JP2013037854A - Separator, and device and method for manufacturing separator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a separator capable of suppressing a nanofiber layer from being peeled to be damaged during a manufacturing process of the separator, to provide a separator manufacturing device capable of manufacturing the separator, and further to provide a separator manufacturing method capable of manufacturing the separator.SOLUTION: A separator 1 comprises: a base material layer 10; a first nanofiber layer 20 including a first nanofiber 22; and a second nanofiber layer 30 including a second nanofiber 32 and an inorganic particle 34. The base material layer 10, the first nanofiber layer 20 and the second nanofiber layer 30 are stacked in the order of the base material layer 10, the first nanofiber layer 20 and the second nanofiber layer 30, and the base material layer 10 and the second nanofiber layer 30 are joined by the first nanofiber 22.

Description

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

  Conventionally, a separator having a substrate layer (porous film) and a nanofiber layer containing nanofibers and inorganic particles (for example, alumina) is known (for example, see Patent Document 1).

According to the conventional separator, since it has a nanofiber layer containing inorganic particles such as alumina, it is possible to obtain a separator having high thermal stability and high affinity for an electrolytic solution.
Moreover, according to the conventional separator, it is possible to obtain a separator having various properties by using a base material layer and a nanofiber layer having different properties.
In addition, according to the conventional separator, it is possible to obtain a separator having more various properties by adding the properties (wide surface area, fine voids, etc.) of the nanofiber layer to the properties of the base material layer. Become.
Also, according to the conventional separator, since the average fiber diameter and voids are provided with a fine nanofiber layer, compared with a separator having a general fiber layer, high electrolyte absorption, low ion resistance and high It has dendrite resistance and can be a separator with a thin total thickness.

  The “base material layer” refers to a layer that becomes a base material for forming the nanofiber layer. The “nanofiber” refers to a fiber made of a polymer material and having an average diameter of several nm to several thousand nm. Furthermore, the “separator” refers to a separator (partition) used for a battery (including a primary battery and a secondary battery), a capacitor (also referred to as a capacitor), and the like.

JP 2010-44935 A

  However, in the conventional separator, since the bonding strength between the base material layer and the nanofiber layer is low, there is a problem that the nanofiber layer may be peeled off and damaged in the manufacturing process of the separator.

  Then, this invention was made | formed in order to solve an above-described problem, and it aims at providing the separator which can suppress that a nanofiber layer peels and damages in the manufacturing process of a separator. . Moreover, it aims at providing the separator manufacturing apparatus which can manufacture the above separators. Furthermore, it aims at providing the separator manufacturing method which can manufacture the above separators.

[1] The separator of the present invention has a base material layer, a first nanofiber layer containing first nanofibers, and a second nanofiber layer containing second nanofibers and inorganic particles, and the base material layer The first nanofiber layer and the second nanofiber layer are laminated in the order of the base material layer, the first nanofiber layer, and the second nanofiber layer, and the base material layer and the second nanofiber layer are laminated. The layer is bonded by the first nanofiber.

  For this reason, according to the separator of this invention, since the base material layer and the 2nd nanofiber layer are joined by the 1st nanofiber, it can suppress that a base material layer and a nanofiber layer peel. As a result, it is possible to suppress the second nanofiber layer (corresponding to a conventional nanofiber layer) from being peeled off and damaged in the manufacturing process of the separator.

  Moreover, according to the separator of the present invention, since it has the second nanofiber layer containing inorganic particles, it is a separator having high thermal stability and high affinity for the electrolytic solution, as in the case of conventional separators. Is possible.

  In addition, according to the separator of the present invention, by using the base material layer and the second nanofiber layer having different properties, it is possible to obtain a separator having various properties as in the case of the conventional separator. .

  In addition, according to the separator of the present invention, by adding the properties of the second nanofiber layer (such as a large surface area and fine voids) to the properties of the base material layer, as with conventional separators, a wider variety can be obtained. A separator having properties can be obtained.

  Further, according to the separator of the present invention, by using the first nanofiber layer having properties different from those of the base material layer and the second nanofiber layer, the properties of the first nanofiber layer are further added to the separator, and more A separator having more various properties can be obtained.

  In addition, according to the separator of the present invention, since the second nanofiber layer having a fine average diameter and voids of the fibers is provided, as compared with a separator having a general fiber layer, the electrolysis is higher than that of a conventional separator. Liquid separator, low ionic resistance and high dendrite resistance are provided, and a separator having a thin total thickness can be obtained.

  In addition, as described above, the “second nanofiber layer” of the present invention corresponds to the “nanofiber layer” in the conventional separator.

[2] In the separator of the present invention, the first nanofibers are made of a resin having thermal bondability, and at least a part of the base material layer and the second nanofiber layer is melted by heat. It is preferable that 1 nanofiber is joined.

  By setting it as such a structure, it becomes possible to join easily by heating a base material layer and a 2nd nanofiber layer.

  The resin having thermal bondability refers to a resin widely including a resin having thermal bondability such as polyurethane in addition to a so-called thermoplastic resin (polyethylene, polypropylene, etc.).

[3] In the separator of the present invention, the melting point of the resin having thermal bondability is lower than both the melting point of the material constituting the base material layer and the melting point of the material constituting the second nanofiber layer. Is preferred.

  By adopting such a configuration, heating is performed at a temperature between the melting point of the material constituting the base layer and the melting point of the material constituting the second nanofiber layer and the melting point of the resin having thermal bondability. One nanofiber can be selectively melted.

[4] In the separator of the present invention, the melting point of the resin having thermal bondability is 10 ° C. above both the melting point of the material constituting the base material layer and the melting point of the material constituting the second nanofiber layer. It is preferable that it is low.

  With such a configuration, there is a sufficient difference between the melting point of the material constituting the base material layer and the melting point of the material constituting the second nanofiber layer, and the melting point of the resin having thermal bondability. This makes it possible to easily melt the first nanofiber selectively.

[5] In the separator of the present invention, it is preferable that an average diameter of the first nanofiber is in a range of 50 nm to 1000 nm.

  By setting it as such a structure, it will become in the state by which the base material layer and the 2nd nanofiber layer were joined with sufficient intensity | strength, and it becomes possible to suppress that the liquid permeability of a separator falls.

  In the present invention, the average diameter of the first nanofibers is in the range of 50 nm to 1000 nm because the base layer and the second nanofiber layer have sufficient strength when the average diameter is smaller than 50 nm. This is because the bonded state may not be obtained, and when the average diameter is larger than 1000 nm, the liquid permeability of the separator may be lowered.

[6] In the separator of the present invention, the average diameter of the second nanofibers is preferably larger than the average diameter of the first nanofibers and in the range of 80 nm to 3000 nm.

  By adopting such a configuration, it is possible to suppress the influence of the second nanofibers upon heating and not to impair the properties (such as a large surface area and fine voids) as the nanofibers. Become.

  In the present invention, the average diameter of the second nanofibers is larger than the average diameter of the first nanofibers and falls within the range of 80 nm to 3000 nm because the average diameter is greater than the average diameter of the first nanofibers. If the average diameter is larger than 3000 nm, the properties as the second nanofibers are impaired when the average diameter is larger than 3000 nm. This is because there is a case.

[7] In the separator of the present invention, the first nanofiber is made of a resin having solubility in a predetermined solvent, and at least a part of the base material layer and the second nanofiber layer is the The first nanofibers dissolved in a predetermined solvent are preferably joined.

  By setting it as such a structure, it becomes possible to join a base material layer and a 2nd nanofiber layer easily using a predetermined | prescribed solvent.

[8] In the separator of the present invention, the first nanofiber layer is preferably thinner than the second nanofiber layer.

  By adopting such a configuration, it is the second nanofiber layer that mainly adds the properties (such as a large surface area and fine voids) that the nanofiber layer has in the separator, and the separator has stable performance. It becomes possible.

[9] In the separator of the present invention, the first nanofibers and the second nanofibers are preferably obtained by an electrospinning method.

  By adopting such a configuration, the first nanofiber layer and the second nanofiber layer having desired properties (composition, thickness, basis weight, average diameter of each nanofiber, melting temperature, solubility in a solvent, etc.) It becomes possible to form.

[10] In the separator of the present invention, the average diameter of the inorganic particles is preferably in the range of 5 nm to 1000 nm.

  By adopting such a configuration, it becomes possible to easily handle the inorganic particles, and it is possible to suppress the collapse of the spatial structure of the second nanofiber layer.

