WO2012128471A2

WO2012128471A2 - Separator, method for manufacturing separator, and apparatus for manufacturing separator

Info

Publication number: WO2012128471A2
Application number: PCT/KR2012/000849
Authority: WO
Inventors: 김익수; 김병석; 와타나베케이; 기무라나오타카; 김규오; 이재환
Original assignee: 주식회사 톱텍; 신슈 다이가쿠
Priority date: 2011-03-18
Filing date: 2012-02-06
Publication date: 2012-09-27
Also published as: WO2012128471A3

Abstract

The present invention relates to a separator, a method for manufacturing a separator, and an apparatus for manufacturing a separator, the separator (100) comprising: one cellulose fiber layer (110); a nanofiber layer (120) which is coupled to one surface of the cellulose fiber layer (110); and another nanfiber layer which is coupled to the other surface of the cellulose fiber layer (110), wherein the cellulose fiber layer (110) has a width of 1μm-40μm, is made from a cellulose fiber having an average diameter of 0.1μm-10μm, and wherein the cellulose fiber layer (110) is made from the cellulose fiber having an average length of at least 2.0mm, thereby providing the separator having high conductivity strength, high conductivity, high durability to dendrite, and high ion conductivity.

Description

Separator, Separator Manufacturing Method and Separator Manufacturing Equipment

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

Conventionally, the separator using the paper which fixed the cellulose fiber is known (for example, refer patent document 1). Since the separator described in patent document 1 uses the paper which beat | dissolved cellulose fiber as a raw material, it has not only high heat resistance but also high mechanical strength compared with the polyolefin type separator used conventionally. Therefore, in the separator of patent document 1, even if the separator is made thin and high ion conductivity, it can be considered that high mechanical strength can be maintained.

However, according to the studies of the inventors of the present invention, in the separator described in Patent Literature 1, when the separator is thinned to increase the ion conductivity, high mechanical strength can be maintained, but there is a problem that the insulation and the dendrite resistance are deteriorated. .

Accordingly, the present invention has been made to solve the above problems, and an object thereof is to provide a separator having high mechanical strength, high insulation, high dendrite resistance, and high ion conductivity. Moreover, it aims at providing the manufacturing method and manufacturing apparatus of the 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 the present invention, since the fiber is provided with a nanofiber layer having thin, fine voids and uniform characteristics, it has high insulation and high dendrite resistance. In addition, since the nanofiber layer also has a large porosity, it has high electrolyte solution retention characteristics and high ion conductivity.

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

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

[2] In the separator of the present invention, the cellulose fiber layer preferably has 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 the present invention, since the thickness of the cellulose fiber layer is 40 µm or less, a thin separator can be manufactured, and a secondary battery or a capacitor having a large capacitance can be manufactured. Moreover, since the thickness of a cellulose fiber layer is 1 micrometer or more, mechanical strength does not fall.

In addition, according to the separator of the present invention, since the cellulose fiber layer is made of cellulose fibers having an average fiber diameter of 0.1 µm or more, it is easy to maintain the strength of the cellulose fiber itself, and can form a cellulose fiber layer having sufficient mechanical strength without being too thick. have. On the other hand, since the cellulose fiber layer is made of cellulose fibers having an average fiber diameter of 10 µm or less, it is possible to manufacture a thin separator and to manufacture a non-aqueous battery having a large electric capacity.

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

With such a structure, since the part which cellulose fibers are entangled becomes many, it becomes possible to comprise the separator which has sufficient mechanical strength, without making it thick.

[4] In the separator of the present invention, the nanofiber layer has a porosity.

) Is in the range of 20% to 80%, and the average pore size is preferably in the range of 0.02 µm to 2 µm.

By setting it as such a structure, since the porosity of a nanofiber layer exists in the range of 20%-80%, it has high electrolyte solution holding characteristic and it becomes possible to obtain high ion conductivity. Moreover, since the average pore size exists in the range of 0.02 micrometer-2 micrometers, and a dendrite does not easily invade a separator, it has high dendrite tolerance.

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

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

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

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

[7] The method for producing a separator according to the present invention is a method for producing a separator for producing the separator according to the present invention, the process for preparing a long sheet made of the cellulose fiber layer and the nanosheet on one side of the long sheet being conveyed. It is characterized by including a step of forming a fiber layer.

For this reason, according to the manufacturing method of the separator of this invention, it becomes possible to manufacture the separator of this invention which has high mechanical strength, high insulation, high dendrite tolerance, and high ion conductivity continuously with high productivity.

Moreover, according to the manufacturing method of the separator of this invention, a cellulose fiber layer in which the nanofiber layer was formed can be commercialized as it is. For this reason, the process of isolate | separating the product of a separator from a long sheet can be skipped, and it becomes possible to improve productivity more.

[8] In the method for producing a separator of the present invention, the method further includes a step of forming the nanofiber layer on the other side of the long sheet being conveyed.

By such a method, it becomes possible to manufacture the separator of the structure in which the nanofiber layer was provided in both surfaces of the cellulose fiber layer.

