JP2012199034A - Separator, and method and apparatus for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a separator having high mechanical strength, high insulation properties, high dendrite resistance and high ion conductivity.SOLUTION: A separator 100 includes: one cellulose fiber layer 110; a nanofiber layer 120 arranged on one surface of the cellulose fiber layer 110; and a nanofiber layer 130 arranged on the other surface of the cellulose fiber layer 110. The cellulose fiber layer 110 has a thickness of 1-40 μm and comprises a cellulose fiber having an average fiber diameter of 0.1-10 μm. The cellulose fiber layer 110 comprises a cellulose fiber having an average fiber length of 2.0 mm or longer.

Description

  The present invention relates to a separator, a separator manufacturing method, and a separator manufacturing apparatus.

  Conventionally, a separator using paper in which cellulose fibers are beaten is known (for example, see Patent Document 1). Since the separator described in Patent Document 1 is made from paper that is beaten cellulose fibers, it has high mechanical strength in addition to high heat resistance compared to conventionally used polyolefin-based separators. . Therefore, in the separator described in Patent Document 1, it is considered that high mechanical strength can be maintained even if the separator is thinned to increase ion conductivity.

JP-A-10-223196

  However, according to the research of the inventors of the present invention, in the separator described in Patent Document 1, when the separator is thinned to increase the ionic conductivity, high mechanical strength can be maintained, but insulation is maintained. And it has been found that there is a problem that the dendrite resistance is lowered.

  Then, this invention is made | formed in order to solve the above problems, and it aims at providing the separator which has high mechanical strength, high insulation, high dendrite resistance, and high ion conductivity. . Moreover, it aims at providing the manufacturing method and manufacturing apparatus of a separator which can manufacture such a separator.

[1] The separator of the present invention includes at least one cellulose fiber layer and at least one nanofiber layer.

  For this reason, according to the separator of this invention, since it has a nanofiber layer which has the characteristics that a fiber is thin and a space | gap is fine and uniform, it has high insulation and high dendrite resistance. In addition, since the nanofiber layer also has a feature that the porosity is large, it has high electrolytic solution retention characteristics and high ionic conductivity.

  Moreover, according to the separator of this invention, since it has a cellulose fiber layer, it has high mechanical strength.

  As a result, the separator of the present invention is a separator having high mechanical strength, high insulation, high dendrite resistance and high ionic conductivity.

[2] In the separator of the present invention, the cellulose fiber layer is preferably composed of cellulose fibers having a thickness of 1 μm to 40 μm and an average fiber diameter of 0.1 μm to 10 μm.

  According to the separator of this invention, since the thickness of a cellulose fiber layer is 40 micrometers or less, it becomes possible to manufacture a thin separator and it becomes possible to manufacture a secondary battery and a capacitor with a large electric capacity. Moreover, since the thickness of a cellulose fiber layer is 1 micrometer or more, mechanical strength does not fall.

  Further, according to the separator of the present invention, since the cellulose fiber layer is composed of cellulose fibers having an average fiber diameter of 0.1 μm or more, it is easy to maintain the strength of the cellulose fibers themselves, and sufficient mechanical strength is obtained without increasing the thickness. The cellulose fiber layer which has can be comprised. On the other hand, since the cellulose fiber layer is composed of cellulose fibers having an average fiber diameter of 10 μm or less, a thin separator can be manufactured, and a non-aqueous battery having a large electric capacity can be manufactured.

[3] In the separator of the present invention, the cellulose fiber layer is preferably composed of cellulose fibers having an average fiber length of 2.0 mm or more.

  By setting it as such a structure, since the location where a cellulose fiber is entangled increases, it becomes possible to comprise the separator which has sufficient mechanical strength, without making it so thick.

[4] In the separator of the present invention, the nanofiber layer has a porosity in the range of 20% to 80% and an average pore size in the range of 0.02 μm to 2 μm. preferable.

  By setting it as such a structure, since the porosity of a nanofiber layer exists in the range of 20%-80%, it has a high electrolyte solution retention characteristic, and it becomes possible to obtain high ion conductivity. Further, since the average pore size is in the range of 0.02 μm to 2 μm and the dendrite is a pore size that is difficult to enter the separator, it has high dendrite resistance.

[5] In the separator of the present invention, the separator preferably has a structure in which the nanofiber layer is disposed on both surfaces of the cellulose fiber layer.

  By setting it as such a structure, it becomes possible to prevent the growth of a dendrite on both surfaces of a cellulose fiber layer, and it becomes possible to comprise the separator which has much higher dendrite tolerance.

[6] In the separator of the present invention, the separator preferably has a structure in which the cellulose fiber layer is disposed on both surfaces of the nanofiber layer.

  By setting it as such a structure, it becomes possible to comprise the separator which has much higher mechanical strength.

[7] The separator manufacturing method of the present invention is a separator manufacturing method for manufacturing the separator of the present invention, comprising a step of preparing a long sheet made of the cellulose fiber layer and the length of the sheet being conveyed. Forming the nanofiber layer on one surface of the length sheet.

  For this reason, according to the separator manufacturing method of the present invention, it is possible to continuously manufacture the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ionic conductivity with high productivity. It becomes.

  Moreover, according to the manufacturing method of the separator of this invention, the cellulose fiber layer in which the nanofiber layer was formed can be made into a product as it is. For this reason, the process of removing the product of the separator from the long sheet can be omitted, and the productivity can be further increased.

[8] The separator manufacturing method of the present invention preferably further includes a step of forming the nanofiber layer on the other surface of the long sheet being conveyed.

  By setting it as such a method, it becomes possible to manufacture the separator of the structure where the nanofiber layer was arrange | positioned on both surfaces of the cellulose fiber layer.

[9] The separator manufacturing method of the present invention is a manufacturing method of the separator for manufacturing the separator of the present invention, wherein the nanofiber layer and the cellulose are formed on one surface of the long sheet being conveyed. It is preferable to produce a separator by sequentially forming fiber layers.