In the present invention, the reason that the average diameter of the inorganic particles is in the range of 5 nm to 1000 nm is that the inorganic particles may be difficult to handle when the average diameter is smaller than 5 nm. This is because if the average diameter is larger than 1000 nm, the spatial structure of the second nanofiber layer may collapse due to the size of the inorganic particles.
From the above viewpoint, the average diameter of the inorganic particles is more preferably in the range of 8 nm to 500 nm, and the average diameter is more preferably in the range of 10 nm to 100 nm.

[11] In the separator of the present invention, the inorganic particles are preferably made of an inorganic oxide, an inorganic nitride, or an inorganic carbide.

  Inorganic oxides, inorganic nitrides, and inorganic carbides are particularly excellent in thermal stability and affinity for the electrolytic solution. By adopting the above-described configuration, higher thermal stability and higher resistance to the electrolytic solution are achieved. It is possible to obtain a separator having high affinity.

  As the inorganic oxide, the inorganic nitride, or the inorganic carbide, those that have low solubility in the nonaqueous electrolytic solution and are difficult to swell can be suitably used. Among the above, inorganic oxides can be suitably used, and specific examples thereof include silica, alumina, and titanium dioxide.

[12] The separator manufacturing apparatus of the present invention uses a polymer solution in which a raw material of the first nanofiber is dissolved by an electrospinning method, and the first nanofiber includes the first nanofiber on one surface of the base material layer. A first electrospinning apparatus having a mechanism for forming a layer, and a mixed polymer solution in which inorganic particles are mixed with a polymer solution in which a raw material of the second nanofiber is dissolved by an electrospinning method. A second electrospinning apparatus having a mechanism for forming “the second nanofiber layer including the second nanofiber and the inorganic particles” on the surface; and the base layer and the second nanofiber by the first nanofiber. And a joining device for joining the layers.

  According to the separator manufacturing apparatus of the present invention, the separator of the present invention as described above can be manufactured.

[13] The separator manufacturing apparatus of the present invention uses a polymer solution in which a raw material of the first nanofiber is dissolved by an electrospinning method, and the first nanofiber includes the first nanofiber on one surface of the base material layer. A first electrospinning apparatus having a mechanism for forming a layer and a polymer solution in which a raw material of the second nanofiber is dissolved by an electrospinning method, and the second nanofiber is included on the surface of the first nanofiber layer. A layer having a mechanism for forming a layer, and an inorganic particle is included in the layer including the second nanofiber during or after the formation of the layer including the second nanofiber, and the layer including the second nanofiber is expressed as “ The second electrospinning apparatus having a mechanism of “the second nanofiber and the second nanofiber layer including the inorganic particles” and the base layer and the second nanofiber layer are joined by the first nanofiber. And a joining device.

  The above-described separator production apparatus of the present invention can also produce the above-described separator of the present invention.

[14] The separator manufacturing apparatus of the present invention uses a polymer solution in which a raw material of the first nanofiber is dissolved by an electrospinning method, and the first nanofiber includes the first nanofiber on one surface of the base material layer. A first electrospinning apparatus having a mechanism for forming a layer and a polymer solution in which a raw material of the second nanofiber is dissolved by an electrospinning method, and the second nanofiber is included on the surface of the first nanofiber layer. A second electrospinning apparatus having a mechanism for forming a layer; and a layer containing the second nanofibers further including inorganic particles, and the layer containing the second nanofibers is referred to as “the second nanofibers and the inorganic particles. An inorganic particle-containing device having a mechanism of “a second nanofiber layer including”, and a bonding device that bonds the base material layer and the second nanofiber layer with the first nanofiber. .

  The above-described separator production apparatus of the present invention can also produce the above-described separator of the present invention.

[15] The separator manufacturing apparatus of the present invention uses a polymer solution in which a raw material of the first nanofiber is dissolved by an electrospinning method, and the first nanofiber includes the first nanofiber on one surface of the base material layer. A first electrospinning apparatus having a mechanism for forming a layer and a polymer solution in which a raw material of the second nanofiber is dissolved by an electrospinning method, and the second nanofiber is included on the surface of the first nanofiber layer. A second electrospinning device having a mechanism for forming a layer, a joining device for joining the base material layer and the layer containing the second nanofiber by the first nanofiber, and a layer containing the second nanofiber. An inorganic particle-containing device having a mechanism that includes inorganic particles and has a layer including the second nanofibers as the second nanofiber layer including the second nanofibers and the inorganic particles. To do.

  The above-described separator production apparatus of the present invention can also produce the above-described separator of the present invention.

[16] In the separator manufacturing apparatus of the present invention, the joining device has the base material layer, the first nanofiber layer, and the second nanofiber layer or the layer containing the second nanofiber laminated. It is preferable to comprise a thermal bonding apparatus that performs thermocompression bonding in a state.

  By setting it as such a structure, when the 1st nanofiber which consists of resin which has heat bondability is used, it becomes possible to join a base material layer and a 2nd nanofiber layer by heating.

[17] The separator manufacturing method of the present invention includes a base material layer preparing step for preparing a base material layer, and a polymer solution in which a raw material of the first nanofiber is dissolved by an electrospinning method. The first electrospinning step of forming the first nanofiber layer including the first nanofibers on the surface of the substrate, and the mixed polymer solution obtained by mixing inorganic particles in the polymer solution in which the raw material of the second nanofibers is dissolved by the electrospinning method A second electrospinning step of forming “the second nanofiber layer including the second nanofibers and the inorganic particles” on the surface of the first nanofiber layer, and the base by the first nanofibers. It includes a joining step for joining the material layer and the second nanofiber layer in this order.

  According to the separator manufacturing method of the present invention, the separator of the present invention as described above can be manufactured.

[18] The separator manufacturing method of the present invention includes a base material layer preparing step for preparing a base material layer, and a polymer solution in which a raw material of the first nanofiber is dissolved by an electrospinning method. A first nanofiber layer including the first nanofiber on the surface thereof, and a first nanofiber using a polymer solution in which a raw material of the second nanofiber is dissolved by an electrospinning method. Forming a layer containing the second nanofibers on the surface of the layer, and including inorganic particles in the layer containing the second nanofibers during or after the formation of the layer containing the second nanofibers; A second electrospinning step in which a layer containing nanofibers is “the second nanofiber layer containing the second nanofibers and the inorganic particles”, and the base layer and the second nanofiber layer are formed by the first nanofibers. And a joining process for joining together in this order To.

  The separator of the present invention as described above can also be manufactured by the separator manufacturing method of the present invention.

[19] The separator manufacturing method of the present invention includes a base material layer preparing step of preparing a base material layer and a polymer solution in which a raw material of the first nanofiber is dissolved by an electrospinning method. Using a first electrospinning step of forming a first nanofiber layer including the first nanofibers on one surface and a polymer solution in which a raw material of the second nanofibers is dissolved by an electrospinning method, A second electrospinning step of forming a layer containing the second nanofibers on the surface of the fiber layer; and a layer containing the second nanofibers further including inorganic particles, An inorganic particle-containing step, which is a “second nanofiber layer containing second nanofibers and the inorganic particles”, and a bonding step of bonding the base material layer and the second nanofiber layer with the first nanofibers. They are included in this order.

  The separator of the present invention as described above can also be manufactured by the separator manufacturing method of the present invention.

[20] The method for producing a separator of the present invention includes a base material layer preparing step for preparing a base material layer and a polymer solution in which a raw material of the first nanofiber is dissolved by an electrospinning method. Using a first electrospinning step of forming a first nanofiber layer including the first nanofibers on one surface and a polymer solution in which a raw material of the second nanofibers is dissolved by an electrospinning method, A second electrospinning step of forming a layer containing the second nanofibers on the surface of the fiber layer; a bonding step of joining the base material layer and the layer containing the second nanofibers by the first nanofibers; Inorganic particle inclusion step of further including inorganic particles in the layer containing the second nanofibers and setting the layer containing the second nanofibers as the “second nanofiber layer containing the second nanofibers and the inorganic particles” Are included in this order.

  The separator of the present invention as described above can also be manufactured by the separator manufacturing method of the present invention.

[21] In the separator manufacturing method of the present invention, in the joining step, the base material layer, the first nanofiber layer, and the second nanofiber layer or the layer containing the second nanofiber are laminated. A thermal bonding step of thermocompression bonding in a state, wherein at least a part of the first nanofibers is melted by heat in the thermal bonding step, and the base layer and the second nanofiber layer are combined with the first nanofibers. It is preferable to join with.

