the hot air downstream of the point B and the point C than the point A (temperature T B and the temperature T C ). More specifically, in the manufacturing method of the electrode for a secondary battery according to an embodiment of the present invention, the temperature T B and the temperature T C, the correlation of the temperature decrease dT at the point A, the map information as shown in FIG. 4 As previously described, it is configured to be obtained through experiments or the like. Then, as measured from the temperature T B and the temperature T C, using the map information, and configured to calculate the temperature decrease dT.
- the temperature T A at the point A it can be seen that becomes low 18 ° C. than the set temperature T S.
- the set temperature T Sn is set by adding (T S +18) ° C. by adding the temperature decrease amount dT to the set temperature T S. It is configured to do.
- the drying efficiency is configured to prevent the lowering.
- map information changes depending on the basis weight and the solid content ratio of the electrode paste 6a
- different map information is prepared according to the specifications of the electrode paste 6a used for manufacturing the secondary battery electrode. Is preferred.
- the temperature T B and the temperature T C advance Chitoku the map information representing the correlation of the temperature decrease dT at point A, and calculates the temperature decrease dT using the map information
- the measurement result of the temperature T B and the temperature T C, performing the direct computation may be configured to calculate the temperature decrease dT.
- the control device 5 controls the temperatures T B and T at points B and C, respectively.
- the temperature drop amount dT at point A is calculated from C.
- the set temperature T S is corrected in consideration of the calculated temperature decrease amount dT
- the corrected set temperature T Sn is calculated
- the control amount is calculated from the difference between the corrected set temperature T Sn and the temperature T A at the point A. and calculates the dT a.
- map information (see FIG. 4) is stored in advance in the control device 5, and calculation is performed using the map information. based on the temperature decrease dT, it is configured to modify the set temperature T S.
- a value (T S + dT) obtained by adding the temperature decrease amount dT to the set temperature T S of the temperature T A is set as a new set temperature T Sn.
- the configuration is set as And this with the new set temperature T Sn, on the basis of the difference dT A between the temperature T A at the point A, the control device 5 (more specifically, indicating controller the controller 5 is provided) by, for heating the hot air
- the output to the heater 10 as the means is adjusted.
- the hot-air drying furnace 21 which is the secondary battery electrode manufacturing apparatus according to the second embodiment of the present invention includes a drying process (FIG. 1) among the processes for manufacturing the secondary battery electrode. .., A plurality of conveying rollers 3..., A plurality of nozzles 24, 24. That is, the hot air drying furnace 21 according to the second embodiment is different from the hot air drying furnace 1 according to the first embodiment in the configuration of the nozzles provided, and the other configurations are common. ing.
- the nozzle 24 has a structure capable of discharging hot air only in one direction upstream from the conveying direction of the electrode foil 6.
- the hot air discharged from the nozzle 24 flows along the surface of the electrode foil 6 (that is, the electrode paste 6a). It flows so that it may wrap around to the back side, and it is comprised so that it may flow toward the connection direction of the exhaust duct 12b after that.
- the other part of the hot air that flows along the surface of the electrode foil 6 that is, the electrode paste 6a
- the hot air is discharged in one direction from the nozzle 24, and therefore the distance until the hot air discharged from the nozzle 24 collides with the hot air discharged from the other nozzles 24 is larger than that in the hot air drying furnace 1. And big. For this reason, in the hot air drying furnace 21, the range of the site where the hot air discharged from the nozzle 24 flows in a laminar flow state is wider than that in the hot air drying furnace 1, and in particular, the distance between the points A and B. Therefore, there is an advantage that the temperature decrease amount dT at the point A can be calculated with higher accuracy.
- the air volume of the conventional hot air drying furnace is 25 m 3 / min
- the air volume of the hot air drying furnace 1 according to the first embodiment of the present invention is 22.5 m 3 / min. That is, the hot air drying furnace 1 according to the first embodiment of the present invention reduces the air volume by 10% compared to the conventional hot air drying furnace.