  For this reason, even with the separator manufacturing method of the present invention, it is possible to continuously manufacture the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ionic conductivity with high productivity. Become.

  Further, by appropriately adjusting the order of forming the nanofiber layer and the cellulose fiber layer, a separator having a structure in which the nanofiber layer is disposed on one surface of the cellulose fiber layer, and the nanofiber layer on both surfaces of the cellulose fiber layer. It is possible to manufacture both the separator having the structure and the separator having the structure in which the cellulose fiber layers are disposed on both surfaces of the nanofiber layer.

[10] The separator manufacturing apparatus of the present invention is a separator manufacturing apparatus for manufacturing the separator of the present invention, and is transported by the transport apparatus that transports a long sheet made of the cellulose fiber layer and the transport apparatus. And an electrospinning apparatus for forming a nanofiber layer on the long sheet.

  Therefore, according to the separator manufacturing apparatus of the present invention, it is possible to continuously manufacture the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ionic conductivity with high productivity. Become.

  Moreover, according to the separator manufacturing apparatus of this invention, the cellulose fiber layer in which the nanofiber layer was formed can be used as a product as it is. For this reason, the process of removing the product of the separator from the long sheet can be omitted, and the productivity can be further increased.

[11] The separator manufacturing device of the present invention is a separator manufacturing device for manufacturing the separator of the present invention, and includes a transport device that transports a long sheet and the long sheet that is transported by the transport device. An electrospinning apparatus that forms a nanofiber layer, and a cellulose fiber layer manufacturing apparatus that forms a cellulose fiber layer on the long sheet conveyed by the conveying apparatus.

  For this reason, even with the separator manufacturing apparatus of the present invention, the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ionic conductivity can be continuously manufactured with high productivity. .

  In addition, by appropriately adjusting the order in which the electrospinning apparatus and the cellulose fiber layer manufacturing apparatus are arranged, a separator having a structure in which the nanofiber layer is disposed on one surface of the cellulose fiber layer, and the nanofiber on both surfaces of the cellulose fiber layer. It is possible to manufacture both a separator having a structure in which a layer is disposed and a separator having a structure in which a cellulose fiber layer is disposed on both sides of a nanofiber layer.

[12] In the separator manufacturing apparatus of the present invention, the cellulose fiber layer manufacturing apparatus is preferably a melt blow spinning apparatus.

  By adopting such a configuration, it becomes possible to adjust the thickness of the cellulose fiber layer, the fiber length of the cellulose fiber, the porosity and the pore size of the cellulose fiber layer, and a cellulose fiber layer having desired characteristics can be obtained. It becomes possible to form. This is suitable for forming a cellulose fiber layer made of cellulose fibers having a relatively large average fiber diameter.

[13] In the separator manufacturing apparatus of the present invention, the cellulose fiber layer manufacturing apparatus is preferably an electrospinning apparatus.

  Even with such a configuration, it becomes possible to adjust the thickness of the cellulose fiber layer, the fiber length of the cellulose fiber, the porosity and the pore size of the cellulose fiber layer, and the cellulose fiber layer having desired characteristics Can be formed. It is suitable for forming a cellulose fiber layer composed of cellulose fibers having a relatively small average fiber diameter.

1 is a cross-sectional view of a separator 100 according to Embodiment 1. FIG. It is sectional drawing of the separator manufacturing apparatus 1 which concerns on Embodiment 1. FIG. It is a figure which shows a mode that the separator 100 is manufactured with the manufacturing method of the separator which concerns on Embodiment 1. FIG. It is sectional drawing of the separator manufacturing apparatus 2 which concerns on Embodiment 2. FIG. It is sectional drawing of the separator 102 which concerns on Embodiment 3. FIG. It is sectional drawing of the separator manufacturing apparatus 3 which concerns on Embodiment 3. FIG. It is a figure which shows a mode that the separator 102 is manufactured with the manufacturing method of the separator which concerns on Embodiment 3. FIG. It is sectional drawing of the separator manufacturing apparatus 4 which concerns on Embodiment 4. FIG. It is sectional drawing of the separator manufacturing apparatus 5 which concerns on Embodiment 5. FIG.

  Hereinafter, the separator of the present invention, a separator manufacturing device, and a separator manufacturing method are explained based on an embodiment shown in a figure.

[Embodiment 1]
1. Configuration of Separator according to Embodiment 1 First, the configuration of the separator 100 according to Embodiment 1 will be described.
FIG. 1 is a cross-sectional view of a separator 100 according to the first embodiment.

  As illustrated in FIG. 1, the separator 100 according to the first embodiment includes one cellulose fiber layer 110 and two nanofiber layers 120 and 130, and the nanofiber layers 120 and 130 are provided on both sides of the cellulose fiber layer 110. It has an arranged structure.

  The cellulose fiber layer 110 is made of cellulose fibers having a thickness of 1 μm to 40 μm and an average fiber diameter of 0.1 μm to 10 μm.

  The nanofiber layers 120 and 130 have a porosity in the range of 20% to 80% and an average pore size in the range of 0.02 μm to 2 μm.

  The separator 100 is obtained by the separator manufacturing method according to Embodiment 1 using the separator manufacturing apparatus 1 according to Embodiment 1 described later.

2. Configuration of Separator Manufacturing Apparatus 1 According to Embodiment 1 FIG. 2 is a cross-sectional view of the separator manufacturing apparatus 1 according to the embodiment. In FIG. 2, the polymer solution supply unit is not shown. The same applies to the following figures described later. FIG. 3 is a diagram illustrating a state in which the separator 100 is manufactured by the separator manufacturing method according to the first embodiment. FIG. 3A to FIG. 3C are process diagrams.