  By setting it as such a method, when the 1st nanofiber which consists of resin which has heat bondability is used, it becomes possible to join a base material layer and a 2nd nanofiber layer by heating.

It is a figure for demonstrating the separator 1 which concerns on Embodiment 1. FIG. 1 is a front view of a separator manufacturing apparatus 100 according to Embodiment 1. FIG. 3 is a flowchart of a separator manufacturing method according to Embodiment 1. It is a figure for demonstrating the separator manufacturing method which concerns on Embodiment 1. FIG. It is a figure shown in order to demonstrate joining process S4 in Embodiment 1. FIG. 6 is a front view of a separator manufacturing apparatus 102 according to Embodiment 2. FIG. 5 is a flowchart of a separator manufacturing method according to Embodiment 2. It is a figure shown in order to demonstrate 2nd electrospinning process S13 which concerns on Embodiment 2, and inorganic particle containing process S14. It is a front view of the separator manufacturing apparatus 104 which concerns on Embodiment 3. FIG. 10 is a flowchart of a separator manufacturing method according to Embodiment 3. It is a front view of the separator manufacturing apparatus 106 which concerns on Embodiment 4. FIG. 6 is a flowchart of a separator manufacturing method according to Embodiment 4. It is a flowchart of the separator manufacturing method which concerns on a modification.

  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 1 According to Embodiment 1 First, the configuration of the separator 1 according to Embodiment 1 will be described.
FIG. 1 is a view for explaining a separator 1 according to the first embodiment. FIG. 1A is a perspective view of the separator 1 wound around a core (not shown), FIG. 1B is an enlarged cross-sectional view of the separator 1, and FIG. It is the schematic diagram (henceforth an enlarged schematic diagram) which expands further and shows the range shown by A of FIG.1 (b).

As illustrated in FIG. 1, the separator 1 according to the first embodiment includes a base material layer 10, a first nanofiber layer 20, and a second nanofiber layer 30, and the base material layer 10 and the first nanofibers. The layer 20 and the second nanofiber layer 30 are laminated in the order of the base material layer 10, the first nanofiber layer 20, and the second nanofiber layer 30. In the separator 1, the base material layer 10 and the second nanofiber layer 30 are joined by the first nanofiber 22. Specifically, as shown in FIG. 1C, the base material layer 10 and the second nanofiber layer 30 are joined by first nanofibers 24 at least partially melted by heat.
The thickness of the separator 1 is in the range of 1 μm to 100 μm, for example, 20 μm.

  As described later, the separator 1 according to the first embodiment can be obtained by performing the separator manufacturing method according to the first embodiment using the separator manufacturing apparatus 100 according to the first embodiment.

The base material layer 10 takes the form of a long sheet, and as the base material layer 10, a non-woven fabric, a woven fabric, a knitted fabric, paper, or the like made of various materials can be used that has air permeability (liquid permeability). . In the first embodiment, a fibrous base material layer is used as the base material layer 10, and reference numeral 12 in FIG. 1C denotes the base material fiber in the base material layer 10. In addition, as the base material layer 10, things other than a fiber (for example, a porous film) can also be used.
The base layer 10 may have a thickness of 1 μm to 90 μm, for example. The length of the base material layer 10 can be, for example, 10 to 10 km.

  The first nanofiber layer 20 is composed of first nanofibers 22. In addition, the 1st nanofiber layer should just contain the 1st nanofiber, and if it is on it, it may contain substances other than the 1st nanofiber. The first nanofiber 22 is made of a resin having thermal bondability. The average diameter of the 1st nanofiber 22 exists in the range of 50 nm-1000 nm, for example, is 100 nm. The first nanofibers 22 can be obtained by an electrospinning method as will be described later.

The second nanofiber layer 30 includes second nanofibers 32 and inorganic particles 34. In addition, the 2nd nanofiber layer should just contain the 2nd nanofiber and the inorganic particle, and if it is on it, it may also contain substances other than the 2nd nanofiber and the inorganic particle.
The average diameter of the 2nd nanofiber 32 is larger than the average diameter of the 1st nanofiber 22, and exists in the range of 80 nm-3000 nm, for example, is 1000 nm. The second nanofiber 32 can be obtained by an electrospinning method as will be described later.
The average diameter of the inorganic particles 34 is in the range of 5 nm to 1000 nm, for example, 50 nm. The inorganic particles 34 are made of an inorganic oxide, an inorganic nitride, or an inorganic carbide, for example, alumina.

In the separator 1, the melting point of the resin having thermal bondability is that of the material constituting the base layer 10 (base fiber 12) and that of the material constituting the second nanofiber layer 30 (second nanofiber 32). It is lower than any of the melting points, more specifically, 10 or lower.
In the separator 1, the first nanofiber layer 20 is thinner than the second nanofiber layer 30 as shown in FIG.

2. Configuration of Separator Manufacturing Apparatus 100 According to Embodiment 1 Next, the configuration of the separator manufacturing apparatus 100 according to Embodiment 1 will be described.
FIG. 2 is a front view of the separator manufacturing apparatus 100 according to the first embodiment. In FIG. 2, some members (such as the casing 200 and the raw material tank 232) are shown as cross-sectional views.

  The separator manufacturing apparatus 100 includes a transport device 110, a first electrospinning device 120, a second electrospinning device 121, and a joining device 130. The separator manufacturing apparatus 100 includes one each of the first electrospinning apparatus 120 and the second electrospinning apparatus 121.

  The transport device 110 transports the base material layer 10 at a predetermined transport speed. The transport device 110 includes a feed roller 111 that feeds the base material layer 10, a take-up roller 112 that winds the base material layer 10, tension rollers 113 and 118 that adjust the tension of the base material layer 10, and the feed roller 111 and the take-up roller 112. Auxiliary roller 114 located between the two. The feed roller 111 and the take-up roller 112 are configured to be rotated by a drive motor (not shown).

The first electrospinning apparatus 120 forms the first nanofiber layer 20 ′ including the first nanofibers 22 on one surface (the lower surface in the first embodiment) of the base material layer 10 by an electrospinning method. It has a mechanism (see FIG. 4B described later).
As shown in FIG. 2, the first electrospinning device 120 includes a housing 200, a nozzle unit 210, a polymer solution supply unit 230, a collector 250, a power supply device 260, and an auxiliary belt device 270. The first electrospinning device 120 discharges the polymer solution from the discharge ports of a plurality of upward nozzles 220, which will be described later, to form the first nanofiber layer 20 ′.

The housing 200 is made of a conductor.
The nozzle unit 210 has a plurality of upward nozzles 220.

  The upward nozzle 220 is a nozzle that discharges the “polymer solution in which the raw material of the first nanofibers 22 is dissolved (polymer solution of resin having thermal bondability)” supplied from the polymer solution supply unit 230 from the discharge port. The upward nozzle 220 discharges the polymer solution upward from the discharge port. As the material constituting the upward nozzle 220, a conductor can be used, and for example, copper, stainless steel, aluminum, or the like can be used.

  The upward nozzles 220 are arranged at a pitch of 1.5 cm to 6.0 cm, for example. The number of upward nozzles 220 may be, for example, 36 (6 × 6 when arranged in the same vertical and horizontal directions) to 21904 (148 × 148 when arranged in the same vertical and horizontal directions).

  In the first embodiment, the upward nozzle 220 is used as the nozzle, but the present invention is not limited to this. A horizontal nozzle may be used as the nozzle, or a downward nozzle may be used.

  The polymer solution supply unit 230 supplies the polymer solution to the nozzle unit 210. The polymer solution supply unit 230 includes a raw material tank 232, a stirring device 233, and a supply device 234. The raw material tank 232 of the first electrospinning apparatus 120 contains a polymer solution in which the raw material of the first nanofibers 22 is dissolved.

The collector 250 is disposed above the nozzle unit 210. The collector 250 is made of a conductor and is attached to the housing 200 via an insulating member 252 as shown in FIG.
The power supply device 260 applies a high voltage between the upward nozzle 220 and the collector 250. The positive electrode of the power supply device 260 is connected to the collector 250, and the negative electrode of the power supply device 260 is connected to the nozzle unit 210 via the housing 200.

  The auxiliary belt device 270 includes an auxiliary belt 272 that rotates in synchronization with the conveyance speed of the base material layer 10, and five auxiliary belt rollers 274 that assist the rotation of the auxiliary belt 272. Of the five auxiliary belt rollers 274, one or more auxiliary belt rollers are drive rollers, and the remaining auxiliary belt rollers are driven rollers. Since the auxiliary belt 272 is disposed between the collector 250 and the base material layer 10, the base material layer 10 is smoothly conveyed without being attracted to the collector 250 to which a positive high voltage is applied. become.