[9] The method for producing a separator according to the present invention is a method for producing a separator for producing the separator according to the present invention, in which a separator is produced by sequentially forming the nanofiber layer and the cellulose fiber layer on one side of a long sheet being conveyed. It is preferable.

For this reason, even by the manufacturing method of the separator of this invention, it becomes possible to manufacture the separator of this invention which has high mechanical strength, high insulation, high dendrite tolerance, and high ion conductivity continuously with high productivity.

Further, by appropriately adjusting the order of forming the nanofiber layer and the cellulose fiber layer, a separator having a structure in which a nanofiber layer is provided on one side of the cellulose fiber layer, a separator having a structure in which the nanofiber layer is provided on both sides of the cellulose fiber layer, and a cellulose fiber layer on both sides of the nanofiber layer It becomes possible to manufacture any separator of the separator of the installed structure.

[10] The separator manufacturing apparatus of the present invention is a separator manufacturing apparatus for producing the separator of the present invention, and the nano-to-long sheet conveyed by the conveying apparatus for conveying the long sheet composed of the cellulose fiber layer and the conveying apparatus is nano. It is characterized by including the field emission device for forming a fiber layer.

For this reason, according to the separator manufacturing apparatus of this invention, it becomes possible to manufacture the separator of this invention which has high mechanical strength, high insulation, high dendrite tolerance, and high ion conductivity continuously with high productivity.

Moreover, according to the separator manufacturing apparatus of this invention, a 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 isolate | separating the product of a separator from a long sheet can be skipped, and it becomes possible to raise productivity more.

[11] The separator manufacturing apparatus of the present invention is a separator manufacturing apparatus for manufacturing the separator of the present invention, and includes a conveying apparatus for conveying a long sheet and an electric field for forming a nanofiber layer in the long sheet being conveyed by the conveying apparatus. A cellulose fiber layer manufacturing apparatus which forms a cellulose fiber layer in the said elongate sheet | seat conveyed by the spinning apparatus and the said conveying apparatus is characterized by the above-mentioned.

For this reason, even with the separator manufacturing apparatus of this invention, it becomes possible to manufacture the separator of this invention which has high mechanical strength, high insulation, high dendrite tolerance, and high ion conductivity continuously with high productivity.

In addition, by appropriately adjusting the order in which the field emission device and the cellulose fiber layer manufacturing apparatus are arranged, the separator having a structure in which a nanofiber layer is provided on one side of the cellulose fiber layer, the separator having a structure in which the nanofiber layer is provided on both sides of the cellulose fiber layer, and both sides of the nanofiber layer. It is possible to manufacture any of the separators having a structure in which a cellulose fiber layer is provided.

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

By such a configuration, it is 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 to form a cellulose fiber layer having desired characteristics. It is suitable for forming a cellulose fiber layer made of cellulose fibers having a relatively large average fiber diameter.

[13] In the separator production apparatus of the present invention, the cellulose fiber layer production apparatus is preferably an electric field emission device.

By such a configuration, it is 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 to form a cellulose fiber layer having desired characteristics. It is suitable for forming a cellulose fiber layer composed of cellulose fibers having a relatively small average fiber diameter.

The present invention provides a separator having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity, and also provides a method and apparatus for manufacturing a separator capable of manufacturing such a separator.

1 is a cross-sectional view of the separator 100 according to the first embodiment.

2 is a cross-sectional view of the separator manufacturing apparatus 1 according to the first embodiment.

3 is a diagram showing that the separator 100 is manufactured by the method for manufacturing a separator according to the first embodiment.

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

5 is a cross-sectional view of the separator 102 according to the third embodiment.

6 is a cross-sectional view of the separator manufacturing apparatus 3 according to the third embodiment.

FIG. 7 is a diagram showing that the separator 102 is manufactured by the method for manufacturing a separator according to the third embodiment.

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

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

EMBODIMENT OF THE INVENTION Hereinafter, the separator, the separator manufacturing apparatus, and the separator manufacturing method of this invention are demonstrated based on embodiment shown in drawing.

[Embodiment 1]

1. Configuration of the separator according to the first embodiment

First, the structure of the separator 100 which concerns on Embodiment 1 is demonstrated.

As shown in FIG. 1, the separator 100 according to Embodiment 1 includes one cellulose fiber layer 110 and two

nanofiber layers

120 and 130, and a nanofiber layer (on both sides of the cellulose fiber layer 110). 120 and 130 are provided.

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 m to 2 m.

The separator 100 is obtained by the manufacturing method of the separator which concerns on Embodiment 1 using the separator manufacturing apparatus 1 which concerns on Embodiment 1 mentioned later.

2.Configuration of Separator Manufacturing Apparatus 1 According to Embodiment 1

2 is a cross-sectional view of the separator manufacturing apparatus 1 according to the embodiment. In addition, illustration of the polymer solution supply part is abbreviate | omitted in FIG. This also applies to the following drawings which will be described later. FIG. 3 is a diagram showing that the separator 100 is manufactured by the method for manufacturing a separator according to the first embodiment. 3 (a) to 3 (c) are respective process diagrams.