  As shown in FIG. 2, the separator manufacturing apparatus 1 according to Embodiment 1 includes a transport device 10 that transports a long sheet composed of a long cellulose fiber layer 110, and a cellulose fiber layer 110 that is transported by the transport device 10. The electrospinning apparatus 20a for forming the nanofiber layer 120 (see FIG. 3B) on one side of the electrode and the electrospinning apparatus for forming the nanofiber layer 130 (see FIG. 3C) on the other side. 20b. Both the electrospinning apparatus 20a and the electrospinning apparatus 20b are upward electrospinning apparatuses having an upward nozzle.

  The conveying device 10 is configured to convey the cellulose fiber layer 110 serving as a base material layer from the electrospinning device 20a to the electrospinning device 20b. When the electrospinning device 20a forms the nanofiber layer 120 (see FIG. 3B described later), the transport device 10 transports the cellulose fiber layer 110 in the first direction (direction A1 in FIG. 2). Then, the cellulose fiber layer 110 is transported from the height position of the electrospinning apparatus 20a to the height position of the electrospinning apparatus 20b in a second direction (A2 direction) substantially perpendicular to the first direction, and the electrospinning apparatus 20b. When forming the nanofiber layer 130 (see FIG. 3C described later), the cellulose fiber layer 110 is conveyed in a third direction (direction A3) opposite to the first direction.

  The conveying device 10 includes a feeding roller 11 for feeding the cellulose fiber layer 110, a winding roller 12 for winding the cellulose fiber layer 110, tension rollers 13 and 18 for adjusting the tension of the cellulose fiber layer 110, and the cellulose fiber layer 110. The plurality of driving rollers 14 to be transported, the first reversing roller 16a that directs the transport direction of the cellulose fiber layer 110 from the electrospinning apparatus 20a upward, and the transport direction of the cellulose fiber layer 110 from the first reversing roller 16a are electrospun. A second reversing roller 16b directed toward the device 20b.

  Among these, the feeding roller 11, the take-up roller 12, the tension rollers 13 and 18, and the plurality of drive rollers 14 constitute a transport mechanism (not shown) that transports the cellulose fiber layer 110. The plurality of driving rollers 14 are driving devices that convey the cellulose fiber layer 110.

  The first reverse roller 16a and the second reverse roller 16b move the cellulose fiber layer 110 so that the direction of one surface of the cellulose fiber layer 110 is opposite to the direction of the other surface while the cellulose fiber layer 110 is being conveyed. The cellulose fiber layer inversion mechanism 15 to be inverted is configured. The cellulose fiber layer reversing mechanism 15 reverses the cellulose fiber layer 110 from the electrospinning device 20a in accordance with the height position of the electrospinning device 20b.

  The electrospinning apparatuses 20a and 20b are attached to the casing 21 via an insulating member 25, and face the collector 24 located on the other surface side of the cellulose fiber 110 and the collector 24 on the one surface side of the cellulose fiber layer 110. A nozzle unit 22 having a plurality of nozzles 23 for discharging a polymer solution supplied from a polymer solution supply unit (not shown) toward the cellulose fiber layer 110, and between the collector 24 and the nozzle unit 22. The power supply apparatus 29 which applies a voltage (for example, 10 kV-80 kV) and the auxiliary | assistant belt apparatus 26 which assists that the cellulose fiber layer 110 is conveyed are provided.

The nozzle unit 22 in the electrospinning apparatuses 20a and 20b has a plurality of upward nozzles 23 that discharge the polymer solution upward from the discharge ports as a plurality of nozzles. The electrospinning apparatus 20a is configured to discharge the polymer solution from the discharge ports of the plurality of upward nozzles 23 to electrospin the nanofibers.
The plurality of upward nozzles 23 are arranged at a pitch of 1.5 cm to 6.0 cm, for example. The number of the plurality of upward nozzles 23 is, for example, 36 (6 × 6 when arranged in the same length and width) to 21904 (148 × 148 when arranged in the same length and width).
Moreover, although the nozzle unit 22 which has various sizes and various shapes can be used for the separator manufacturing apparatus of the present invention, the nozzle unit 22 has, for example, a side of 0.5 m to 3 m when viewed from the upper surface. It has a size and shape that looks like a rectangle (including a square).

  The collector 24 is attached to the casing 21 having conductivity through an insulating member. The positive electrode of the power supply device 29 is connected to the collector 24, and the negative electrode of the power supply device 29 is connected to the casing 21 and the nozzle unit 22.

  The auxiliary belt device 26 includes an auxiliary belt 27 that rotates in synchronization with the conveyance speed of the cellulose fiber layer 110, and five auxiliary belt rollers 28 that assist the rotation of the auxiliary belt 27. Of the five auxiliary belt rollers 28, one or more auxiliary belt rollers are drive rollers, and the remaining auxiliary belt rollers are driven rollers. Since the auxiliary belt 27 is disposed between the collector 24 and the cellulose fiber layer 110, the cellulose fiber layer 110 is smoothly conveyed without being attracted to the collector 24 to which a positive high voltage is applied. become.

3. Method for Producing Separator According to Embodiment 1 Hereinafter, a method for producing a separator 100 using the separator production apparatus 1 according to Embodiment 1 configured as described above (a method for producing a separator according to Embodiment 1) will be described. .

(A) Preparation for spinning A polymer solution is prepared in each of the two electrospinning apparatuses 20 a and 20 b, and the polymer solution is supplied to the nozzle unit 22. Further, the long cellulose fiber layer 110 (see FIG. 3A) is set in the transport device 10, and then the cellulose fiber layer 110 is transported from the feeding roller 11 toward the take-up roller 12 at a predetermined transport speed. To do.

(B) Electrospinning (1)
Next, the nanofiber layer 120 is formed on one surface of the cellulose fiber layer 110 being conveyed by the electrospinning apparatus 20a (see FIG. 3B).