The second electrospinning device 121 uses a mixed polymer solution in which inorganic particles 34 are mixed with a polymer solution in which the raw material of the second nanofibers 32 is dissolved by an electrospinning method, on the surface of the first nanofiber layer 20 ′. It has a mechanism for forming the “second nanofiber layer 30 including the second nanofibers 32 and the inorganic particles 34”.
Although the detailed description of the second electrospinning device 121 is omitted, the basic mechanical configuration is the same as that of the first electrospinning device 120, but the detailed structure is different in order to form the second nanofiber layer. In FIG. 2, in order to simplify the explanation, the constituent elements of the second electrospinning apparatus 121 are the same as those having the same basic configuration and role as the corresponding constituent elements in the first electrospinning apparatus 120. The code | symbol of was attached.
The raw material tank 232 of the second electrospinning apparatus 121 contains a mixed polymer solution in which inorganic particles 34 are mixed with a polymer solution in which the raw material of the second nanofibers 32 is dissolved.
The second electrospinning device 121 uses a mixed polymer solution in which inorganic particles 34 are mixed in a polymer solution in which the raw material of the second nanofiber 32 is dissolved, and the “second nanofiber 32” is formed on one surface of the base material layer 10. As a mechanism for forming the second nanofiber layer 30 including the inorganic particles 34, the second nanofiber layer 30 has a larger diameter than the inorganic particles 34. Specifically, it is preferable to have a diameter of 100 times or more with respect to the particle diameter of the inorganic particles 34.

  The bonding device 130 is a device that bonds the base material layer 10 and the second nanofiber layer 30 using the first nanofibers 22. The joining device 130 is composed of a thermal joining device that performs thermocompression bonding in a state where the base material layer 10, the first nanofiber layer 20, and the second nanofiber layer 30 are laminated. As the joining apparatus 130, as shown in FIG. 2, the thermal joining apparatus provided with the calendar roll can be illustrated. In addition, as a means for heating, what incorporated the heater function (not shown) in the calendar roll can be used, for example, but besides this, for example, a resistance heater, an infrared heater, It is also possible to use a dryer, a hot air generator or the like. In FIG. 2, the calender roll is illustrated as having a configuration in which the second laminated body 50 is sandwiched between upper and lower rollers, but is not limited to such a configuration, and two upper and lower calender rolls. It is possible to use a calendar roll having various configurations, such as those having a roller.

3. Separator Manufacturing Method According to Embodiment 1 Next, a separator manufacturing method according to Embodiment 1 will be described.
FIG. 3 is a flowchart of the separator manufacturing method according to the first embodiment.
FIG. 4 is a diagram for explaining the separator manufacturing method according to the first embodiment. FIG. 4A is an enlarged cross-sectional view of the base material 10 in the base material preparation step S1, and FIG. 4B is an enlarged cross-sectional view of the first laminate 40 after the first electrospinning step S2. FIG.4 (c) is an expanded sectional view of the 2nd laminated body after 2nd electrospinning process S3.
FIG. 5 is a view for explaining the joining step S4 in the first embodiment. FIG. 5A is an enlarged schematic diagram before the joining step S4, and FIG. 5B is an enlarged schematic diagram after the joining step S4.

  As shown in FIG. 3, the separator manufacturing method according to Embodiment 1 includes a base material layer preparation step S1, a first electrospinning step S2, a second electrospinning step S3, and a joining step S4 in this order. . The separator manufacturing method according to the first embodiment is performed using the separator manufacturing apparatus 100 according to the first embodiment.

1. Base material layer preparation step S1
The base material preparation step S1 is a step of preparing the base material layer 10 as shown in FIG. In the first embodiment, the base material layer 10 takes the form of a long sheet. In addition, in the separator manufacturing method of this invention, the base material layer of the various shapes which take forms other than a long sheet can also be used.
In the first embodiment, after preparing the base material layer 10, the base material layer 10 that is a long sheet is set on the transport device 110, and the base material layer 10 is transported from the feeding roller 111 at a predetermined transport speed.

2. First electrospinning process S2
As shown in FIG. 4 (b), the first electrospinning step S2 uses one of the polymer layers in which the raw material of the first nanofibers 22 is dissolved by electrospinning. ) To form a first nanofiber layer 20 ′ including the first nanofibers 22.
Specifically, first, the polymer solution is supplied to the nozzle unit 210 through the polymer solution supply unit 230 in the first electrospinning apparatus 120. Next, a voltage is applied between the collector 250 and the nozzle unit 210 to discharge the polymer solution from the upward nozzle 220, and the first nanofiber layer 20 ′ is formed on the lower surface of the base material layer 10 which is a long sheet. The first laminated body 40 is formed.
The first electrospinning step S2 is performed using the electrospinning apparatus 120 described above.

3. Second electrospinning step S3
As shown in FIG. 4C, the second electrospinning step S3 uses a mixed polymer solution in which inorganic particles 34 are mixed with a polymer solution in which the raw material of the second nanofibers 32 is dissolved by an electrospinning method. This is a step of forming the “second nanofiber layer 30 including the second nanofibers 32 and the inorganic particles 34” on the surface of the first nanofiber layer 20 ′ in the one laminate 40.
Specifically, first, the mixed polymer solution is supplied to the nozzle unit 210 through the polymer solution supply unit 230 in the second electrospinning apparatus 121. Next, a voltage is applied between the collector 250 and the nozzle unit 210 to discharge the mixed polymer solution from the upward nozzle 220, and the second nanofibers are formed on the lower surface of the already formed first nanofiber layer 20 ′. The layer 30 is formed to form the second stacked body 50.
The second electrospinning step S3 is performed using the electrospinning apparatus 121 described above.

4). Joining step S4
As shown in FIG. 5, the joining step S <b> 4 is a step of joining the base material layer 10 and the second nanofiber layer 30 using the first nanofibers 22. The joining step S4 is a thermal joining step in which thermocompression bonding is performed in a state in which the base material layer 10, the first nanofiber layer 20, and the second nanofiber layer 30 are laminated, and the first nanofiber is formed by the thermal joining step. At least a part of 22 is melted by heat, and the base material layer 10 and the second nanofiber layer 30 are joined by the first nanofiber 22.
The joining step S4 is performed using the joining device 130 described above.

  Below, the spinning conditions in Embodiment 1 are shown as an example.

  Examples of the material of the first nanofiber 22 include a resin having thermal bonding properties, such as polyvinylidene fluoride (PVDF), polylactic acid (PLA), polypropylene (PP), polyethylene (PE), polyvinyl acetate (PVAc), and polyethylene. Terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyamide (PA), polyurethane (PUR), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyimide (PI), polyetherimide ( PEI), polycaprolactone (PCL), polylactic acid glycolic acid (PLGA) and the like can be used.

  Examples of the raw material of the second nanofiber 32 include polyvinylidene fluoride (PVDF), polylactic acid (PLA), polypropylene (PP), polyethylene (PE), polyvinyl acetate (PVAc), polyethylene terephthalate (PET), and polybutylene. Terephthalate (PBT), polyethylene naphthalate (PEN), polyamide (PA), polyurethane (PUR), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyimide (PI), polyetherimide (PEI), polycaprolactone (PCL) ), Polylactic acid glycolic acid (PLGA), silk, cellulose, chitosan and the like can be used.

  As a solvent for producing various polymer solutions, for example, dichloromethane, dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, chloroform, acetone, water, formic acid, acetic acid, cyclohexane, THF and the like can be used. Moreover, you may mix and use multiple types of solvent as a solvent. The polymer solution may contain an additive such as a conductivity improver.

  A conveyance speed can be set to 0.2 m / min-100 m / min, for example. The voltage applied to the upward nozzle 220, the collector 250, and the nozzle unit 210 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 25, for example. The humidity of the spinning area can be set to 30%, for example.

  Hereinafter, effects of the separator 1, the separator manufacturing apparatus 100, and the separator manufacturing method according to the first embodiment will be described.

