Abstract
A small diameter roll is provided on the upstream side of a heating and sucking roll, an electrode slurry is applied by using a slot nozzle on the small diameter roll or an OFF roll, and an electrode is formed by instantaneously evaporating a solvent by the heating and sucking roll.
Claims
1-10. (canceled)
11. A method for producing a battery by continuously or intermittently moving a long substrate for a battery and applying an electrode slurry to the substrate to form an electrode using a slot nozzle, comprising: providing a heating and sucking roll capable of adsorption of the substrate; providing at least one small diameter roll upstream of the heating and sucking roll, the at least one small diameter roll being close to the heating and sucking roll and having a smaller diameter than the heating and sucking roll; and applying the electrode slurry, by using a slot nozzle, on the substrate located from a position on the small diameter roll to a position where the substrate comes into contact with the heating and sucking roll; wherein the heating and sucking roll being a heating and moving means for heating and moving a substrate to which an electrode slurry is applied.
12. The method according to claim 11, wherein the heating and moving means is selected from a heating and sucking roll, a heating roll, a heating belt or a heating and sucking belt as a moving means of a substrate, and the substrate moves under a tension of 5 to 150 newtons at a position where the substrate is detached from the moving means.
13. The method according to claim 11, further comprising: applying a tension of 5 to 150 newtons to the substrate before and after the small diameter roll; and applying the electrode slurry on an off roll before and after the small diameter roll.
14. The method according to claim 11, wherein the slot nozzle is an air assist slot nozzle or a mist ejection slit nozzle, further comprising setting a distance between the substrate and a nozzle head to 0 to 30 mm.
15. A method for producing a battery being a second battery or a fuel battery, comprising: selecting at least one of a heating and sucking roll, a heating roll, a heating belt or a heating and sucking belt as a heating and moving means of a substrate; and applying an electrode slurry to a substrate moved by the heating and moving means while an air assist slot nozzle, a mist ejection nozzle with compressed gas or a melt blown type spray nozzle head using an air curtain with compressed gas is faced to the heating and moving means and moved relative to the heating and moving means.
16. The method according to claim 12, wherein the heating and sucking roll or the heating roll has a roundness of ±50 micrometers or less, and further comprising applying an electrode ink on an off roll immediately before the heating and sucking roll or the heating roll comes into contact with a substrate.
17. The method according to claim 11, wherein the substrate is selected from a current collector, an electrolyte membrane, a separator and an electrode layer/electrolyte layer forming current collector, and the electrode slurry is selected from an electrode slurry, an electrolyte slurry and an electrolyte solution.
18. The method according to claim 15, wherein the second battery is an all-solid battery or a semi-solid battery.
19. The method according to claim 11, wherein a temperature of the slot nozzle or the slurry is equal to or lower than a boiling point of a solvent contained in the slurry, wherein a temperature of the heating and sucking roll is 30° C. or more higher than the temperature of the slot nozzle or the slurry.
20. The method according to claim 19, further comprising handling the slurry at a room temperature.
21. The method according to claim 15, wherein the substrate is selected from a current collector, an electrolyte membrane, a separator and an electrode layer/electrolyte layer forming current collector, and the electrode slurry is selected from an electrode slurry, an electrolyte slurry and an electrolyte solution.
22. The method according to claim 15, wherein a temperature of the slot nozzle or the slurry is equal to or lower than a boiling point of a solvent contained in the slurry, wherein a temperature of the heating and sucking roll is 30° C. or more higher than the temperature of the slot nozzle or the slurry.
23. The method according to claim 22, further comprising handling the slurry at a room temperature.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0116] FIG. 1 shows a schematic cross-sectional diagram of an arrangement of a heating (sucking) roll, a small diameter roll, a substrate and a slot nozzle according to the present embodiment.
[0117] FIG. 2 shows a schematic cross-sectional diagram of a combination of a heating (sucking) roll, a small diameter roll, a substrate and a slot nozzle according to the present embodiment.
[0118] FIG. 3 shows a schematic cross-sectional diagram of an arrangement of a heating (sucking) roll, a substrate, a small diameter roll, a slot nozzle, etc. and a moving direction of a breathable substrates, etc. according to the present embodiment.
[0119] FIG. 4 shows a schematic cross-sectional diagram of an inverted substrate for forming a second electrode and other constructs according to the present embodiment.