(C) Long sheet reversal Next, with the long sheet reversing mechanism 15 (reversing rollers 16a and 16b), the orientation of one surface of the cellulose fiber layer 110 is set so that one surface of the cellulose fiber layer 110 is on the lower side. The direction of the other surface is reversed.

d) Electrospinning (2)
Next, the nanofiber layer 130 is formed on the other surface of the cellulose fiber layer 110 being conveyed by the electrospinning apparatus 20b (see FIG. 3C). Thereby, the separator 100 having a structure in which the nanofiber layers 120 and 130 are disposed on both surfaces of the cellulose fiber layer 110 is completed.

  The spinning conditions in the separator manufacturing method according to Embodiment 1 will be exemplified below.

  Examples of the polymer used as a raw material for the nanofiber include polylactic acid (PLA), polypropylene (PP), polyvinyl acetate (PVAc), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), Polyamide (PA), polyurethane (PUR), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyetherimide (PEI), polycaprolactone (PCL), polylactic glycolic acid (PLGA), silk, cellulose, chitosan, etc. Can be used.

  Examples of the solvent used in the polymer solution include dichloromethane, dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, chloroform, acetone, water, formic acid, acetic acid, cyclohexane, and THF. A plurality of types of solvents may be mixed and used. The polymer solution may contain an additive such as a conductivity improver.

  As plant fiber used as a raw material of cellulose fiber, for example, conifers, Manila hemp, Mitsumata, kouzo and the like can be used. A plurality of types of fibers may be mixed and used.

  A conveyance speed can be set to 0.2 m / min-100 m / min, for example. The voltage applied between the collector 24 and the nozzle unit 22 can be set to 10 kV to 80 kV, and is preferably set to around 50 kV.

  The temperature of the spinning zone can be set to 10 ° C. to 40 ° C., for example. The humidity of the spinning area can be set to 20% to 60%, for example.

4). Effect of Separator 100 According to Embodiment 1 According to the separator 100 according to Embodiment 1, since the nanofiber layers 120 and 130 having the characteristics that the fibers are thin and the voids are fine and uniform are provided, high insulation and high dendrite are provided. Tolerant. In addition, since the nanofiber layer also has a feature that the porosity is large, it has high electrolytic solution retention characteristics and high ionic conductivity.

  Moreover, according to the separator 100 which concerns on Embodiment 1, since it has the cellulose fiber layer 110, it has high mechanical strength.

  As a result, the separator 100 according to the first embodiment is a separator having high mechanical strength, high insulation, high dendrite resistance, and high ionic conductivity.

  Further, according to the separator 100 according to the first embodiment, since the thickness of the cellulose fiber layer 110 is 40 μm or less, it is possible to manufacture a thin separator, and it is possible to manufacture a non-aqueous battery having a large electric capacity. It becomes. Moreover, since the thickness of the cellulose fiber layer 110 is 1 μm or more, the mechanical strength is not lowered.

  Moreover, according to the separator 100 which concerns on Embodiment 1, since the cellulose fiber layer 110 consists of a cellulose fiber with an average fiber diameter of 0.1 micrometer or more, it becomes easy to maintain the intensity | strength of cellulose fiber itself, and it is enough, without making it so thick. A cellulose fiber layer having mechanical strength can be formed. On the other hand, since the cellulose fiber layer 110 is made of cellulose fibers having an average fiber diameter of 10 μm or less, a thin separator can be manufactured and a non-aqueous battery having a large electric capacity can be manufactured.

  Moreover, according to the separator 100 which concerns on Embodiment 1, since the location where a cellulose fiber entangles increases, it becomes possible to comprise the separator which has sufficient mechanical strength, without making it so thick.

  Moreover, according to the separator 100 which concerns on Embodiment 1, since the porosity of the nanofiber layers 120 and 130 exists in the range of 20%-80%, it has a high electrolyte solution retention characteristic, and high ionic conductivity. Can be obtained. Further, since the average pore size is in the range of 0.02 μm to 2 μm and the dendrite is a pore size that is difficult to enter the separator, it has high dendrite resistance.

  In addition, according to the separator 100 according to the first embodiment, it is possible to prevent the growth of dendrite on both surfaces of the cellulose fiber layer 110, and it is possible to configure a separator having higher dendrite resistance.

5). Effect of Separator Manufacturing Method According to Embodiment 1 According to the separator manufacturing method according to Embodiment 1, the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ionic conductivity is continuously provided. And can be manufactured with high productivity.

  Moreover, according to the manufacturing method of the separator which concerns on Embodiment 1, the cellulose fiber layer 110 in which the nanofiber layers 120 and 130 were formed can be used as a product as it is. For this reason, the process of removing the product of the separator from the long sheet can be omitted, and the productivity can be further increased.

6). Effects of separator manufacturing apparatus 1 according to Embodiment 1 According to the separator manufacturing apparatus 1 according to Embodiment 1, the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ionic conductivity is continuously provided. And can be manufactured with high productivity.

  Moreover, according to the separator manufacturing apparatus 1 which concerns on Embodiment 1, the cellulose fiber layer 110 in which the nanofiber layers 120 and 130 were formed can be used as a product as it is. For this reason, the process of removing the product of the separator from the long sheet can be omitted, and the productivity can be further increased.

[Embodiment 2]
FIG. 4 is a cross-sectional view of the separator manufacturing apparatus 2 according to the second embodiment.

  As shown in FIG. 4, the separator manufacturing apparatus 2 according to the second embodiment has basically the same configuration as the separator manufacturing apparatus 1 according to the first embodiment, but the configuration of the electrospinning apparatus according to the first embodiment. Different from the case of the separator manufacturing apparatus 1. That is, in the separator manufacturing apparatus 2 according to the second embodiment, as shown in FIG. 4, the electrospinning apparatus 20a for forming the nanofiber layer 120 on one surface of the cellulose fiber layer 110 being conveyed, and the other surface And an electrospinning apparatus 20c for forming the nanofiber layer 130. The electrospinning device 20c is a downward electrospinning device having a downward nozzle.