  According to the separator 1 according to the first embodiment, the first nanofiber layer 20 including the first nanofibers 22 is included, and the base material layer 10 and the second nanofiber layer 30 are joined by the first nanofibers 22. Therefore, it becomes possible to suppress peeling of the base material layer and the second nanofiber layer (corresponding to the conventional nanofiber layer), and as a result, the second nanofiber layer peels off during the manufacturing process of the separator. Damage can be suppressed.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since it has the 2nd nanofiber layer 30 containing the inorganic particle 34, similarly to the conventional separator, high thermal stability and high affinity with respect to electrolyte solution are provided. It becomes possible to set it as the separator which has.

  Moreover, according to the separator 1 which concerns on Embodiment 1, it is set as the separator which has a various property similarly to the conventional separator by using the base material layer 10 and the 2nd nanofiber layer 30 which each have a different property. It becomes possible.

  Moreover, according to the separator 1 which concerns on Embodiment 1, by adding the property (a wide surface area, a fine space | gap, etc.) which the 2nd nanofiber layer 30 has to the property which the base material layer 10 has, it is the same as that of the conventional separator. In addition, it is possible to obtain a separator having more various properties.

  Moreover, according to the separator 1 which concerns on Embodiment 1, the property which the 1st nanofiber layer has further added to a separator by using the 1st nanofiber layer which has a property different from a base material layer or a 2nd nanofiber layer. In addition, it becomes possible to obtain a separator having even more diverse properties.

  In addition, according to the separator 1 according to the first embodiment, since the second nanofiber layer 30 having a fine fiber average diameter and voids is provided, as compared with a separator having a general fiber layer, as in the case of a conventional separator. Thus, it is possible to obtain a separator having a high electrolyte solution absorbability, a low ionic resistance and a high dendrite resistance, and a thin total thickness.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the 1st nanofiber 22 consists of resin which has heat bondability, it joins easily by heating a base material layer and a 2nd nanofiber layer. Is possible.

  Moreover, according to the separator 1 which concerns on Embodiment 1, melting | fusing point of resin which has heat bondability is lower than both of melting | fusing point of the material which comprises the base material layer 10, and melting | fusing point of the material which comprises the 2nd nanofiber layer 30 Therefore, the first nanofibers are selectively selected by heating at a temperature between the melting point of the material constituting the base material layer and the melting point of the material constituting the second nanofiber layer and the melting point of the resin having thermal bondability. It becomes possible to melt.

  Further, according to the separator 1 according to the first embodiment, the melting point of the resin having thermal bondability is 10 higher than both the melting point of the material constituting the base material layer 10 and the melting point of the material constituting the second nanofiber layer 30. Since the melting point of the material constituting the base material layer and the melting point of the material constituting the second nanofiber layer are sufficiently different from the melting point of the resin having thermal bondability, the first temperature is increased by heating. One nanofiber can be easily selectively melted.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the average diameter of the 1st nanofiber 22 exists in the range of 50 nm-1000 nm, the base material layer and the 2nd nanofiber layer were joined with sufficient intensity | strength. It becomes possible to prevent the liquid permeability of the separator from being lowered.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the average diameter of the 2nd nanofiber 32 is larger than the average diameter of the 1st nanofiber 22, and exists in the range of 80 nm-3000 nm, it heats. Thus, it is possible to suppress the influence of the second nanofibers and to prevent the properties as a nanofiber (such as a large surface area and fine voids) from being impaired.

  Further, according to the separator 1 according to the first embodiment, since the second nanofiber layer 30 is thicker than the first nanofiber layer 20, the properties of the nanofiber layer in the separator (such as a large surface area and fine voids) are added. This is mainly the second nanofiber layer, and a separator having stable performance can be obtained.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the 1st nanofiber 22 and the 2nd nanofiber 32 were obtained by the electrospinning method, desired properties (composition, thickness, basis weight, each nanometer) It is possible to form a first nanofiber layer and a second nanofiber layer having an average fiber diameter, a melting temperature, solubility in a solvent, and the like.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the average diameter of the inorganic particle 34 exists in the range of 5 nm-1000 nm, it becomes possible to make handling of an inorganic particle easy, and 2nd nano It is possible to suppress the collapse of the spatial structure of the fiber layer.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the inorganic particle 34 consists of an inorganic oxide, an inorganic nitride, or an inorganic carbide, the separator which has higher thermal stability and higher affinity with respect to electrolyte solution, It becomes possible to do.

  According to the separator manufacturing apparatus 100 according to the first embodiment, since the first electrospinning apparatus 120, the second electrospinning apparatus 121, and the joining apparatus 130 are provided, the separator 1 according to the first embodiment as described above is manufactured. It becomes possible to do.

  Moreover, according to the separator manufacturing apparatus 100 which concerns on Embodiment 1, the joining apparatus 130 is the heat | fever which carries out thermocompression bonding in the state which laminated | stacked the base material layer 10, the 1st nanofiber layer 20, and the 2nd nanofiber layer 30. FIG. Since it consists of a joining device, when the 1st nanofiber which consists of resin which has thermal bondability is used, it becomes possible to join a base material layer and the 2nd nanofiber layer by heating.

  According to the separator manufacturing method according to the first embodiment, since the base layer preparation step S1, the first electrospinning step S2, the second electrospinning step S3, and the joining step S4 are included in this order, as described above. It becomes possible to manufacture the separator 1 which concerns on Embodiment 1. FIG.

  Moreover, according to the separator manufacturing method which concerns on Embodiment 1, joining process S4 is the thermobonding which thermocompression-bonds in the state which laminated | stacked the base material layer 10, the 1st nanofiber layer 20, and the 2nd nanofiber layer 30. FIG. In this process, at least a part of the first nanofibers 22 is melted by heat and the base material layer 10 and the second nanofiber layer 30 are joined by the first nanofibers 22 in the thermal joining process. In the case where the first nanofibers made of a resin having a property are used, the base material layer and the second nanofiber layer can be joined by heating.

[Embodiment 2]
FIG. 6 is a front view of the separator manufacturing apparatus 102 according to the second embodiment.
FIG. 7 is a flowchart of the separator manufacturing method according to the second embodiment.
FIG. 8 is a view for explaining the second electrospinning step S13 and the inorganic particle containing step S14 according to the second embodiment. FIG. 8A is an enlarged schematic view after the second electrospinning step S13, and FIG. 8B is an enlarged schematic view after the inorganic particle containing step S14.

  In the second embodiment, a separator manufacturing apparatus and a separator manufacturing method for manufacturing the separator 1 will be described, which are different from the separator manufacturing apparatus 100 and the separator manufacturing method according to the first embodiment.

  The separator manufacturing apparatus 102 according to the second embodiment basically has the same configuration as the separator manufacturing apparatus 100 according to the first embodiment, but further includes a configuration of the second electrospinning apparatus and an inorganic particle containing apparatus. Is different from the case of the separator manufacturing apparatus 100 according to the first embodiment. Details will be described below.

  As shown in FIG. 6, the second electrospinning device 122 in the separator manufacturing apparatus 102 has basically the same configuration as the second electrospinning device 121 in the first embodiment, but dissolves the raw material of the second nanofibers 32. The difference is that the polymer solution is used to form a layer 31 including the second nanofibers 32 on the surface of the first nanofiber layer 20 ′.

Although the detailed description of the second electrospinning device 122 is omitted, although the basic mechanical configuration is the same as that of the second electrospinning device 121, the details of the second electrospinning device 122 for forming the layer 31 including the second nanofibers 32 are omitted. The structure is different. In FIG. 6, for simplicity of explanation, the same components and components of the second electrospinning device 122 as those of the corresponding components of the second electrospinning device 121 have the same basic configuration and role. A reference is attached.
In addition, the polymer solution which melt | dissolved the raw material of the 2nd nanofiber 32 enters into the raw material tank 232 of the 2nd electrospinning apparatus 122. FIG.

  The inorganic particle inclusion device 140 further includes a mechanism for forming the “second nanofiber layer 30 including the second nanofibers 32 and the inorganic particles 34” by further including the inorganic particles 34 in the layer 31 including the second nanofibers 32. (See FIG. 8). Specifically, the inorganic particle containing device 140 is disposed between the second electrospinning device 122 and the bonding device 130 and injects the inorganic particles 34 together with the solvent toward the layer 31 including the second nanofibers 32. It is a device to do. As the solvent, a solvent that does not damage each nanofiber can be used. Although the solvent which can be used changes with kinds of nanofiber to be used, various alkanes, acetone, water, cyclohexane, THF, etc. can be used, for example. In addition, you may mix and use multiple types of solvent as a solvent. Moreover, you may inject only an inorganic particle, without using a solvent.