The separator manufacturing apparatus 1 which concerns on Embodiment 1 is conveyed by the conveying apparatus 10 and the conveying apparatus 10 which convey the long sheet which consists of the elongate cellulose fiber layer 110, as shown in FIG. The field emission device 20a which forms the nanofiber layer 120 (refer to FIG. 3 (b)) on one side of the thin cellulose fiber layer 110, and the nanofiber layer 130 (FIG. 3 (c) on the other side). Field emission device 20b). The field radiating device 20a and the field radiating device 20b are both top direction field radiating devices provided with top direction nozzles.

The conveying apparatus 10 is comprised so that the cellulose fiber layer 110 used as a base material layer may be conveyed from the field radiating apparatus 20a toward the field radiating apparatus 20b. The conveying apparatus 10 moves the cellulose fiber layer 110 in the first direction (the A1 direction in FIG. 2) when the field radiating device 20a forms the nanofiber layer 120 (see FIG. 3B). The cellulosic fiber layer 110 from the height position of the field radiating device 20a to the height position of the field radiating device 20b in the second direction (A2 direction) substantially perpendicular to the first direction, When the device 20b forms the nanofiber layer 130 (see FIG. 3C to be described later), the cellulose fiber layer 110 is conveyed in the third direction (A3 direction) opposite to the first direction.

The conveying apparatus 10 includes an feeding roller 11 for feeding the cellulose fiber layer 110, a winding roller 12 for winding the cellulose fiber layer 110, and a tension roller 13 for adjusting the pulling of the cellulose fiber layer 110. 18, the plurality of drive rollers 14 for conveying the cellulose fiber layer 110, the first reverse roller 16a for directing the conveyance direction of the cellulose fiber layer 110 from the field radiating device 20a, and And a second reverse roller 16b for directing the conveyance direction of the cellulose fiber layer 110 from the first reverse roller 16a toward the field radiating device 20b.

Among these, the feed roller 11, the winding roller 12, the

tension rollers

13 and 18, and the some drive roller 14 comprise the conveyance mechanism (not shown) which conveys the cellulose fiber layer 110. do. The plurality of drive rollers 14 are drive devices for transporting the cellulose fiber layer 110.

The first reversing roller 16a and the second reversing roller 16b are formed such that the cellulose fiber layer 110 is reversed so that the direction of one side of the cellulose fiber layer 110 and the direction of the other side are reversed while the cellulose fiber layer 110 is being conveyed. The cellulose fiber layer inversion mechanism 15 which inverts this is comprised. The cellulose fiber layer inversion mechanism 15 inverts the cellulose fiber layer 110 from the field emission device 20a in accordance with the height position of the field emission device 20b.

The

field radiating apparatuses

20a and 20b are mounted on the housing body 21 via an insulating member 25, and the collector 24 located on the other side of the cellulose fiber 110 and one of the cellulose fiber layers 110 are provided. A nozzle unit 22 located at a position opposite to the collector 24 on the surface side and having a plurality of nozzles 23 for discharging the polymer solution supplied from a polymer solution supply unit (not shown) toward the cellulose fiber layer 110; Between the collector 24 and the nozzle unit 22, a power supply 29 for applying a high voltage (for example, 10 kV to 80 kV), and an auxiliary belt device 26 to assist the cellulose fiber layer 110 to be conveyed. Equipped.

The nozzle unit 22 of the electric

field radiating apparatus

20a, 20b is equipped with the some upward direction nozzle 23 which discharges a polymer solution from a discharge port to an upward direction as a some nozzle. The field radiating device 20a is configured to discharge the polymer solution from the discharge ports of the plurality of top direction nozzles 23 to electrospin the nanofibers.

The plurality of upward direction nozzles 23 are arranged at a pitch of, for example, 1.5 cm to 6.0 cm. The number of the some upward direction nozzles 23 is 36 pieces (6 * 6 pieces when it arranges in vertical or horizontal same number)-21904 pieces (148 * 148 pieces when it is arranged in vertical and horizontal same number), for example.

In addition, although the nozzle unit which has a various size and a various shape can be used for the separator manufacturing apparatus of this invention, the nozzle unit 22 is a rectangle (square being 0.5m-3m in one side, for example from an upper surface). Inclusive).

The collector 24 is attached to the conductive housing body 21 via 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 housing body 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. One of the five auxiliary belt rollers 28, or two or more rollers for the auxiliary belt, is a drive roller, and the remaining auxiliary belt rollers are driven rollers. Since the auxiliary belt 27 is provided between the collector 24 and the cellulose fiber layer 110, the cellulose fiber layer 110 is smoothly conveyed without being pulled by the collector 24 to which a positive high voltage is applied.

3. Manufacturing method of separator according to Embodiment 1

Hereinafter, the method (manufacturing method of the separator which concerns on Embodiment 1) which manufactures the separator 100 using the separator manufacturing apparatus 1 concerning Embodiment 1 comprised as mentioned above is demonstrated.