  In the separator manufacturing apparatus 2 according to the second embodiment, as shown in FIG. 4, the electrospinning apparatus 20 a and the electrospinning apparatus 20 c are arranged in the same straight line along the conveying direction of the cellulose fiber layer 110 in this order. Has been placed.

  The electrospinning device 20c is attached to the support base 35 via an insulating member, and is located at a position facing the collector 34 located on one side of the cellulose fiber 110 and the collector 34 on the other side of the cellulose fiber layer 110. A nozzle unit 32 having a plurality of downward nozzles 33 positioned, a power supply device 29, and an auxiliary belt device 36 for assisting the conveyance of the cellulose fiber layer 110 are provided.

  The nozzle unit 32 is attached to the housing 31 and has a plurality of downward nozzles 33 for discharging the polymer solution downward from the discharge port as a plurality of nozzles.

  The collector 34 is attached to a support base 35 having conductivity via an insulating member. The positive electrode of the power supply device 29 is connected to the collector 34, and the negative electrode of the power supply device 29 is connected to the housing 35 and the nozzle unit 32.

  The auxiliary belt device 36 includes an auxiliary belt 37 that rotates in synchronization with the conveyance speed of the cellulose fiber layer 110, and five auxiliary belt rollers 38 that assist the rotation of the auxiliary belt 37.

  As described above, the separator manufacturing apparatus 2 according to the second embodiment is different from the separator manufacturing apparatus 1 according to the first embodiment in the configuration of the electrospinning apparatus, but is similar to the separator manufacturing apparatus 1 according to the first embodiment. The separator of the present invention having mechanical strength, high insulation, high dendrite resistance and high ionic conductivity can be continuously produced with high productivity.

  Moreover, according to the separator manufacturing apparatus 2 which concerns on Embodiment 2, the cellulose fiber layer 110 in which the nanofiber layers 120 and 130 were formed can be used as a product as it is. For this reason, the process of removing the product of the separator from the long sheet can be omitted, and the productivity can be further increased.

  Moreover, according to the separator manufacturing apparatus 2 which concerns on Embodiment 2, the separator which has the structure by which the nanofiber layer was arrange | positioned on both surfaces of the cellulose fiber layer is manufactured, without making the installation height of a separator manufacturing apparatus so high. It becomes possible.

  In addition, since the separator manufacturing apparatus 2 which concerns on Embodiment 2 has the structure similar to the case of the separator manufacturing apparatus 1 which concerns on Embodiment 1 except the structure of an electrospinning apparatus, the separator manufacturing apparatus 1 which concerns on Embodiment 1 has. It has a corresponding effect among the effects.

[Embodiment 3]
1. Configuration of Separator 102 According to Embodiment 3 The configuration of the separator 102 according to Embodiment 3 will be described.
FIG. 5 is a cross-sectional view of the separator 102 according to the third embodiment.

  As shown in FIG. 5, the separator 102 according to the third embodiment has basically the same configuration as the separator 100 according to the first embodiment, but the configuration of the cellulose fiber layer is the separator 100 according to the first embodiment. And different. That is, the separator 102 according to Embodiment 3 includes a cellulose fiber layer 112 manufactured by a cellulose fiber layer manufacturing apparatus 40 described later, as shown in FIG.

  The separator 102 is obtained by the separator method according to the third embodiment using the separator manufacturing apparatus 3 according to the third embodiment which will be described later.

2. Configuration of Separator Manufacturing Apparatus 3 According to Embodiment 3 FIG. 6 is a cross-sectional view of the separator manufacturing apparatus 3 according to Embodiment 3. FIG. 7 is a diagram illustrating a state in which the separator 102 is manufactured by the separator manufacturing method according to the third embodiment.

  The separator manufacturing apparatus 3 according to the third embodiment basically has the same configuration as the separator manufacturing apparatus 1 according to the first embodiment, but the first embodiment is further provided with a configuration of a transport device and a cellulose fiber layer manufacturing apparatus. This is different from the case of the separator manufacturing apparatus 1 according to the above. That is, as shown in FIG. 6, the separator manufacturing apparatus 3 according to the third embodiment includes a conveyance device 60 that conveys the long sheet W, electrospinning devices 20 a and 20 b, and a cellulose fiber layer that forms the cellulose fiber layer 112. And a manufacturing apparatus 40.

  In the separator manufacturing apparatus 3 according to Embodiment 3, as shown in FIG. 6, an electrospinning apparatus 20a, a long sheet reversing mechanism 65a described later, a cellulose fiber layer manufacturing apparatus 40, and a long sheet reversing mechanism described later. 65b and the electrospinning device 20b are arranged in this order along the conveying direction of the long sheet W.

A long sheet conveying device 60 is provided as a conveying device.
The long sheet conveying device 60 includes a feeding roller 61 for feeding out the long sheet W, a take-up roller 62 for winding up the long sheet W, tension rollers 63 and 68 for adjusting the tension of the long sheet W, and a long length. A plurality of drive rollers 64 for conveying the sheet W, first reverse rollers 66a and 66c, and second reverse rollers 66b and 66d are provided.

  Among these, the feeding roller 61, the take-up roller 62, the tension rollers 63 and 68, and the plurality of drive rollers 64 constitute a conveyance mechanism 60 that conveys the long sheet W. The plurality of driving rollers 64 are driving devices that convey the long sheet W.

  The first reversing roller 66a and the second reversing roller 66b move the long sheet W so that the direction of one surface of the long sheet W and the direction of the other surface are opposite while the long sheet W is being conveyed. A long sheet reversing mechanism 65a for reversing is configured. Further, the first reverse roller 66c and the second reverse roller 66d are long sheets so that the direction of one surface of the long sheet W and the direction of the other surface are opposite while the long sheet W is being conveyed. A long sheet reversing mechanism 65b for reversing W is configured.

  The electrospinning apparatuses 20a and 20b have the same configuration as the electrospinning apparatuses 20a and 20b used in the first embodiment.