  The separator manufacturing method according to the second embodiment is basically the same method as the separator manufacturing method according to the first embodiment, but the embodiment further includes the contents of the second electrospinning step and the inorganic particle-containing step. This is different from the case of the separator manufacturing method according to 1. Details will be described below.

As shown in FIG. 7, the separator manufacturing method according to the second embodiment includes a base material layer preparation step S11, a first electrospinning step S12, a second electrospinning step S13, an inorganic particle-containing step S14, and bonding. Step S15 is included in this order.
Among these, base material layer preparation process S11 is the process similar to base material layer preparation process S1 in Embodiment 1. FIG. The first electrospinning step S12 is the same step as the first electrospinning step S2 in the first embodiment. Furthermore, the joining step S15 is a step similar to the joining step S4 in the first embodiment. Therefore, description of these steps is omitted.

In the second electrospinning step S13, the layer 31 including the second nanofibers 32 is formed on the surface of the first nanofiber layer 20 ′ by using the polymer solution in which the raw material of the second nanofibers 32 is dissolved by the electrospinning method. (See FIG. 8).
In the second embodiment, the formation of the layer 31 including the second nanofibers 32 is performed using the second electrospinning device 122 described above.

In the inorganic particle inclusion step S <b> 14, the layer 31 including the second nanofiber 32 further includes the inorganic particle 34, and the layer 31 including the second nanofiber 32 is changed to “the second nanofiber 32 and the second particle including the inorganic particle 34. This is a step of forming the nanofiber layer 30 ".
The inorganic particle containing step S14 is performed using the inorganic particle containing device 140 described above.

  According to the separator manufacturing apparatus 102 according to the second embodiment, as described above, the first electrospinning apparatus 120, the second electrospinning apparatus 122, the inorganic particle containing apparatus 140, and the joining apparatus 130 are provided. The separator 1 can be manufactured.

  According to the separator manufacturing method according to Embodiment 2, as described above, the base material layer preparation step S11, the first electrospinning step S12, the second electrospinning step S13, the inorganic particle inclusion step S14, and the bonding Since step S15 is included in this order, the separator 1 can be manufactured.

[Embodiment 3]
FIG. 9 is a front view of the separator manufacturing apparatus 104 according to the third embodiment.
FIG. 10 is a flowchart of the separator manufacturing method according to the third embodiment.

  In the third embodiment, a separator manufacturing apparatus and a separator manufacturing method for manufacturing the separator 1 are different from the separator manufacturing apparatus 100 and the separator manufacturing method according to the first embodiment, and the separator manufacturing according to the second embodiment. What is different from the apparatus 102 and the separator manufacturing method will be described.

  The separator manufacturing apparatus 104 according to the third embodiment has basically the same configuration as the separator manufacturing apparatus 100 according to the first embodiment, but the configuration of the second electrospinning apparatus is that of the separator manufacturing apparatus 100 according to the first embodiment. Not the case. Details will be described below.

  As shown in FIG. 9, the second electrospinning apparatus 123 in the separator manufacturing apparatus 104 has basically the same configuration as the second electrospinning apparatus 121 in the first embodiment, but dissolves the raw material of the second nanofibers 32. The polymer solution has a mechanism for forming the layer 31 including the second nanofibers 32 on the surface of the first nanofiber layer 20 ′, and the second layer after the formation of the layer 31 including the second nanofibers 32. The layer 31 including the nanofibers 32 includes the inorganic particles 34, and the layer 31 including the second nanofibers 32 has the mechanism of “the second nanofiber layer 30 including the second nanofibers 32 and the inorganic particles 34”. Is different.

Although the detailed description of the second electrospinning device 123 is omitted, the basic mechanical configuration is the same as that of the second electrospinning device 121, but further includes an inorganic particle containing device 142 immediately after the nozzle unit 210. In FIG. 9, in order to simplify the explanation, the same components and elements of the second electrospinning device 123 as those of the corresponding components in the second electrospinning device 121 are the same. A reference is attached.
In addition, the polymer solution which melt | dissolved the raw material of the 2nd nanofiber 32 enters into the raw material tank 232 of the 2nd electrospinning apparatus 123. FIG.

  The inorganic particle inclusion device 142 includes the layer 31 including the second nanofibers 32 to include the inorganic particles 34, and the layer 31 including the second nanofibers 32 is changed to “the second nanofibers 32 and the second nanofibers including the inorganic particles 34. This is a device having a mechanism called “fiber layer 30”. Since the inorganic particle containing device 142 has basically the same configuration as the inorganic particle containing device 140 in Embodiment 2 except that it is a part of the second electrospinning device 123, detailed description thereof is omitted. .

  The separator manufacturing method according to Embodiment 3 is basically the same method as the separator manufacturing method according to Embodiment 1, but the content of the second electrospinning step is the case of the separator manufacturing method according to Embodiment 1. Different. Details will be described below.

As shown in FIG. 10, the separator manufacturing method according to Embodiment 3 includes a base material layer preparation step S21, a first electrospinning step S22, a second electrospinning step S23, and a joining step S24 in this order. .
Among these, base material layer preparation process S21 is the same process as base material layer preparation process S1 in Embodiment 1. FIG. Moreover, 1st electrospinning process S22 is a process similar to 1st electrospinning process S2 in Embodiment 1. FIG. Furthermore, the joining step S24 is the same step as the joining step S4 in the first embodiment. Therefore, description of these steps is omitted.

In the second electrospinning step S23, a layer 31 containing the second nanofibers 32 is formed on the surface of the first nanofiber layer 20 ′ by using a polymer solution in which the raw material of the second nanofibers 32 is dissolved by an electrospinning method. In addition, after the formation of the layer 31 including the second nanofiber 32, the layer 31 including the second nanofiber 32 includes the inorganic particles 34, and the layer 31 including the second nanofiber 32 is referred to as “the second nanofiber 32 and In this step, the second nanofiber layer 30 including the inorganic particles 34 is used.
In the third embodiment, the second nanofiber layer 30 is formed using the second electrospinning device 123 described above.

  According to the separator manufacturing apparatus 104 according to the third embodiment, as described above, since the first electrospinning apparatus 120, the second electrospinning apparatus 123, and the joining apparatus 130 are provided, the separator 1 can be manufactured. It becomes.

  According to the separator manufacturing method according to the third embodiment, as described above, the base layer preparation step S21, the first electrospinning step S22, the second electrospinning step S23, and the joining step S24 are included in this order. Therefore, the separator 1 can be manufactured.

[Embodiment 4]
FIG. 11 is a front view of the separator manufacturing apparatus 106 according to the fourth embodiment.
FIG. 12 is a flowchart of the separator manufacturing method according to the fourth embodiment.

  In the fourth embodiment, a separator manufacturing apparatus and a separator manufacturing method for manufacturing the separator 1 are different from the separator manufacturing apparatus 100 and the separator manufacturing method according to the first embodiment, and the separator manufacturing according to the second embodiment. What is different from the apparatus 102 and the separator manufacturing method and further different from the separator manufacturing apparatus 104 and the separator manufacturing method according to the third embodiment will be described.

  The separator manufacturing apparatus 104 according to the fourth embodiment has basically the same configuration as the separator manufacturing apparatus 102 according to the second embodiment, but the positions of the inorganic particle containing apparatus and the joining apparatus are the separator according to the second embodiment. This is different from the manufacturing apparatus 102. Details will be described below.

  In the separator manufacturing apparatus 106, as shown in FIG. 11, the positions of the inorganic particle containing apparatus 140 and the joining apparatus 130 are opposite to those of the separator manufacturing apparatus 102. Therefore, in the fourth embodiment, the joining device 130 is a device that joins the base layer 10 and the layer 31 including the second nanofibers 32 with the first nanofibers 22, and the inorganic particle inclusion device 140 includes: An apparatus having a mechanism in which inorganic particles 34 are included in a layer including the second nanofibers 32 and the layer including the second nanofibers 32 is the “second nanofiber layer 30 including the second nanofibers 32 and the inorganic particles 34”. It is. In the fourth embodiment, the bonding apparatus 130 includes a thermal bonding apparatus that performs thermocompression bonding in a state where the base material layer 10, the first nanofiber layer 20, and the layer 31 including the second nanofiber 32 are stacked. .

  The separator manufacturing method according to the fourth embodiment is basically the same method as the separator manufacturing method according to the second embodiment, but the order of the inorganic particle containing device and the joining device is the separator manufacturing method according to the second embodiment. It is different from the case of. Details will be described below.