[0120] FIG. 5 shows a schematic cross-sectional diagram of a moving direction of a substrate, etc. in the advanced version of forming a second electrode according to the present embodiment.
[0121] FIG. 5-2 shows a schematic diagram of applying while traversing a melt-blown spray head perpendicular to a traveling direction of a substrate on a heating (sucking) roll according to the present embodiment.
[0122] FIG. 6 shows a schematic cross-sectional diagram of electrodes formed on both sides of a substrate according to the present embodiment.
[0123] FIG. 7 shows a schematic cross-sectional diagram of an air assist slot nozzle according to the present embodiment.
[0124] FIG. 8 shows a schematic cross-sectional diagram of a pattern coat on a substrate by a mist ejection slit nozzle according to the present embodiment.
[0125] FIG. 9 shows a schematic diagram of a pattern coat by a melt-blown spray nozzle head with an air curtain means using compressed gas according to the present embodiment.
[0126] FIG. 9-2 shows a schematic diagram of a pattern coat by a melt-blown spray nozzle head with an air curtain means using compressed gas, according to the present embodiment.
[0127] FIG. 10 shows a cross-sectional diagram of a spray from a melt-blown spray nozzle head with an air curtain means according to the present embodiment.
DETAILED DESCRIPTION
[0128] Now, a preferred embodiment of the present invention will be described with reference to the drawings. However, the embodiment below is only an example for facilitating the understanding of the present invention. Addition, replacement, deformation, or the like executable by those skilled in the art can be made thereto without departing from the technical idea of the present invention.
[0129] The drawings schematically show the preferred embodiment of the present invention.
[0130] In FIG. 1, a small diameter roll 4 having a diameter smaller than a heating and sucking drum 1 is provided upstream of the heating and sucking drum 1, a substrate 2 unwound by an unwinding device 5 is fed so as to pass through a nip roll 10, applied with an electrode slurry etc. (not shown) by a slot nozzle 3 on a off roll between the small diameter roll 4 and the heating and sucking drum 1, and then wound by a downstream winding device 6. The heating and sucking drum 1 can wind one or more micrometer-order breathable substrates (not shown) thereon. An electrode may be formed on the opposite side of the substrate 2. Further, an applying to the substrate 2 by the slot nozzle 3 may be performed by an on roll on the small diameter roll 4 or by an off roll before and after the small diameter roll 4 up to the heating and sucking roll 1. It is ideal in terms of dryness because a heating and an sucking start almost at the same time as the applying when the applying is performed on the off roll just before the heating and sucking drum 1. Especially when the applying is performed on the off roll, it is desirable that a tension of 5 to 150 newtons is applied to the substrate 2. Because an open/close valve mechanism in the slot nozzle 3 can perform a clean cut by using a sackback type (not shown) commonly used in the industry, it is possible to form a rectangular or square electrode pattern. Further, by assembling a shim having a desired pattern dimension, it is possible to provide a plurality of patterns orthogonal to a moving direction.
[0131] FIG. 2 shows a diagram in which a plurality of small diameter rolls 14, 14′ are installed in a configuration of FIG. 1. A slot nozzle 13 may be arranged on the on roll on the small diameter rolls 14, 14′ or on the off roll before and after the small diameter rolls 14, 14′. Further, the small diameter rolls 14, 14′ may be heated.
[0132] In FIG. 3, the electrode slurry is applied to a substrate 32 by a slot nozzle 33 with the on roll on a small diameter roll 34 to form an electrode pattern 205. A protective substrate 38 unwound and fed from a protective substrate unwinding device 39 is laminated on the substrate 32 and the electrode 205 dried on the heating and sucking roll 31 to be wound up as a composite by a winding device 36. The protective substrate may be a breathable substrate without limiting material, type and shape, and may be selected from those that are the cheapest in terms of cost and that do not transfer or are difficult to transfer an electrode thereto. It is possible to perform an applying using a slot nozzle on a heated small diameter roll having good roundness. An air assist slot nozzle, a mist ejection slit nozzle, and a meltblown type spray are effective on the heated small diameter roll, and by using them, it is possible to perform an applying on the heating and sucking roll.