- the slit width of the blowout port formed in the nozzle 4 is 5 mm, and the air supply fan 11a and the exhaust fan are controlled by the control device 5 so that the wind speed of the hot air blown from the nozzle 4 is 22.5 m / s. It is set as the structure which adjusts the air volume of 11b. In addition, the number of nozzles 4 is six.
- the furnace length of the hot air drying furnace 1 is 6 m
- the conveying speed of the electrode foil 6 in the inside is 30 m / min
- the drying time is 12 seconds. That is, in the hot air drying furnace 1, the time from when the electrode foil 6 is introduced into the furnace body 2 to when it is discharged is set to 12 seconds, and during this 12 seconds, it is included in the electrode paste 6a. It is set as the structure dried so that the quantity of a solvent may become below a predetermined standard value.
- the electrode foil 6 is a copper foil
- the electrode paste 6a uses a paste generated using graphite as a negative electrode active material as a main material.
- the solid content rate of the electrode paste 6a is 50%
- the basis weight is 8 mg / cm 2 .
- the manufacturing method of the electrode for a secondary battery includes a transport roller 3, 3... For transporting the electrode foil 6 in a state where the electrode paste 6 a is applied, and the web.
- the nozzles 4, 4,... Or nozzles 24, 24,... For discharging hot air, which is a heated gas (air in the present embodiment) sprayed on the electrode paste 6a, and hot air are applied to the nozzles 4 or 24.
- An air supply fan 11a and an air supply duct 11b for supplying, a heater 10 for heating air supplied to the nozzle 4 or the nozzle 24, arranged in the air supply duct 11b, and an output of the heater 10 are adjusted.
- Each of the hot air drying furnaces 1 and 2 includes a control device 5 for exhausting the exhaust air and an exhaust fan 12a and an exhaust duct 12b for exhausting the hot air discharged from the nozzle 4 or the nozzle 24.
- a manufacturing method according to the hot-air temperature T A of the first position the barrel point A is a blowout position of the nozzle 4 or nozzle 24 is measured by the first temperature sensor 7, blown out of the nozzle 4 or nozzle 24
- the temperature T B of the hot air at the second position B which is the flow field of the hot air blown from the nozzle 4 or the nozzle 24, which is located downstream of the point A in the flow direction of the hot air, is the second temperature sensor.
- the control device 5 was measured by the second temperature sensor 8 temperature And B, and the temperature T C as measured by the third temperature sensor 9, on the basis of, calculating the temperature drop amount dT of the hot air in the point A due to the latent heat of vaporization of the electrode paste 6a, setting of hot air at point A
- the calculated temperature drop amount dT is added to the temperature T S to calculate a corrected hot air set temperature T Sn at the point A, and the corrected hot air set temperature T Sn and the temperature measured by the first temperature sensor 7 are calculated. according to the difference dT a of T a, and adjusts the output to the heater 10.
- the control apparatus 5 has the temperature fall amount dT of the hot air in the point A resulting from the evaporation latent heat of the electrode paste 6a, and the hot air in the point B. and the temperature T B which includes a map information, measured by the second temperature sensor 8 at the temperature T B and the point C is information acquired in advance the correlation between the temperature T C of the hot air, the third temperature sensor and the temperature T C as measured by 9, based on, using the map information, and calculates the temperature decrease amount dT of the hot air at the point a.
- each hot-air drying furnace 1.21 which concerns on one Embodiment of this invention has the conveyance roller 3,3 ... for carrying the web of the electrode foil 6 of the state by which the paste 6a for electrodes was coated, and an electrode ... Or nozzles 24....
- hot air which is a heated gas (air in this embodiment) sprayed on the paste 6 a, and hot air is supplied to the nozzles 4 or 24.