As shown in FIG. 6, the cellulose fiber layer manufacturing apparatus 40 forms the cellulose fiber layer 112 on the long sheet W conveyed by the long sheet conveying apparatus 60.
The cellulose fiber layer manufacturing apparatus 40 includes a nozzle unit 42 having a plurality of downward nozzles 43 that discharge a cellulose solution supplied from a cellulose solution supply unit (not shown) toward the long sheet W, and a high-temperature airflow toward the cellulose solution. A high-temperature air flow supply unit 44 for spraying and a high-temperature air flow suction device 47 are provided.

  The nozzle unit 42 is attached to the housing 21, and as a plurality of nozzles, a plurality of downward nozzles 43 that discharge the cellulose solution downward from the discharge port, and a high-temperature air flow supply that will be described later in a direction along the cellulose solution discharge direction A high-temperature air flow path (not shown) through which the high-temperature air supplied from the unit 44 flows. The plurality of downward nozzles 43 are arranged at a pitch of 1.5 cm to 6.0 cm, for example. As the nozzle unit 42, nozzle units having various sizes and various shapes can be used.

The high temperature air flow supply unit 44 includes a suction pump 45 and a heater 46.
The high-temperature air flow supply unit 44 forms a high-temperature air flow by heating the air taken in from the outside by the suction pump 84 by the heater 46. The high temperature air flow is guided to a high temperature air flow path (not shown) in the nozzle unit 42. The heater 46 can adjust the output so that the high-temperature airflow has a predetermined temperature in the range of 120 ° C to 500 ° C.

The high temperature air flow suction device 47 is disposed on the back side of the long sheet W when viewed from the nozzle unit 42, and includes a mesh member 48, a high temperature air flow suction unit 50, and a discharge pump 51.
The high temperature airflow that has flowed from the high temperature airflow path (not shown) is sucked by the high temperature airflow suction unit 50 through the mesh member 44 in which a large number of holes for airflow passage are formed, and is discharged to the outside by the discharge pump 51. Discharged.

3. Method for Producing Separator According to Embodiment 3 Hereinafter, a method for producing a separator using the separator production apparatus 3 according to Embodiment 3 configured as described above (a separator production method according to Embodiment 3) will be described.

  FIG. 7 is a diagram illustrating a state in which the separator 102 is manufactured by the separator manufacturing method according to the third embodiment. Fig.7 (a)-FIG.7 (e) are each process drawing.

(A) Preparation for spinning A cellulose solution is prepared in one cellulose fiber layer manufacturing apparatus 40, and the cellulose solution is supplied to the nozzle unit 42. In addition, a polymer solution is prepared in each of the two electrospinning apparatuses 20 a and 20 b, and the polymer solution is supplied to each nozzle unit 22. Further, the long sheet W is set in the long sheet conveyance device 60, and then the long sheet W is conveyed from the feeding roller 61 toward the take-up roller 62 at a predetermined conveyance speed (see FIG. 7A). ). The cellulose solution is obtained by melting cellulose used as the material of the cellulose fiber layer 112 or dissolving it with a solvent.

(B) Electrospinning (1)
Next, while conveying the long sheet 110, the nanofiber layer 120 is formed on one surface of the long sheet W by the electrospinning apparatus 20a (see FIG. 7B).

(C) Long sheet reversal (1)
Next, the orientation of one side and the orientation of the other side of the long sheet W are reversed by the long sheet reversing mechanism 65a (reversing rollers 66a and 66b) so that the one side is on the upper side.

(D) Cellulose Fiber Layer Production Next, the cellulose fiber layer 112 is formed on one surface of the long sheet W by the cellulose fiber production apparatus 40 while conveying the long sheet W on which the nanofiber layer 120 is formed ( (See FIG. 7 (c)). Thereby, the nanofiber layer 120 and the nanofiber layer 130 are laminated in this order on one surface of the long sheet W.

(C) Long sheet reversal (2)
Next, the direction of one surface and the other surface of the long sheet W are reversed by the long sheet reversing mechanism 65b (reversing rollers 66c and 66d) so that one surface is on the lower side.

(E) Electrospinning (2)
Next, the nanofiber layer 130 is formed on one surface of the long sheet W by the electrospinning apparatus 20b while conveying the long sheet W on which the nanofiber layer 120 and the cellulose fiber layer 112 are laminated (FIG. 7D). )reference.). Thereby, the lamination sheet by which the nanofiber layer 120, the cellulose fiber layer 112, and the nanofiber layer 130 were laminated | stacked in this order on the one side of the elongate sheet W is manufactured. Thereafter, the laminated sheet is taken up from the take-up roller 12.

(F) Separation of Separator and Long Sheet Thereafter, the separator and the long sheet are separated while feeding the laminated sheet to manufacture the separator 102 (see FIG. 5E).
The separator 102 can be manufactured by the above method.

  As the long sheet, a nonwoven fabric, a woven fabric, a knitted fabric, a film, paper, or the like made of various materials can be used. For example, a long sheet having a thickness of 5 μm to 500 μm can be used. The length of the long sheet can be, for example, 10 m to 10 km.

4). Effect of Separator Manufacturing Apparatus 3 According to Embodiment 3 A separator manufacturing apparatus 3 according to Embodiment 3 is different from the separator manufacturing apparatus 1 according to Embodiment 1 in that the separator manufacturing apparatus 3 further includes a configuration of a transport device and a cellulose fiber layer manufacturing apparatus. However, like the separator manufacturing apparatus 1 according to Embodiment 1, the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ionic conductivity can be manufactured continuously with high productivity. It becomes possible.

  Moreover, according to the separator manufacturing apparatus 3 which concerns on Embodiment 3, it becomes possible to adjust the thickness of a cellulose fiber layer, the fiber length of a cellulose fiber, the porosity and pore size of a cellulose fiber layer, and a desired characteristic. It becomes possible to form the cellulose fiber layer which has. This is suitable for forming a cellulose fiber layer made of cellulose fibers having a relatively large average fiber diameter.