[0133] In FIG. 4, a backsheet 165 is peeled off and wound by a backsheet winding device 102 upstream of a position where a first electrode is formed on the substrate 42. A position where the first electrode is formed on one side of the substrate 42 is detected by a detection sensor, and the electrode slurry is applied by the slot nozzle 43 to form the second electrode or the same electrode on the outer side of the substrate 42. A breathable substrate 138 moves on the heating and sucking drum while protecting the first electrode is wound by the breathable substrate winding device 101. A substrate having the first and second electrodes thereon is wound together with new protecting substrate 148 by a winding device 46. The protecting substrate may be a breathable substrate, one that does not affect the electrode surface and has a low cost can be selected as the protecting substrate.
[0134] FIG. 5 shows a schematic cross-sectional diagram in which a forming an electrode is performed by a spray method instead of the slot nozzle. Except for the spray method, a configuration in FIG. 5 can be almost the same as the configuration in FIG. 4. An air assist slot nozzle applying method that applies an electrode ink with compressed gas along an electrode ink flowing out from a slot nozzle or a mist ejection slit nozzle for using an electrode slurry as mist or is preferable. Alternatively, according to an applying method using a melt blown type spray nozzle head 203 that consists of a narrow angle spray group combined an air curtain means by compressed gas, it is possible to eliminate a mask. However, in other general spray method, due to large scattering of spray particles, a mask with a desired pattern shape should be installed. The substrate may be an electrolyte membrane for a fuel cell or a separator for a lithium ion battery. Further, this method is not limited to a formation of a second electrode and can form an electrode or an electrolyte layer on only one side of the substrate.
[0135] FIG. 5-2 is a diagram that shows a pattern being applied to the substrate on the heating drum (roll) 51 of FIG. 5 by the melt blown type spray nozzle head 203 that traverses perpendicular to travelling direction of the substrate. By increasing a number of spray nozzle of the spray head 203, it is possible to widen a total applying pattern width.
[0136] In a cross-sectional diagram of FIG. 6, a first electrode 305 and a second electrode 305′ are formed on both sides of a substrate 302 and a protecting substrate 348 is laminated on the second electrode 305′. It is suitable for a fuel cell in which the substrate is an electrolyte membrane and a positive electrode and a negative electrode are formed. When stacking a current collector and an electrode in multiple layers in a second battery, the second electrode may be an electrode having the same pole as the first electrode.
[0137] FIG. 7 shows a schematic cross-sectional diagram of an air assist slot nozzle (MS). An electrode slurry 770 passes through an inside of the MS as a liquid film and is discharged from a tip of a head of the MS. At the same time, the liquid film is assisted by compressed gas flowing out from both sides of the head and is applied to a substrate 702 to become an electrode. In particular, when applying intermittently to form a square pattern, it is possible to form a sharp edge of an electrode pattern 705 by adjusting an on/off timing of compressed gas with respect to an on/off of the electrode slurry. An outflow of compressed gas may be continuous or intermittent. When a surface of the substrate is uneven, it is particularly effective because the slurry can be pushed in the surface by a force of compressed gas. By mixing a solvent fine particle in the compressed gas, it is possible to moisten a tip of a nozzle and prevent a buildup of solid matter.
[0138] FIG. 8 shows a schematic cross-sectional diagram of a mist ejection slit nozzle 803. It is possible to form an electrode 805 by applying an electrode mist 880, which is mist, to a substrate 802 while moving a mist ejection slit nozzle 803 and the substrate 802 relative to each other. A mist can be atomized by ultrasonic waves, bubblers or colliding spray particles with a liquid surface, etc. at a close distance upstream of the slit nozzle, and can be moved to an inside of the slit nozzle by a carrier gas. Alternatively, it is possible to spray an electrode slurry with compressed gas to make spray particles in a slit nozzle having a wide slit groove width, and eject the electrode slurry from an opening of the slit nozzle. In the slit nozzle, the slit groove width 890 extends to a desired length in a substrate width direction orthogonal to a moving direction of the substrate 802 to form a slit opening section. It is noted that the slit groove width 890 may be 1 to 30 mm in a moving direction relative to the substrate, and a slit length can be longer than the slit groove, for example 50 to 1500 mm. For example, when an applying to a substrate having an applying width of 1000 mm is performed, a slit nozzle having a slit length of 1000 mm may be used, and the slit nozzle may be arranged orthogonal or substantially orthogonal to a traveling direction of the substrate. When using a nozzle having a narrow width, for example 100 mm slit length, it is possible to perform applying to make a 1000 mm×100 mm pattern by traversing a 100 mm narrow slit nozzle orthogonally to a traveling direction of the substrate. In the case of intermittent pattern applying, by setting a slit groove width to 5 mm or less with respect to a moving direction of the substrate, it is possible to maintain the sharpness and film thickness distribution with respect to an edge of a pattern at the start and end of applying. Further, when the slit groove width is 10 mm or more, it is suitable for a continuous applying method because the same effect as thin film lamination is obtained. Of course, it goes without saying that it is better to arrange a plurality of mist ejection slit nozzles in a plurality of rows in the moving direction of the substrate.