- An air supply fan 11a and an air supply duct 11b, a heater 10 for raising the temperature of air supplied to the nozzle 4 or the nozzle 24, and an output of the heater 10 are adjusted.
- an exhaust fan 12a and an exhaust duct 12b for exhausting hot air discharged from the nozzle 4 or the nozzle 24.
- the first temperature sensor 7 for detecting the temperature T A of the hot air in the first position the barrel point A is a blowout position of the nozzle 4 or nozzle 24, discharged from the nozzle 4 or nozzle 24 hot air 2 for detecting the temperature T B of the hot air at the point B, which is the second position, which is the flow field of the hot air discharged from the nozzle 4 or the nozzle 24, which is located downstream of the point A in the flow direction of.
- a temperature decrease amount dT of the map information is information acquired in advance the correlation between the temperature T C of the hot air at the temperature T B and the point C of the hot air at the point B, and is stored, the control unit 5, first and the temperature T B as measured by second temperature sensor 8, and a temperature T C as measured by the third temperature sensor 9, on the basis of, using the map information, and calculates the temperature decrease amount dT of hot air at point a , by adding the hot air temperature decrease dT of the calculated point a hot air set temperature T S at point a, to calculate the set temperature T Sn of the hot modified at the point a, the hot air that fixes the set temperature T Sn
- the temperature T a measured by the first temperature sensor 7, based on the difference to adjust the output of the heater 10, and controls the temperature T a of the hot air at the point
- the work in this embodiment, electrode paste 6a
- the work can be reliably prevented from exceeding the allowable upper limit temperature. Therefore, it is possible to reduce the air conditioning load and reduce the manufacturing cost of the secondary battery.