(a) Preparation for spinning

In each of the two

field radiating apparatuses

20a and 20b, a polymer solution is prepared, and the polymer solution is supplied to the nozzle unit 22. In addition, the elongate cellulose fiber layer 110 (refer to FIG. 3 (a)) is set in the conveying apparatus 10, and the cellulose fiber layer 110 is then moved from the feeding roller 11 toward the winding roller 12. It conveys at a predetermined conveyance speed.

(b) field radiation (1)

Subsequently, the nanofiber layer 120 is formed on one side of the cellulose fiber layer 110 being conveyed by the field emission device 20a (see FIG. 3B).

(c) long sheet reversal

Then, by the long sheet reversing mechanism 15 (

inversion rollers

16a and 16b), the direction of one side of the cellulose fiber layer 110 and the direction of the other side so that one side of the cellulose fiber layer 110 is lowered. Invert

d) field emission (2)

Then, the nanofiber layer 130 is formed in the other surface of the cellulose fiber layer 110 conveyed by the field emission apparatus 20b (refer FIG.3 (c)). As a result, the separator 100 having the structure in which the nanofiber layers 120 and 130 are provided on both surfaces of the cellulose fiber layer 110 is completed.

Hereinafter, the spinning conditions of the manufacturing method of the separator which concerns on Embodiment 1 are shown by way of example.

As a polymer used as a raw material of a nanofiber, for example, 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 acid glycolic acid ( PLGA), silk, cellulose, chitosan and the like.

As a solvent used for a polymer solution, dichloromethane, dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, chloroform, acetone, water, formic acid, acetic acid, cyclohexane, THF, etc. can be used, for example. You may mix and use multiple types of solvent. The polymer solution may contain additives such as conductivity enhancers.

As a plant fiber used as a raw material of a cellulose fiber, coniferous, manila hemp, cedar, a white, etc. can be used, for example. You may mix and use multiple types of fiber.

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

The temperature of a spinning zone can be set to 10 to 40 degreeC, for example. The humidity of a radiation zone can be set to 20%-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 are characterized by thin fibers and fine pores, they have high insulation and high dendrite resistance. In addition, since the nanofiber layer also has a large porosity, it has high electrolyte solution retention characteristics and high ion conductivity.

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

As a result, the separator 100 according to Embodiment 1 becomes a separator having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity.

Moreover, according to the separator 100 which concerns on Embodiment 1, since the thickness of the cellulose fiber layer 110 is 40 micrometers or less, it becomes possible to manufacture a thin separator and to manufacture a non-aqueous battery with a large electric capacity. In addition, since the thickness of the cellulose fiber layer 110 is 1 µm or more, the mechanical strength does not decrease.

Moreover, according to the separator 100 which concerns on Embodiment 1, since the cellulose fiber layer 110 consists of cellulose fiber of 0.1 micrometer or more of average fiber diameters, it becomes easy to maintain the strength of the cellulose fiber itself, and it does not thicken enough mechanical enough. It is possible to construct a cellulose fiber layer having strength. On the other hand, since the cellulose fiber layer 110 consists of cellulose fiber of 10 micrometers or less of average fiber diameters, it becomes possible to manufacture a thin separator and to manufacture a non-aqueous battery with a large electric capacity.

Moreover, according to the separator 100 which concerns on Embodiment 1, since the part which cellulose fibers intertwine increases, it becomes possible to comprise the separator which has sufficient mechanical strength, without making it 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 high electrolyte solution holding property and can obtain high ion conductivity. Moreover, since the average pore size exists in the range of 0.02 micrometer-2 micrometers, and a dendrite does not easily invade a separator, it has high dendrite tolerance.

Moreover, according to the separator 100 which concerns on Embodiment 1, it becomes possible to prevent growth of dendrites on both surfaces of the cellulose fiber layer 110, and it becomes possible to comprise the separator with higher dendrite tolerance.

5.Effect of the manufacturing method of the separator concerning Embodiment 1

According to the method for manufacturing a separator according to Embodiment 1, the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance, and high ion conductivity can be continuously 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 isolate | separating the product of a separator from a long sheet can be skipped, and it becomes possible to improve productivity more.

6.Effect of the separator manufacturing apparatus 1 which concerns on Embodiment 1

According to the separator manufacturing apparatus 1 which concerns on Embodiment 1, it becomes possible to manufacture the separator of this invention which has high mechanical strength, high insulation, high dendrite tolerance, and high ion conductivity continuously 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 isolate | separating the product of a separator from a long sheet can be skipped, and it becomes possible to raise productivity more.

[Embodiment 2]

As shown in FIG. 4, the separator manufacturing apparatus 2 according to the second embodiment has the same configuration as that of the separator manufacturing apparatus 1 according to the first embodiment, but the configuration of the electric field radiating apparatus is the first embodiment. It differs from the case of the separator manufacturing apparatus 1 which concerns. That is, in the separator manufacturing apparatus 2 which concerns on Embodiment 2, as shown in FIG. 4, the field emission apparatus 20a which forms the nanofiber layer 120 in one surface of the cellulose fiber layer 110 to be conveyed, and The field emission device 20c which forms the nanofiber layer 130 on the other side is provided. The field emission device 20c is a downward direction field emission device having a downward direction nozzle.