[0139] In FIG. 9, a plurality of narrow angle spray nozzles of a melt blown spray nozzle head are arranged in a row so that adjacent spray patterns 903 interfere with each other, and it is possible to overpaint finally in the end while shifting a spray timing in a pulsed manner by two independent opening/closing mechanisms upstream of adjacent spray nozzles to prevent a spray flow from interfering in an air. Further, it is possible to form an electrode 905 while flowing a fine compressed gas to closest positions to the both ends of a spray pattern by each air curtain nozzle 990 so that spray particles do not flow outside. In FIG. 9-2, a plurality of nozzles of the melt blown type spray nozzle head are arranged in two rows, and it is possible to obtain the same effect.
[0140] FIG. 10 shows spray flows 1100 from multiple spray nozzles 1003 arranged in a row on a melt blown type spray nozzle head and formation of air curtains by flowing compressed gas from each air curtain nozzle 1200 for not scattering particles outside both of the outermost ends of a spray flows sprayed on a substrate 1002 outside. When a substrate is a fuel cell electrolyte membrane, it is possible to form an electrode having a width between air curtains at both ends without a mask by traversing a melt blown spray nozzle head perpendicular to a traveling direction of the electrolyte membrane. It is possible to obtain a uniform distribution by performing spraying in a pulsed manner and moving at pitch so that spray patterns overlap. It is possible to increase uniformity by arranging multiple spray nozzles in 2 to 5 rows and increase productivity by increasing traverse speed.
[0141] The present invention is particularly effective for next generation secondary battery such as all-solid batteries and semi-solid batteries among secondary battery and is able to be applied more widely. It is effective for forming an electrode of supercapacitor. It is effective for forming an electrode of a fuel cell. Further, it is effective for products to which a coating agent or a glue/adhesive containing a functional material for applying a liquid or a melt to a long substrate in a roll-to-roll method is applied. It is effective for a wide range application in different fields other than wallpaper and labels, etc. as building materials, etc., for example resist coating in an electronics field, coating in a flat panel display field and coating on pharmaceutical patches, etc. as new delivery system, etc.
DESCRIPTION OF THE REFERENCE NUMERAL
[0142] 1, 11, 31, 41, 51 Heating (Heating and sucking) drum [0143] 2, 12, 32, 42, 302, 702, 802, 902 Substrate [0144] 3, 13, 33, 43 Slot nozzle [0145] 4, 14, 14′, 34, 34′, 44 Small diameter roll [0146] 5, 25, 35, 45, 55 Substrate unwinding device [0147] 6, 26, 36, 46, 56 Substrate winding device [0148] 7, 17 Current collector/electrode [0149] 10, 20, 30, 40, 50 Nip roll [0150] 38, 138, 148, 248, 348 Electrode protecting substrate (Breathable substrate) [0151] 39, 49, 59 Electrode protecting substrate unwinding device [0152] 101, 201 Electrode protecting substrate winding device [0153] 102, 202 Backseat winding device [0154] 203 Spray applying head (Melt blown type spray nozzle head) [0155] 205, 705, 805, 905 Electrode [0156] 305 First electrode [0157] 305′ Second electrode [0158] 703 Air assist slot nozzle [0159] 770 Electrode slurry [0160] 780, 1300 Compressed gas line [0161] 803 Mist ejection slit nozzle [0162] 880 Electrode mist [0163] 903 Spray applying pattern [0164] 990, 1200 Air curtain nozzle [0165] 1003 Spray nozzle [0166] 1100 Spray flow [0167] 1500 Air curtain