- the present invention can be widely applied not only to a hot air drying furnace used for manufacturing a secondary battery but also to a hot air drying furnace used in a process of drying a paste coated in a film shape. It is possible to apply as a technique for manufacturing the etc.
- Hot air drying furnace (first embodiment) 4 Nozzle (first embodiment) DESCRIPTION OF SYMBOLS 5 Control apparatus 6 Electrode foil 6a Electrode paste 7 Temperature sensor 8 Temperature sensor 9 Temperature sensor 10 Heater 11a Air supply fan 11b Air supply duct 21 Hot air drying furnace (2nd embodiment) 24 nozzles (second embodiment)
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Abstract
Description
熱風乾燥炉を用いて電極用ペーストを乾燥させる工程の概要は、表面に電極用ペーストが塗工された電極箔を熱風乾燥炉の内部にウェブ搬送し、熱風乾燥炉の内部で、電極箔の上の電極用ペーストにノズルから熱風を吹き付けて、電極用ペーストに含まれる溶媒(NMP(N-メチルピロリドン)や水等)を蒸発させて、溶媒を除去する構成としている。
尚、ここでいう「除去」とは、溶媒の残留量を所定の規格値以下にすることを含む概念であり、溶媒を完全に除去することのみを意味するものではない。
二次電池用電極には、乾燥後における溶媒の残留量についての規格値が設定されているが、熱風の温度低下が生じると、溶媒の残留量が多くなってしまうことが判っている。
従来の熱風乾燥炉では、熱風の風量を多くすることによって、蒸発潜熱による温度低下の影響を抑えて、溶媒の残留量が規格値以下となる乾燥条件を確保する構成としている。
外気導入量の増加は、熱風乾燥炉を設置するエリアにおける空調負荷の増大に直結することから、従来は、熱風乾燥炉のランニングコストが多大となり、二次電池のコスト低減を阻害する要因ともなっていた。
特許文献1に開示されている従来技術では、電極用ペーストを塗工した後の乾燥工程において、熱風の温度を、蒸発潜熱による温度低下分を予め考慮した温度に設定し、蒸発潜熱による温度低下を相殺することで、ワークの許容上限温度を超えずに、熱風の風量を削減する構成としている。
そして、特許文献1に開示されている従来技術では、電極用ペーストの熱容量が小さいため、乾燥工程の始動当初のように溶媒の蒸発量が少ないタイミングでは、蒸発潜熱による温度の低下幅が小さくなって、熱風の温度が、バインダの固化する温度を超えてしまうような場合があった。
一方、バインダの固化を防止するために熱風の温度を下げたとすると、溶媒の残留量を所定の規格値以下にするのに時間を要する(即ち、乾燥効率が低下する)こととなる。
即ち従来は、熱風乾燥炉における風量を低減しようとするときには、熱風の温度を確実に所定の温度以下に調整しつつ、乾燥効率を確保することが困難であった。
これにより、空調負荷の低減を図って、二次電池の製造コストの低減を実現できる。
まず始めに、二次電池の製造工程の概要について、図1を用いて説明をする。
二次電池を製造するための各工程は、図1に示すような流れとなっている。
即ち、二次電池は、電極用ペースト作成工程(Step-1)、塗工工程(Step-2)、乾燥工程(Step-3)、スリット工程(Step-4)、プレス工程(Step-5)、電極体製造工程(Step-6)、組み立て工程(Step-7)、初充電およびエージング工程(Step-8)等の各工程を経て、出荷(Step-9)される。
正極用の電極用ペーストは、例えば、正極活物質たるニッケルマンガンコバルト酸リチウム、導電材たるアセチレンブラック、結着材たるPVDFを溶媒(例えば、NMP)とともに混練し、さらに希釈等して生成される。