  In addition, since the separator manufacturing apparatus 3 which concerns on Embodiment 3 has the structure similar to the case of the separator manufacturing apparatus 1 which concerns on Embodiment 1 except the point further equipped with the structure of a conveying apparatus and a cellulose fiber layer manufacturing apparatus, Embodiment 1 has a corresponding effect among the effects of the separator manufacturing apparatus 1 according to 1.

  In the present invention, the nanofiber layer is arranged on one surface of the cellulose fiber layer by appropriately changing the order of arranging the electrospinning device and the cellulose fiber layer production device from that of the separator production device 3 according to Embodiment 3. The separator having the structure provided, the separator having the structure in which the nanofiber layer is disposed on both sides of the cellulose fiber layer, and the separator having the structure in which the cellulose fiber layer is disposed on both sides of the nanofiber layer are manufactured. Is possible.

[Embodiment 4]
FIG. 8 is a cross-sectional view of the separator manufacturing apparatus 4 according to the fourth embodiment.

  The separator manufacturing apparatus 4 according to the fourth embodiment has basically the same configuration as the separator manufacturing apparatus 3 according to the third embodiment, except that the configuration of the electrospinning apparatus is the separator manufacturing apparatus 3 according to the third embodiment. Different. That is, in the separator manufacturing apparatus 4 according to the fourth embodiment, as shown in FIG. 8, the downward electrospinning apparatus 20 d that forms the nanofiber layer 120 on the long sheet W that is being conveyed, and the length that is being conveyed. And a downward-type electrospinning apparatus 20c for forming the nanofiber layer 130 on the length sheet W.

  In the separator manufacturing apparatus 4 according to Embodiment 4, as shown in FIG. 8, the electrospinning apparatus 20d, the cellulose fiber layer manufacturing apparatus 40, and the electrospinning apparatus 20c are arranged in this order in the conveying direction of the long sheet W. It is arranged to be on the same straight line.

  As described above, the separator manufacturing apparatus 4 according to the fourth embodiment is different from the separator manufacturing apparatus 3 according to the third embodiment in the configuration of the electrospinning apparatus, but is similar to the separator manufacturing apparatus 3 according to the third embodiment. The separator of the present invention having mechanical strength, high insulation, high dendrite resistance and high ionic conductivity can be continuously produced with high productivity.

  Moreover, according to the separator manufacturing apparatus 4 which concerns on Embodiment 4, a nanofiber layer is arrange | positioned by the one side of a cellulose fiber layer by adjusting suitably the order which arrange | positions an electrospinning apparatus and a cellulose fiber layer manufacturing apparatus. It is possible to manufacture a separator having a structure in which a nanofiber layer is disposed on both sides of a cellulose fiber layer and a separator having a structure in which a cellulose fiber layer is disposed on both sides of a nanofiber layer. It becomes.

  Moreover, according to the separator manufacturing apparatus 4 which concerns on Embodiment 4, the separator which has the structure by which the nanofiber layer was arrange | positioned on both surfaces of the cellulose fiber layer is manufactured, without making the installation height of a separator manufacturing apparatus so high. It becomes possible.

  In addition, since the separator manufacturing apparatus 4 according to Embodiment 4 has the same configuration as that of the separator manufacturing apparatus 3 according to Embodiment 3 except for the configuration of the electrospinning apparatus, the separator manufacturing apparatus 3 according to Embodiment 3 has. It has a corresponding effect among the effects.

[Embodiment 5]
FIG. 9 is a cross-sectional view of the separator manufacturing apparatus 5 according to the fifth embodiment.

  The separator manufacturing apparatus 5 according to the fifth embodiment has basically the same configuration as the separator manufacturing apparatus 4 according to the fourth embodiment, but the configuration of the cellulose fiber layer manufacturing apparatus is the same as that of the separator manufacturing apparatus 4 according to the fourth embodiment. Different from the case. That is, the separator manufacturing apparatus 5 according to Embodiment 5 includes an electrospinning apparatus 20e as a cellulose fiber layer manufacturing apparatus as shown in FIG. The electrospinning device 20e is an upward type electrospinning device having an upward type nozzle.

  As described above, the separator manufacturing apparatus 5 according to the fifth embodiment is different from the separator manufacturing apparatus 4 according to the fourth embodiment in the configuration of the cellulose fiber manufacturing apparatus, but similarly to the separator manufacturing apparatus 4 according to the fourth embodiment, The separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ionic conductivity can be continuously produced with high productivity.

  Moreover, according to the separator manufacturing apparatus 5 which concerns on Embodiment 5, a nanofiber layer is arrange | positioned by the one side of a cellulose fiber layer by adjusting the order which arrange | positions an electrospinning apparatus and a cellulose fiber layer manufacturing apparatus suitably. It is possible to manufacture a separator having a structure in which a nanofiber layer is disposed on both sides of a cellulose fiber layer and a separator having a structure in which a cellulose fiber layer is disposed on both sides of a nanofiber layer. It becomes.

  Moreover, according to the separator manufacturing apparatus 5 which concerns on Embodiment 5, it becomes possible to adjust the thickness of a cellulose fiber layer, the fiber length of a cellulose fiber, the porosity and pore size of a cellulose fiber layer, and a desired characteristic. It becomes possible to form the cellulose fiber layer which has. It is suitable for forming a cellulose fiber layer composed of cellulose fibers having a relatively small average fiber diameter.

  Moreover, according to the separator manufacturing apparatus 5 which concerns on Embodiment 5, the separator which has the structure by which the nanofiber layer was arrange | positioned on both surfaces of the cellulose fiber layer is manufactured, without making the installation height of a separator manufacturing apparatus so high. It becomes possible.