In the separator manufacturing apparatus 2 which concerns on Embodiment 2, as shown in FIG. 4, the field radiating apparatus 20a and the field radiating apparatus 20c are the same straight line along the conveyance direction of the cellulose fiber layer 110 in this order. It is arrange | positioned so that it may become a phase.

The field radiating device 20c is mounted on the support 35 through an insulating member, and is disposed on one side of the cellulose fiber 110 and the collector 34 on the other side of the cellulose fiber layer 110. It is provided with the nozzle unit 32 which has the several downward direction nozzle 33 located in the position which opposes, the power supply 29, and the auxiliary belt apparatus 36 which assists the cellulose fiber layer 110 to be conveyed. do.

The nozzle unit 32 is attached to the housing body 31 and has a some lower direction nozzle 33 which discharges a polymer solution from a discharge port to a downward direction as a some nozzle.

The collector 34 is mounted on the conductive support 35 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 the housing body 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 rollers 38 for assisting belts 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 case of the separator manufacturing apparatus 1 according to the first embodiment, although the configuration of the field radiating device is the same as that of the separator manufacturing apparatus 1 according to the first embodiment. It becomes possible to manufacture the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity continuously 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 layer 120,130 was formed can be manufactured as it is. For this reason, the process of isolate | separating the product of a separator from a long sheet can be skipped, and it becomes possible to raise productivity more.

Moreover, according to the separator manufacturing apparatus 2 which concerns on Embodiment 2, it becomes possible to manufacture the separator which has a structure in which the nanofiber layer was provided in both surfaces of a cellulose fiber layer, without making the installation height of a separator manufacturing apparatus very high.

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 the field emission apparatus, the separator manufacturing apparatus which concerns on Embodiment 1 ( It has one of the effects that 1) has.

[Embodiment 3]

1. Configuration of Separator 102 According to Embodiment 3

The structure of the separator 102 which concerns on Embodiment 3 is demonstrated.

As shown in FIG. 5, the separator 102 according to the third embodiment basically has the same configuration as the separator 100 according to the first embodiment, but the structure of the cellulose fiber layer is the separator 100 according to the first embodiment. It is different from the case. That is, the separator 102 which concerns on Embodiment 3 is equipped with the cellulose fiber layer 112 manufactured by the cellulose fiber layer manufacturing apparatus 40 mentioned later as shown in FIG.

The separator 102 is obtained by the separator method which concerns on Embodiment 3 using the separator manufacturing apparatus 3 which concerns on Embodiment 3 mentioned later.

2.Configuration of Separator Manufacturing Apparatus 3 According to Embodiment 3

6 is a cross-sectional view of the separator manufacturing apparatus 3 according to the third embodiment. FIG. 7 is a diagram showing that the separator 102 is manufactured by the method for manufacturing a separator according to the third embodiment.

The separator manufacturing apparatus 3 which concerns on Embodiment 3 basically has the same structure as the separator manufacturing apparatus 1 which concerns on Embodiment 1, but Embodiment 1 is the point which further comprises the structure of a conveying apparatus, and a cellulose fiber layer manufacturing apparatus. It differs from the case of the separator manufacturing apparatus 1 which concerns on this. That is, the separator manufacturing apparatus 3 which concerns on Embodiment 3 has the conveying apparatus 60 which conveys the long sheet W, the

field emission apparatus

20a, 20b, and the cellulose fiber layer (as shown in FIG. 6). The cellulose fiber layer manufacturing apparatus 40 which forms 112 is provided.

In the separator manufacturing apparatus 3 which concerns on Embodiment 3, as shown in FIG. 6, the field emission apparatus 20a, the elongate sheet inversion mechanism 65a mentioned later, the cellulose fiber layer manufacturing apparatus 40, and later mentioned The long sheet reversing mechanism 65b and the electric field radiating device 20b are arranged along the conveyance direction of the long sheet W in this order.

The long sheet conveying apparatus 60 is provided as a conveying apparatus.

The long sheet conveying device 60 includes an feeding roller 61 for feeding the long sheet W, a winding roller 62 for winding the long sheet W, and a tension roller for adjusting the pulling of the long sheet W ( 63, 68, the some drive roller 64 which conveys the long sheet W, the 1st

reverse roller

66a, 66c, and the 2nd

reverse roller

66b, 66d.

Among these, the feed roller 61, the winding roller 62, the

tension rollers

63 and 68, and the some drive roller 64 comprise the conveyance mechanism 60 which conveys the long sheet W. As shown in FIG. The some drive roller 64 is a drive apparatus which conveys the long sheet W. As shown in FIG.

The 1st reversing roller 66a and the 2nd reversing roller 66b have the long sheet W so that the direction of the one surface of the long sheet W and the other surface may be reversed while the long sheet W is conveyed. ), A long sheet reversing mechanism 65a for reversing the structure is formed. In addition, the 1st reversing roller 66c and the 2nd reversing roller 66d are a long sheet | seat so that the direction of the one surface of the long sheet W and the other surface may be reversed while the long sheet W is conveyed. The long sheet inversion mechanism 65b which inverts (W) is constituted.