また、負極用の電極用ペーストは、例えば、負極活物質たる黒鉛、増粘剤たるCMC、結着剤たるSBRを溶媒(例えば、水)とともに混練し、さらに希釈等して生成される。
乾燥工程(STEP-3)は、本実施形態では熱風乾燥炉を用いて行われる。
そして、スリット工程(Step-5)は、長さ方向に連続する電極箔および合材層を、電極体を構成するのに適した所定の長さおよび所定の幅で切断する工程である。
そして、組み立てられた二次電池に初充電を施すとともに、所定のエージング処理等を施して(Step-8)、その後二次電池を出荷する(Step-9)構成としている。
尚、二次電池の製造工程には、図1で示した(Step-1)~(Step-9)の他に、セパレータを製造するための工程やケースを製造するための工程等、その他種々の工程が存在しているが、説明の便宜上、ここではそれらの説明を省略している。
図2に示す如く、本発明の第一の実施形態に係る熱風乾燥炉1は、二次電池用電極を製造する各工程のうち、乾燥工程(図1参照)において用いられる装置であって、炉本体2、複数の搬送ローラ3・3・・・、複数のノズル4・4・・・、制御装置5、複数の温度センサ7・8・9等を備える構成としている。
また、制御装置5は、複数(3系統)の各温度センサ7・8・9と接続され、各温度センサ7・8・9による温度の測定結果が入力される構成としている。
そして、本実施形態では、各ノズル4・4・・・に供給する「気体」として空気(外気)を使用する構成としている。
尚、熱風乾燥炉1において、各ノズル4・4・・・に供給する「気体」は、空気に限定されるものではなく、例えば、不活性ガス等の空気以外の「気体」を採用することも可能である。
尚、以下では、給気設備11により供給される、ヒータ10によって加熱された気体(本実施形態では空気)のことを「熱風」と呼ぶものとする。
そして、給気設備11の給気ダクト11bは、炉本体2の内部に設けた分岐ダクト13に接続しており、該分岐ダクト13によって、給気設備11より供給される熱風を各ノズル4・4・・・に分配する構成としている。
さらに、給気ファン11aおよび排気ファン12aは、制御装置5と接続されており、制御装置5から出力する信号に応じて、各ファン11a・12aのファン回転数(より詳しくは、各ファン11a・12aが備える各インバータの設定周波数)を変更して、各ファン11a・12aの風量を調整することができる構成としている。
そして、熱風乾燥炉1では、ノズル4から吹き出される熱風の流れに沿う位置に、複数(本実施形態では3個)の温度センサ7・8・9を配置する構成としている。
図3(a)(b)に示す如く、ノズル4から放出された熱風は、電極箔6の表面(即ち、電極用ペースト6a)に沿って流れ、その後、その一部は、電極箔6の裏側に回り込むようにして流れ、その後、排気ダクト12bの接続方向に向けて流れるように構成されている。
尚、電極箔6の表面(即ち、電極用ペースト6a)に沿って流れた熱風のその他の一部は、ノズル4に隣接する他のノズル4から放出された熱風と衝突して巻き上がるように流れるため、炉本体2の内部においては、熱風が乱流化している部位も存在している。
そして、熱風乾燥炉1では、ヒータ10からの流路長さが最も短いノズル4を選んで、そのノズル4から吹き出される熱風の流れに沿って、各温度センサ7・8・9を配置する構成としている。
そして、このヒータ10からの流路長が最も短いノズル4から吹き出される熱風の温度を、所定の温度以下に調整することによって、熱風乾燥炉1全体における熱風の温度を、合材層の硬化が生じない温度未満に調整する構成としている。
熱風乾燥炉1では、温度センサ7により温度を検出する対象たるノズル4以外の他のノズル4・4・・・では、そこから放出される熱風の温度は成り行きとなっている。
また、この点Aにおける熱風の狙い温度を設定温度TSと規定し、ノズル4から吹き出される熱風の温度が、点Aにおいて、設定温度TSに一致するように、制御装置5(図2参照)によって、ヒータ10(図2参照)への出力を調整する構成としている。
即ち、ノズル4の下面における吹き出し位置の高さは、電極箔6の上方5mmの位置としている。
また、点Bは、他のノズル4から放出される熱風等の影響により熱風の流れが乱流化している部分を避けて、各ノズル4・4から放出される熱風同士が衝突する部位よりも熱風の流れ方向における上流側の熱風が層流状に流れている位置選択するようにしている。
点Bにおける熱風の温度TBは、熱風が電極箔6に沿って流れる間に点Aよりもさらに電極用ペースト6aの蒸発潜熱による影響を受けるため、温度TAに比して低くなっている。