  In addition, since the separator manufacturing apparatus 5 which concerns on Embodiment 5 has the structure similar to the case of the separator manufacturing apparatus 4 which concerns on Embodiment 4 except the structure of a cellulose fiber layer manufacturing apparatus, the separator manufacturing apparatus 4 which concerns on Embodiment 4 Has the corresponding effect among the effects of

  As mentioned above, although this invention was demonstrated based on said embodiment, this invention is not limited to said embodiment. The present invention can be implemented in various modes without departing from the spirit thereof, and for example, the following modifications are possible.

(1) In the above embodiments, two electrospinning apparatuses are used as the nanofiber layer forming apparatus, but the present invention is not limited to this. For example, one or three or more electrospinning apparatuses may be used as the nanofiber layer forming apparatus.

(2) In Embodiments 3 to 5, one cellulose fiber layer manufacturing apparatus was used as the cellulose fiber layer manufacturing apparatus, but the present invention is not limited to this. For example, two or more cellulose fiber layer manufacturing apparatuses may be used. Moreover, although the melt blow spinning apparatus or the electrospinning apparatus was used as a cellulose fiber layer manufacturing apparatus, this invention is not limited to this. For example, a spunbond spinning device, a needle punch spinning device, or other spinning device may be used.

(3) In each of the above embodiments, a separator having a structure in which nanofiber layers are disposed on both sides of a cellulose fiber layer is manufactured, but the present invention is not limited to this. For example, a separator having a nanofiber layer disposed on one side of the cellulose fiber layer may be manufactured, or a separator having a cellulose fiber layer disposed on both sides of the nanofiber layer may be manufactured. Alternatively, a separator having a structure in which two or more cellulose fiber layers and nanofiber layers are alternately laminated may be manufactured.

(4) In each of the above embodiments, the positive electrode of the power supply device 29 is connected to the collector 24 and the negative electrode of the power supply device 29 is connected to the nozzle unit 22, but the present invention is not limited to this. For example, the positive electrode of the power supply device may be connected to the nozzle, and the negative electrode of the power supply device may be connected to the collector.

1, 2, 3, 4, 5 ... separator manufacturing apparatus, 10 ... transport device, 11, 61 ... feeding roller, 12, 62 ... take-up roller, 13, 18, 63, 68 ... tension roller, 14, 64 ... drive Roller, 15 ... cellulose fiber layer reversing mechanism, 16a, 66a, 66c ... first reversing roller, 16b, 66b, 66d ... second reversing roller, 20a, 20b, 20e ... (upward type) electrospinning apparatus, 20c, 20d ... (Downward type) electrospinning device, 21, 31 ... casing, 22, 32 ... nozzle unit, 23, 33 ... nozzle, 24, 34 ... collector, 25 ... insulating member, 26, 36 ... auxiliary belt device, 27, 37 Auxiliary belt 28, 38 Auxiliary belt roller 29 Power supply 35 Support base 40 Cellulose fiber layer manufacturing apparatus 41 Housing 42 Nozzle unit (for fiber layer manufacturing apparatus), 43... (For cellulosic fiber layer manufacturing apparatus), 44... High-temperature air supply unit, 45... Suction pump, 46. DESCRIPTION OF SYMBOLS ... High temperature airflow suction part, 51 ... Discharge pump, 60 ... Long sheet conveyance apparatus, 65a, 65b ... Long sheet inversion mechanism, 100, 102 ... Separator, 110, 112 ... Cellulose fiber layer, 120, 130 ... Nano fiber layer , W ... Long sheet

Claims (13)

At least one cellulose fiber layer;
A separator comprising at least one nanofiber layer. The separator according to claim 1, wherein
The cellulose fiber layer has a thickness of 1 μm to 40 μm and is made of cellulose fibers having an average fiber diameter of 0.1 μm to 10 μm. The separator according to claim 1 or 2,
The said cellulose fiber layer consists of a cellulose fiber with an average fiber length of 2.0 mm or more, The separator characterized by the above-mentioned. In the separator in any one of Claims 1-3,
The nanofiber layer has a porosity in the range of 20% to 80% and an average pore size in the range of 0.02 μm to 2 μm. In the separator in any one of Claims 1-4,
The separator has a structure in which the nanofiber layer is disposed on both surfaces of the cellulose fiber layer. In the separator in any one of Claims 1-4,
The separator has a structure in which the cellulose fiber layer is disposed on both surfaces of the nanofiber layer. It is a manufacturing method of the separator for manufacturing the separator in any one of Claims 1-6,
Preparing a long sheet comprising the cellulose fiber layer;
And a step of forming the nanofiber layer on one surface of the long sheet being conveyed. In the manufacturing method of the separator according to claim 7,
The manufacturing method of the separator characterized by further including the process of forming the said nano fiber layer in the other surface in the said elongate sheet conveyed. It is a manufacturing method of the separator for manufacturing the separator in any one of Claims 1-6,
A separator manufacturing method, wherein a separator is manufactured by sequentially forming the nanofiber layer and the cellulose fiber layer on one surface of a long sheet being conveyed. A separator manufacturing apparatus for manufacturing the separator according to claim 1,
A conveying device for conveying a long sheet comprising the cellulose fiber layer;
An apparatus for producing a separator, comprising: an electrospinning device that forms a nanofiber layer on the long sheet conveyed by the conveying device. A separator manufacturing apparatus for manufacturing the separator according to claim 1,
A conveying device for conveying a long sheet;
An electrospinning device for forming a nanofiber layer on the long sheet being conveyed by the conveying device;
A separator manufacturing apparatus, comprising: a cellulose fiber layer manufacturing apparatus that forms a cellulose fiber layer on the long sheet transported by the transport apparatus. In the separator manufacturing apparatus according to claim 11,
The separator manufacturing apparatus, wherein the cellulose fiber layer manufacturing apparatus is a melt blow spinning apparatus. In the separator manufacturing apparatus according to claim 11,
The cellulose fiber layer manufacturing apparatus is an electrospinning apparatus.

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