The

field emission devices

20a and 20b have the same configuration as the

field emission devices

20a and 20b used in the first embodiment.

The cellulose fiber layer manufacturing apparatus 40 forms the cellulose fiber layer 112 in the long sheet W conveyed by the long sheet conveying apparatus 60, as shown in FIG.

The cellulose fiber layer manufacturing apparatus 40 has a nozzle unit 42 having a plurality of downward direction nozzles 43 for discharging the cellulose solution supplied from the cellulose solution supply unit (not shown) toward the long sheet W, and toward the cellulose solution. The high temperature airflow supply part 44 which injects high temperature airflow, and the high temperature airflow suction apparatus 47 are provided.

The nozzle unit 42 is attached to the housing body 21 and described later in the direction along the cellulose solution discharge direction and the plurality of downward direction nozzles 43 for discharging the cellulose solution downward from the discharge port as a plurality of nozzles. It has a high temperature airflow path (not shown) which flows the high temperature airflow supplied from the high temperature airflow supply part 44. As shown in FIG. The plurality of downward direction nozzles 43 are arranged at a pitch of, for example, 1.5 cm to 6.0 cm. The nozzle unit 42 may use a nozzle unit having various sizes and various shapes.

The hot airflow supply 44 includes a suction pump 45 and a heater 46.

The high temperature airflow supply 44 forms the high temperature airflow by heating the air blown in from the outside by the suction pump 84 with the heater 46. The hot air flow is led to a hot air flow path (not shown) of the nozzle unit 42. The heater 46 can adjust the output so that a high temperature airflow may be a predetermined temperature within a range of 120 ° C to 500 ° C.

The high temperature airflow suction device 47 is disposed on the inner surface side of the long sheet W as viewed from the nozzle unit 42, and the mesh member 48, the high temperature airflow suction unit 50, and the discharge pump 51 are disposed. Equipped.

The high temperature airflow flowing 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 plurality of holes for airflow passage are formed, and is discharged to the discharge pump 51. Is discharged to the outside.

3. Manufacturing method of separator according to Embodiment 3

Hereinafter, the method (separator manufacturing method which concerns on Embodiment 3) which manufactures a separator using the separator manufacturing apparatus 3 which concerns on Embodiment 3 comprised as mentioned above is demonstrated.

FIG. 7 is a diagram showing that the separator 102 is manufactured by the method for manufacturing a separator according to the third embodiment. 7A to 7E are respective process diagrams.

(a) Preparation for spinning

The 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, in each of the two

field radiating apparatuses

20a and 20b, a polymer solution is prepared, and the polymer solution is supplied to each nozzle unit 22. Moreover, the long sheet W is set to the long sheet conveying apparatus 60, and the long sheet W is conveyed from the input roller 61 toward the winding roller 62 at a predetermined conveyance speed after that (FIG. See (a) of 7). The cellulose solution is obtained by melting cellulose, which is a material of the cellulose fiber layer 112, or dissolving it in a solvent.

(b) field radiation (1)

Subsequently, the nanofiber layer 120 is formed on one surface of the long sheet W by the field emission device 20a while conveying the long sheet 110 (see FIG. 7B).

(c) Long sheet reversal (1)

Subsequently, the direction of one side of the long sheet W and the direction of the other side are reversed by the long sheet reversing mechanism 65a (inverting

rollers

66a, 66b) so that one side becomes the upper side.

(d) Cellulose Fiber Layer Preparation

Subsequently, the cellulose fiber layer 112 is formed on one surface of the long sheet W by the cellulose fiber manufacturing apparatus 40 while conveying the long sheet W in which the nanofiber layer 120 was formed (FIG. 7 ( c)). Thereby, the nanofiber layer 120 and the nanofiber layer 130 are laminated | stacked in this order on one surface of the elongate sheet W. As shown in FIG.

(c) Long sheet reversal (2)

Subsequently, the long sheet reversing mechanism 65b (reversing

rollers

66c, 66d) reverses the direction of the one surface of the long sheet W and the direction of the other surface such that one surface becomes the lower side.

(e) field radiation (2)

Subsequently, the nanofiber layer 130 is formed on one side of the long sheet W by the field emission device 20b while conveying the long sheet W on which the nanofiber layer 120 and the cellulose fiber layer 112 are laminated. (See FIG. 7D). Thereby, the laminated sheet by which the nanofiber layer 120, the cellulose fiber layer 112, and the nanofiber layer 130 were laminated | stacked in this order on one side of the elongate sheet | seat W is manufactured. Thereafter, the laminated sheet is wound by the winding roller 12.

(f) Separation of separator and long sheet

Thereafter, the separator 102 and the long sheet are separated while the laminated sheet is introduced to manufacture the separator 102 (see FIG. 5E).

By the above method, the separator 102 can be manufactured.