また、点Cは、他のノズル4から放出される熱風等の影響により熱風の流れが乱流化している部分を避けて、各ノズル4・4から放出される熱風が合流する部位よりも熱風の流れ方向における上流側の熱風が層流状に流れている位置を選択するようにしている。
点Cにおける熱風の温度TCは、熱風が電極箔6に沿って流れる間に点Bよりもさらに電極用ペースト6aの蒸発潜熱による影響を受けるため、温度TBに比して低くなっている。
より詳しくは、本発明の一実施形態に係る二次電池用電極の製造方法では、温度TBおよび温度TCと、点Aにおける温度低下量dTの相関を、図4に示すようなマップ情報として予め実験等により知得しておく構成としている。
そして、測定した、温度TBおよび温度TCから、マップ情報を用いて、温度低下量dTを算出する構成としている。
そして、点Aにおける温度低下量dTが判ると、設定温度TSが現状のままでは、点Aにおける温度TAが、設定温度TSに比して18℃低くなってしまうことが判る。
これにより、溶媒の蒸発潜熱によって、熱風の温度が設定温度TSに比して低くなり、乾燥効率が低下することを防止する構成としている。
例えば従来は、図5(b)に示すように、点Aにおける温度TAと設定温度の差分から直接制御量dTAを算出していたが、温度TAは感度が鈍く、電極用ペースト6aの蒸発潜熱に起因する温度変化を精度よく検出できないため、ヒータ10の制御が安定しなかった。
そして、算出した温度低下量dTを考慮して設定温度TSを修正して、修正した設定温度TSnを算出するとともに、修正した設定温度TSnと点Aにおける温度TAの差分から制御量dTAを算出している。
このような構成にすることで、電極用ペースト6aの蒸発潜熱に起因する温度変化量dTを考慮することができるため、ヒータ10の制御の応答性を向上させることが可能になる。
そして、この新たな設定温度TSnと、点Aにおける温度TAとの差分dTAに基づいて、制御装置5(より詳しくは、制御装置5が備える指示調節計)によって、熱風を加熱するための手段たるヒータ10に対する出力を調整する構成としている。
図6に示す如く、本発明の第二の実施形態に係る二次電池用電極の製造装置である熱風乾燥炉21は、二次電池用電極を製造する各工程のうち、乾燥工程(図1参照)において用いられる装置であって、炉本体2、複数の搬送ローラ3・3・・・、複数のノズル24・24・・・、制御装置5等を備える構成としている。
即ち、第二の実施形態に係る熱風乾燥炉21は、第一の実施形態に係る熱風乾燥炉1に比して、備えているノズルの構成が相違しており、その他の構成については共通している。
尚、電極箔6の表面(即ち、電極用ペースト6a)に沿って流れた熱風のその他の一部は、ノズル24に隣接する他のノズル24から放出された熱風と衝突して巻き上がるように流れるため、炉本体2の内部においては、熱風が乱流化している部位も存在している。
このため、熱風乾燥炉21では、ノズル24から放出された熱風が層流状態で流れている部位の範囲が、熱風乾燥炉1の場合に比して広くなり、特に点Aと点Bの距離を確保しやすくなるため、点Aにおける温度低下量dTをより精度よく算出できるという利点がある。
図8には、従来の(風量の多い)熱風乾燥炉を用いた場合と、本発明の第一の実施形態に係る熱風乾燥炉1を用いた場合の、それぞれにおける乾燥後の合材層における溶媒の残留量を比較した実験結果を示している。
即ち、本発明の第一の実施形態に係る熱風乾燥炉1は、従来の熱風乾燥炉に比して風量を10%低減している。
また、ノズル4の配置個数は、6個としている。
即ち、熱風乾燥炉1では、電極箔6が炉本体2に導入されてから、排出されるまでの時間を12秒に設定しており、この12秒の間に、電極用ペースト6aに含まれる溶媒の量を所定の規格値以下となるように乾燥させる構成としている。
また、電極用ペースト6aの固形分率は50%とし、その目付量を8mg/cm2としている。
また、従来の熱風乾燥炉と熱風乾燥炉1のそれぞれに対して、8個ずつ(合計16個)のサンプルを用意して、これらの各サンプルにおける水分率の測定結果を図8にまとめた。
即ち、図8に示す実験結果から、本発明の第一の実施形態に係る熱風乾燥炉1を用いれば、従来の熱風乾燥炉に比して10%の風量低下を実現しながら、従来の熱風乾燥炉を用いた場合と同等の乾燥効率を維持することが可能であることが確認できた。
またこれにより、空調負荷の低減を図って、二次電池の製造コストの低減を実現できる。
4 ノズル(第一の実施形態)
5 制御装置
6 電極箔
6a 電極用ペースト
7 温度センサ
8 温度センサ
9 温度センサ
10 ヒータ
11a 給気ファン
11b 給気ダクト