As shown in FIG. 12, the separator manufacturing method according to Embodiment 4 includes a base material layer preparation step S31, a first electrospinning step S32, a second electrospinning step S33, a joining step S34, and inclusion of inorganic particles. S35 is included in this order.
Among these, base material layer preparation process S31 is the same process as base material layer preparation process S11 in Embodiment 2. The first electrospinning step S32 is the same step as the first electrospinning step S12 in the second embodiment. Furthermore, the second electrospinning step S33 is the same as the second electrospinning step S13 in the second embodiment. Therefore, description of these steps is omitted.
The separator manufacturing method according to Embodiment 4 is performed using the separator manufacturing apparatus 106 described above.

The joining step S <b> 34 is a step of joining the base material layer 10 and the layer 31 including the second nanofibers 32 with the first nanofibers 22. The joining step S34 is a thermal joining step in which thermocompression bonding is performed in a state where the base material layer 10, the first nanofiber layer 20, and the layer 31 containing the second nanofiber are laminated, and the first joining step S34 is performed. At least a part of the nanofibers 22 is melted by heat, and the base layer 10 and the layer 31 containing the second nanofibers are joined by the first nanofibers 22.
The joining step S34 is performed using the joining device 130 described above.
In the inorganic particle inclusion step S35, the layer including the second nanofibers 32 further includes the inorganic particles 34, and the layer including the second nanofibers 32 is referred to as “second nanofibers including the second nanofibers 32 and the inorganic particles 34”. This is the step of “layer 30”.
The inorganic particle containing step S35 is performed using the inorganic particle containing device 140 described above.

  According to the separator manufacturing apparatus 106 according to the fourth embodiment, as described above, the first electrospinning apparatus 120, the second electrospinning apparatus 122, the joining apparatus 130, and the inorganic particle containing apparatus 140 are provided. The separator 1 can be manufactured.

  According to the separator manufacturing method according to Embodiment 4, as described above, the base material layer preparation step S31, the first electrospinning step S32, the second electrospinning step S33, the joining step S34, and the inclusion of inorganic particles. Since step S35 is included in this order, the separator 1 can be manufactured.

  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 forms without departing from the spirit thereof, and for example, the following modifications are possible.

(1) The number, positional relationship, and size of each component in each of the above embodiments are examples, and the present invention is not limited to this.

(2) In each of the above embodiments, the separator of the present invention has been described by taking the separator composed of the base material layer 10, the first nanofiber layer 20, and the second nanofiber layer 30 as an example. However, the present invention is not limited to this. It is not something. For example, it is good also as a separator further provided with components (a reinforcing member etc.) other than a base material layer, a 1st nanofiber layer, and a 2nd nanofiber layer.

(3) Although the separator 1 which concerns on each said embodiment shall be manufactured using the separator manufacturing apparatus which concerns on each embodiment, this invention is not limited to this. For example, the separator of the present invention may be manufactured using a separator manufacturing apparatus in which a first electrospinning apparatus, a second electrospinning apparatus, and a joining apparatus are separately provided. Thus, the separator of this invention can be manufactured using various separator manufacturing apparatuses.

(4) Although the separator 1 which concerns on each said embodiment shall be manufactured with the separator manufacturing method which concerns on each embodiment, this invention is not limited to this. For example, the separator of the present invention may be manufactured by a separator manufacturing method in which the first electrospinning process and the second electrospinning process are performed simultaneously. Thus, the separator of the present invention can be manufactured using various separator manufacturing methods.

(5) Although the separator manufacturing method according to each embodiment described above is performed using the separator manufacturing apparatus according to each embodiment, the present invention is not limited to this. For example, the separator manufacturing method of the present invention may be performed using a separator manufacturing apparatus in which the first electrospinning apparatus, the second electrospinning apparatus, and the joining apparatus are separate from each other. Thus, the separator manufacturing method of the present invention can be performed using various separator manufacturing apparatuses.

(6) The embodiment 3 has a mechanism for forming the layer 31 including the second nanofibers 32 on the surface of the first nanofiber layer 20 using a polymer solution in which the raw material of the second nanofibers 32 is dissolved. In addition, after the formation of the layer 31 including the second nanofibers 32, the layer 31 including the second nanofibers 32 includes the inorganic particles 34, and the layer 31 including the second nanofibers 32 is referred to as “the second nanofibers 32 and Although the second electrospinning device 123 having the mechanism of “the second nanofiber layer 30 including the inorganic particles 34” is used, the present invention is not limited to this. Using a polymer solution in which the raw material of the second nanofiber is dissolved, the first nanofiber layer has a mechanism for forming a layer containing the second nanofiber on the surface, and the layer containing the second nanofiber is being formed. A second electrospinning apparatus having a mechanism in which inorganic particles are included in the layer containing the second nanofibers, and the layer containing the second nanofibers is a “second nanofiber layer containing the second nanofibers and inorganic particles”. It may be used. As such a second electrospinning device, for example, a second electrospinning device in which an inorganic particle containing device is arranged between nozzles in a plurality of nozzles, or an inorganic particle containing device is arranged on the side surface side of the nozzle unit. The 2nd electrospinning apparatus etc. which are made can be used.

(7) In the case of (6) above, as the second electrospinning step, a second nanofiber layer is formed on the surface of the first nanofiber layer using a polymer solution in which the raw material of the second nanofiber is dissolved by an electrospinning method. A layer containing fibers is formed, and during the formation of the layer containing second nanofibers, the layer containing the second nanofibers contains inorganic particles, and the layer containing the second nanofibers is referred to as “second nanofibers and inorganic”. A separator can be obtained by performing the second electrospinning step of “second nanofiber layer containing particles”.

(8) In each of the above-described embodiments, the first nanofiber made of a resin having thermal bondability is used, and the base layer 10 and the second nanofiber layer 30 are at least partially melted by heat. Although the present invention has been described by taking the separator joined by the fibers 22 as an example, the separator of the present invention is not limited to this. FIG. 13 is a flowchart of a separator manufacturing method according to a modification. For example, first nanofibers made of a resin that is soluble in a predetermined solvent are used, and the base material layer and the second nanofiber layer are joined by the first nanofibers at least partially dissolved in the predetermined solvent. It is good also as a separator. For example, as shown in FIG. 13, such a separator is formed by immersing the second laminate in a solvent having appropriate solubility with respect to the first nanofibers, or through the second laminate in the vapor of the solvent. It can manufacture by performing the process (joining process (dissolution joining process) S44) which joins a layer and a 2nd nanofiber layer. By setting it as such a structure, it becomes possible to join a base material layer and a 2nd nanofiber layer easily using a predetermined | prescribed solvent.

(9) In each of the above-described embodiments, the present invention has been described by taking as an example a separator manufacturing apparatus including one first electrospinning apparatus and one second electrospinning apparatus, but the present invention is not limited to this. . For example, a separator manufacturing apparatus including two or more first electrospinning apparatuses and second electrospinning apparatuses can be applied to the present invention.

(10) In Embodiments 2 to 4, the layer including the second nanofibers is set as the “second nanofiber layer including the second nanofibers and the inorganic particles” by injecting the inorganic particles 34. The invention is not limited to this. For example, by applying a solution containing inorganic particles, the layer containing the second nanofibers may be set as the “second nanofiber layer containing the second nanofibers and inorganic particles”.