As the long sheet, nonwoven fabric, woven fabric, knitted fabric, film, paper, etc. made of various materials can be used. As for the thickness of a long sheet, the thing of 5 micrometers-500 micrometers can be used, for example. As for the length of a long sheet, the thing of 10m-10km can be used, for example.

4.Effect of the separator manufacturing apparatus 3 which concerns on Embodiment 3

Although the separator manufacturing apparatus 3 which concerns on Embodiment 3 differs from the case of the separator manufacturing apparatus 1 which concerns on Embodiment 1 in that the structure of a conveying apparatus and the cellulose fiber layer manufacturing apparatus differ from the case of the separator manufacturing apparatus 1 which concerns on Embodiment 1, Like (1), it becomes possible to continuously manufacture the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity with high productivity.

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 the pore size of a cellulose fiber layer, and form the cellulose fiber layer which has a desired characteristic. It becomes possible. It 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 having the structure of a conveying apparatus and the cellulose fiber layer manufacturing apparatus further, it implements. It has a corresponding effect among the effects which the separator manufacturing apparatus 1 which concerns on the form 1 has.

In the present invention, the order in which the field radiating device and the cellulose fiber layer manufacturing device are disposed is appropriately changed in the separator manufacturing apparatus 3 according to the third embodiment, so that both sides of the separator and the cellulose fiber layer having a structure in which the nanofiber layer is provided on one side of the cellulose fiber layer. It is possible to manufacture either the separator of the structure in which the nanofiber layer was provided, and the separator of the structure in which the cellulose fiber layer was provided on both surfaces of the nanofiber layer.

[Embodiment 4]

Although the separator manufacturing apparatus 4 which concerns on Embodiment 4 has the structure similarly to the separator manufacturing apparatus 3 which concerns on Embodiment 3, the structure of the separator manufacturing apparatus 3 which concerns on Embodiment 3 is a structure of the field emission apparatus. ) Is different. That is, in the separator manufacturing apparatus 4 which concerns on Embodiment 4, as shown in FIG. 8, 20 d of lower direction electric field emission apparatuses which form the nanofiber layer 120 in the elongate sheet W to be conveyed, The downward direction field emission device 20c which forms the nanofiber layer 130 in the elongate sheet W conveyed is provided.

In the separator manufacturing apparatus 4 which concerns on Embodiment 4, as shown in FIG. 8, the field radiating apparatus 20d, the cellulose fiber layer manufacturing apparatus 40, and the field radiating apparatus 20c are long sheets (in this order). It is arrange | positioned so that it may become the same linear form along the conveyance direction of W).

In this manner, the separator manufacturing apparatus 4 according to the fourth embodiment is different from the case of the separator manufacturing apparatus 3 according to the third embodiment, although the configuration of the field emission device is the same as that of the separator manufacturing apparatus 3 according to the third embodiment. It becomes possible to manufacture the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance and high ion conductivity continuously with high productivity.

Moreover, according to the separator manufacturing apparatus 4 which concerns on Embodiment 4, the separator and the cellulose fiber layer of the structure by which the nanofiber layer was provided in one side of a cellulose fiber layer by adjusting the order which arrange | positions an electric field radiating device and a cellulose fiber layer manufacturing apparatus appropriately. It becomes possible to manufacture either the separator of the structure in which the nanofiber layer was provided in both surfaces, and the separator of the structure in which the cellulose fiber layer was provided in both surfaces of the nanofiber layer.

Moreover, according to the separator manufacturing apparatus 4 which concerns on Embodiment 4, it becomes possible to manufacture the separator which has a structure in which the nanofiber layer was provided in both surfaces of a cellulose fiber layer, without making the installation height of a separator manufacturing apparatus very high.

In addition, since the separator manufacturing apparatus 4 which concerns on Embodiment 4 has the structure similar to the case of the separator manufacturing apparatus 3 which concerns on Embodiment 3 except the structure of the field emission apparatus, the separator manufacturing apparatus which concerns on Embodiment 3 ( It has a corresponding effect among the effects that 3) has.

[Embodiment 5]

The separator manufacturing apparatus 5 according to the fifth embodiment basically has the same configuration as the separator manufacturing apparatus 4 according to the fourth embodiment, but the structure of the cellulose fiber layer manufacturing apparatus according to the fourth exemplary embodiment is the separator manufacturing apparatus 4 according to the fourth exemplary embodiment. It is different from the case. That is, in the separator manufacturing apparatus 5 which concerns on Embodiment 5, as shown in FIG. 9, the field emission apparatus 20e is provided as a cellulose fiber layer manufacturing apparatus. The field radiator 20e is a top direction field radiator having a top direction nozzle.

Thus, although the structure of a cellulose fiber manufacturing apparatus differs from the case of the separator manufacturing apparatus 4 which concerns on Embodiment 4, the separator manufacturing apparatus 5 which concerns on Embodiment 5 differs from the separator manufacturing apparatus 4 which concerns on Embodiment 4, Likewise, the separator of the present invention having high mechanical strength, high insulation, high dendrite resistance, and high ion conductivity can be continuously manufactured with high productivity.