21 熱風乾燥炉(第二の実施形態)
24 ノズル(第二の実施形態)
Claims (3)
- 電極用ペーストが塗工された電極箔を搬送するための搬送ローラと、
前記電極用ペーストに加熱された気体である熱風を吹き付けるためのノズルと、
前記ノズルに熱風を供給するための給気ファンおよび給気ダクトと、
前記給気ダクトの途中に配置される、前記ノズルに供給する気体を加熱するためのヒータと、
前記ヒータの出力を調整するための制御装置と、
前記電極用ペーストに吹き付けられた後の熱風を排気するための排気ファンおよび排気ダクトと、
を備えた熱風乾燥炉による二次電池用電極の製造方法であって、
前記ノズルの吹き出し位置である第一の位置における熱風の温度を第一の温度センサによって測定し、
前記ノズルから吹き出された熱風の流れ方向において、前記第一の位置よりも下流側に位置する、前記ノズルから吹き出された熱風の流れ場である第二の位置における熱風の温度を第二の温度センサによって測定し、
前記ノズルから吹き出された熱風の流れ方向において、前記第二の位置よりも下流側に位置する、前記ノズルから吹き出された熱風の流れ場である第三の位置における熱風の温度を第三の温度センサによって測定し、
前記制御装置によって、
前記第二の温度センサにより測定した熱風の温度と、
前記第三の温度センサにより測定した熱風の温度と、に基づいて、
前記電極用ペーストの蒸発潜熱に起因する前記第一の位置における熱風の温度低下量を算出し、
前記第一の位置における熱風の設定温度に、算出した前記温度低下量を加算して、前記第一の位置における修正した熱風の設定温度を算出し、
前記修正した熱風の設定温度と前記第一の温度センサにより測定した熱風の温度の差分に応じて、
前記ヒータへの出力を調整する、
ことを特徴とする二次電池用電極の製造方法。 - 前記制御装置は、
前記電極用ペーストの蒸発潜熱に起因する前記第一の位置における熱風の温度低下量と、前記第二の位置における熱風の温度および前記第三の位置における熱風の温度との相関を予め取得しておいた情報であるマップ情報を備え、
前記第二の温度センサによる前記第二の位置における熱風の測定温度と、
前記第三の温度センサによる前記第三の位置における熱風の測定温度と、に基づいて、
前記マップ情報を用いて、
前記第一の位置における熱風の温度低下量を算出する、
ことを特徴とする請求項1に記載の二次電池用電極の製造方法。 - 電極用ペーストが塗工された状態の電極箔をウェブ搬送するための搬送ローラと、
前記電極用ペーストに吹き付ける加熱された気体である熱風を放出させるためのノズルと、
前記ノズルに熱風を供給するための給気ファンおよび給気ダクトと、
前記給気ダクトの途中に配置される、前記ノズルに供給する気体を昇温するためのヒータと、
前記ヒータの出力を調整するための制御装置と、
前記ノズルから放出された熱風を排気するための排気ファンおよび排気ダクトと、
を備える熱風乾燥炉であって、
前記制御装置には、
前記ノズルの吹き出し位置である第一の位置における熱風の温度を検出するための第一の温度センサと、
前記ノズルから放出された熱風の流れ方向において、前記第一の位置よりも下流側に位置する、前記ノズルから放出された熱風の流れ場である第二の位置における熱風の温度を検出するための第二の温度センサと、
前記ノズルから放出された熱風の流れ方向において、前記第二の位置よりも下流側に位置する、前記ノズルから放出された熱風の流れ場である第三の位置における熱風の温度を検出するための第三の温度センサと、
が接続されるとともに、
前記電極用ペーストの蒸発潜熱に起因する前記第一の位置における熱風の温度低下量と、前記第二の位置における熱風の温度および前記第三の位置における熱風の温度との相関を予め取得しておいた情報であるマップ情報、が記憶され、
前記制御装置は、
前記第二の温度センサにより測定した熱風の温度と、
前記第三の温度センサにより測定した熱風の温度と、
に基づいて、
前記マップ情報を用いて、前記第一の位置における熱風の温度低下量を算出するとともに、
算出した前記第一の位置における熱風の温度低下量を前記第一の位置における熱風の設定温度に加算して、前記第一の位置における修正した熱風の設定温度を算出し、
前記修正した熱風の設定温度と、前記第一の温度センサにより測定した熱風の温度と、の差分に基づいて、前記ヒータの出力を調整して、
前記第一の位置における熱風の温度を制御する、
ことを特徴とする熱風乾燥炉。
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