DESCRIPTION OF SYMBOLS 1 ... Separator, 10 ... Base material layer, 12 ... Base material fiber, 20 ... 1st nanofiber layer (after joining process), 20 '... 1st nanofiber layer (before joining process), 22 ... 1st nano Fibers: 24 ... Molten first nanofibers, 30 ... Second nanofiber layers, 31 ... Layers containing second nanofibers, 32 ... Second nanofibers, 34 ... Inorganic particles, 40 ... First laminate, 50 ... Second laminated body, 100, 102, 104 ... separator manufacturing device, 110 ... transport device, 111 ... feeding roller, 112 ... winding roller, 113, 118 ... tension roller, 114 ... auxiliary roller, 120 ... first electrospinning device 121, 122, 123 ... second electrospinning device, 130 ... joining device, 140,142 ... inorganic particle containing device, 200 ... housing, 210 ... nozzle unit, 220 ... upward nozzle, 250 ... collect Chromatography, 252: insulating member, 260 ... power supply 270 ... auxiliary belt apparatus 272 ... auxiliary belt, 274 ... auxiliary belt rollers

Claims (21)

A base material layer;
A first nanofiber layer comprising first nanofibers;
A second nanofiber layer comprising second nanofibers and inorganic particles,
The base material layer, the first nanofiber layer, and the second nanofiber layer are laminated in the order of the base material layer, the first nanofiber layer, and the second nanofiber layer,
The separator, wherein the base material layer and the second nanofiber layer are joined by the first nanofiber. The separator according to claim 1, wherein
The first nanofiber is made of a resin having thermal bondability,
The separator is characterized in that the base material layer and the second nanofiber layer are joined by first nanofibers at least partially melted by heat. The separator according to claim 2,
The melting point of the resin having thermal bondability is lower than both the melting point of the material constituting the base material layer and the melting point of the material constituting the second nanofiber layer. The separator according to claim 3,
The melting point of the resin having thermal bondability is 10 ° C. or more lower than the melting point of the material constituting the base material layer and the melting point of the material constituting the second nanofiber layer. In the separator in any one of Claims 2-4,
The average diameter of the first nanofiber is in the range of 50 nm to 1000 nm. In the separator according to any one of claims 2 to 5,
The average diameter of said 2nd nanofiber is larger than the average diameter of said 1st nanofiber, and exists in the range of 80 nm-3000 nm, The separator characterized by the above-mentioned. The separator according to claim 1, wherein
The first nanofiber is made of a resin having solubility in a predetermined solvent,
The separator is characterized in that the base material layer and the second nanofiber layer are joined by first nanofibers at least partially dissolved in the predetermined solvent. In the separator according to any one of claims 1 to 7,
The separator is characterized in that the first nanofiber layer is thinner than the second nanofiber layer. In the separator according to any one of claims 1 to 8,
The first nanofiber and the second nanofiber are obtained by an electrospinning method. In the separator according to claim 1-9,
The average diameter of the said inorganic particle exists in the range of 5 nm-1000 nm, The separator characterized by the above-mentioned. In the separator in any one of Claims 1-10,
The said inorganic particle consists of an inorganic oxide, an inorganic nitride, or an inorganic carbide, The separator characterized by the above-mentioned. First electrospinning having a mechanism for forming a first nanofiber layer including the first nanofibers on one surface of a base material layer using a polymer solution in which a raw material of the first nanofibers is dissolved by an electrospinning method Equipment,
Using a mixed polymer solution in which inorganic particles are mixed with a polymer solution in which the raw material of the second nanofibers is dissolved by electrospinning, “the second nanofibers and the inorganic particles are applied to the surface of the first nanofiber layer. A second electrospinning apparatus having a mechanism for forming a "second nanofiber layer including";
A separator manufacturing apparatus comprising: a joining device that joins the base material layer and the second nanofiber layer with the first nanofibers. First electrospinning having a mechanism for forming a first nanofiber layer including the first nanofibers on one surface of a base material layer using a polymer solution in which a raw material of the first nanofibers is dissolved by an electrospinning method Equipment,
The electrospinning method has a mechanism for forming a layer containing the second nanofibers on the surface of the first nanofiber layer using a polymer solution in which the raw material of the second nanofibers is dissolved, and the second During or after the formation of the layer containing nanofibers, inorganic particles are included in the layer containing the second nanofibers, and the layer containing the second nanofibers is referred to as “second nanofibers containing the second nanofibers and the inorganic particles. A second electrospinning apparatus having a mechanism of “fiber layer”;
A separator manufacturing apparatus comprising: a joining device that joins the base material layer and the second nanofiber layer with the first nanofibers. First electrospinning having a mechanism for forming a first nanofiber layer including the first nanofibers on one surface of a base material layer using a polymer solution in which a raw material of the first nanofibers is dissolved by an electrospinning method Equipment,
A second electrospinning apparatus having a mechanism for forming a layer containing the second nanofibers on the surface of the first nanofiber layer by using a polymer solution in which a raw material of the second nanofibers is dissolved by an electrospinning method;
Inorganic particles having a mechanism in which inorganic particles are further included in the layer including the second nanofibers, and the layer including the second nanofibers is the “second nanofiber layer including the second nanofibers and the inorganic particles”. An inclusion device;
A separator manufacturing apparatus comprising: a joining device that joins the base material layer and the second nanofiber layer with the first nanofibers. First electrospinning having a mechanism for forming a first nanofiber layer including the first nanofibers on one surface of a base material layer using a polymer solution in which a raw material of the first nanofibers is dissolved by an electrospinning method Equipment,
A second electrospinning apparatus having a mechanism for forming a layer containing the second nanofibers on the surface of the first nanofiber layer by using a polymer solution in which a raw material of the second nanofibers is dissolved by an electrospinning method;
A joining device for joining the base material layer and the layer containing the second nanofibers by the first nanofibers;
Contains inorganic particles in the layer containing the second nanofibers, and contains inorganic particles having a mechanism that makes the layer containing the second nanofibers "the second nanofiber layer containing the second nanofibers and the inorganic particles" A separator manufacturing apparatus comprising: In the separator manufacturing apparatus in any one of Claims 12-15,
The bonding apparatus includes a thermal bonding apparatus that performs thermocompression bonding in a state in which the base material layer, the first nanofiber layer, and the second nanofiber layer or the layer containing the second nanofiber are stacked. A separator manufacturing apparatus. A base material layer preparation step of preparing a base material layer;
A first electrospinning step of forming a first nanofiber layer including the first nanofibers on one surface of the base material layer using a polymer solution in which a raw material of the first nanofibers is dissolved by an electrospinning method; ,
Using a mixed polymer solution in which inorganic particles are mixed with a polymer solution in which the raw material of the second nanofibers is dissolved by electrospinning, “the second nanofibers and the inorganic particles are applied to the surface of the first nanofiber layer. A second electrospinning step of forming a “second nanofiber layer comprising”;
The separator manufacturing method characterized by including the joining process which joins the said base material layer and the said 2nd nanofiber layer with the said 1st nanofiber in this order. A base material layer preparation step of preparing a base material layer;
A first electrospinning step of forming a first nanofiber layer including the first nanofibers on one surface of the base material layer using a polymer solution in which a raw material of the first nanofibers is dissolved by an electrospinning method; ,
A layer containing the second nanofibers is formed on the surface of the first nanofiber layer by using a polymer solution in which the raw material of the second nanofibers is dissolved by electrospinning, and the second nanofibers are included. During or after the formation of the layer, the layer containing the second nanofibers is made to contain inorganic particles, and the layer containing the second nanofibers is referred to as “the second nanofiber layer containing the second nanofibers and the inorganic particles”. A second electrospinning step,
The separator manufacturing method characterized by including the joining process which joins the said base material layer and the said 2nd nanofiber layer with the said 1st nanofiber in this order. A base material layer preparation step of preparing a base material layer;
A first electrospinning step of forming a first nanofiber layer including the first nanofibers on one surface of the base material layer using a polymer solution in which a raw material of the first nanofibers is dissolved by an electrospinning method; ,
A second electrospinning step of forming a layer containing the second nanofibers on the surface of the first nanofiber layer using a polymer solution obtained by dissolving the raw material of the second nanofibers by an electrospinning method;
Inorganic particle inclusion step of further including inorganic particles in the layer containing the second nanofibers and setting the layer containing the second nanofibers as the “second nanofiber layer containing the second nanofibers and the inorganic particles” When,
The separator manufacturing method characterized by including the joining process which joins the said base material layer and the said 2nd nanofiber layer with the said 1st nanofiber in this order. A base material layer preparation step of preparing a base material layer;
A first electrospinning step of forming a first nanofiber layer including the first nanofibers on one surface of the base material layer using a polymer solution in which a raw material of the first nanofibers is dissolved by an electrospinning method; ,
A second electrospinning step of forming a layer containing the second nanofibers on the surface of the first nanofiber layer using a polymer solution obtained by dissolving the raw material of the second nanofibers by an electrospinning method;
A bonding step of bonding the base layer and the layer containing the second nanofibers by the first nanofibers;
Inorganic particle inclusion step of further including inorganic particles in the layer containing the second nanofibers and setting the layer containing the second nanofibers as the “second nanofiber layer containing the second nanofibers and the inorganic particles” In this order. In the separator manufacturing method in any one of Claims 17-20,
The bonding step is a heat bonding step of thermocompression bonding in a state where the base material layer, the first nanofiber layer, and the second nanofiber layer or the layer containing the second nanofiber are laminated, The separator manufacturing method characterized by melt | dissolving at least one part of said 1st nanofiber with a heat | fever by the said heat joining process, and joining the said base material layer and said 2nd nanofiber layer with said 1st nanofiber.

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