Moreover, according to the separator manufacturing apparatus 5 which concerns on Embodiment 5, the separator of the structure in which the nanofiber layer was provided in one side of a cellulose fiber layer, and both surfaces of a cellulose fiber layer by adjusting the order which arrange | positions an electric field radiating device and a cellulose fiber layer manufacturing apparatus suitably. It is possible to manufacture either the separator of the structure in which the nanofiber layer was provided, and the separator of the structure in which the cellulose fiber layer was provided on both surfaces of the nanofiber layer.

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 the pore size of a cellulose fiber layer, and form the cellulose fiber layer which has a desired characteristic. It becomes possible. 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, it becomes possible to manufacture the separator which has a structure in which the nanofiber layer was provided in both surfaces of a cellulose fiber layer, without making the installation height of a separator manufacturing apparatus very high.

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 which concerns on Embodiment 4 It has a corresponding effect among the effects of (4).

As mentioned above, although this invention was demonstrated based on the said embodiment, this invention is not limited to the said embodiment. Various forms can be implemented in the range which does not deviate from the meaning, For example, the following modification is also possible.

(1) In each said embodiment, although two field emission apparatuses were used as a nanofiber layer forming apparatus, this invention is not limited to this. As the nanofiber layer forming apparatus, for example, one, three or more field radiating apparatuses may be used.

(2) In Embodiments 3 to 5, one cellulose fiber layer production apparatus was used as the cellulose fiber layer production apparatus, but the present invention is not limited thereto. For example, two or more cellulose fiber layer production apparatuses may be used. . In addition, although the melt blow spinning apparatus or the field spinning apparatus was used as a cellulose fiber layer manufacturing apparatus, this invention is not limited to this. For example, you may use a spanbond spinning apparatus, a needle punch spinning apparatus, or another spinning apparatus.

(3) In each said embodiment, although the separator of the structure which provided the nanofiber layer on both surfaces of the cellulose fiber layer was manufactured, this invention is not limited to this. For example, the separator which provided the nanofiber layer on one side of a cellulose fiber layer may be manufactured, and the separator which provided the cellulose fiber layer on both surfaces of a nanofiber layer may be manufactured. Moreover, you may manufacture the separator of the structure in which a cellulose fiber layer and a nanofiber layer were laminated | stacked alternately two or more layers, respectively.

(4) Although the anode of the power supply device 29 is connected to the collector 24 and the cathode of the power supply device 29 is connected to the nozzle unit 22 in each said embodiment, this invention is not limited to this. . For example, the anode of the power supply device may be connected to the nozzle, and the cathode of the power supply device may be connected to the collector.

Claims

At least one cellulose fiber layer,

A separator comprising at least one nanofiber layer.
The method of claim 1,

The cellulose fiber layer has a thickness of 1 μm to 40 μm and an average fiber diameter of 0.1 μm to 10 μm.
The method according to claim 1 or 2,

The cellulose fiber layer is a separator, characterized in that consisting of cellulose fibers having an average fiber length of 2.0mm or more.
The method according to any one of claims 1 to 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.
The method according to any one of claims 1 to 4,

The separator has a structure characterized in that the nanofiber layer is provided on both sides of the cellulose fiber layer.
The method according to any one of claims 1 to 4,

The separator has a structure characterized in that the cellulose fiber layer is provided on both sides of the nanofiber layer.
In the manufacturing method of the separator for manufacturing the separator of any one of Claims 1-6,

Preparing a long sheet composed of the cellulose fiber layer, and

A method for producing a separator, comprising the step of forming the nanofiber layer on one side of the long sheet being conveyed.
The method of claim 7, wherein

A method for producing a separator, further comprising the step of forming the nanofiber layer on the other side of the long sheet being conveyed.
In the manufacturing method of the separator for manufacturing the separator of any one of Claims 1-6,

The separator is manufactured by forming the said nanofiber layer and the said cellulose fiber layer in order on one side of the elongate sheet | seat conveyed, The manufacturing method of the separator characterized by the above-mentioned.
In the separator manufacturing apparatus for manufacturing the separator as described in any one of Claims 1-6,

A conveying apparatus for conveying a long sheet of the cellulose fiber layer, and

The separator manufacturing apparatus characterized by including the field emission apparatus which forms a nanofiber layer in the said elongate sheet conveyed by the said conveying apparatus.
In the separator manufacturing apparatus for manufacturing a separator as described in any one of Claims 1-6,

A conveying device for conveying a long sheet,

An electrospinning apparatus for forming a nanofiber layer on the long sheet being conveyed by the conveying apparatus, and

A cellulose fiber layer manufacturing apparatus which forms a cellulose fiber layer in the said elongate sheet conveyed by the said conveying apparatus, The separator manufacturing apparatus characterized by the above-mentioned.
The method of claim 11,

The apparatus for producing a cellulose fiber layer is a separator manufacturing apparatus, characterized in that the melt blow spinning device.
The method of claim 11,

The cellulose fiber layer manufacturing apparatus is a separator manufacturing apparatus, characterized in that the field radiating device.