JP2013037853A - 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; and a nanofiber layer 20 including "a joining nanofiber 22 used for a join with the base material layer 10" and an inorganic particle 26. The base material layer 10 and the nanofiber layer 20 are joined by the joining 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 includes a base material layer, “joining nanofibers used for joining to the base material layer”, and nanofiber layers containing inorganic particles, and the base material layer and the nanofibers. The layer is bonded by the bonded nanofiber.

  For this reason, according to the separator of the present invention, since the base material layer and the nanofiber layer are joined by the joint nanofiber, it is possible to suppress the base material layer and the nanofiber layer from being separated, As a result, it is possible to suppress the 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 a nanofiber layer containing inorganic particles, it is possible to provide a separator having high thermal stability and high affinity for an electrolyte solution as in the case of conventional separators. It becomes.

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

  In addition, according to the separator of the present invention, by adding the properties of the nanofiber layer (such as a large surface area and fine voids) to the properties of the base material layer, as with conventional separators, more diverse properties can be obtained. It becomes possible to set it as the separator which has.

  In addition, according to the separator of the present invention, since the fiber has a nanofiber layer with a fine average diameter and voids, the electrolytic solution absorption is higher than that of a separator having a general fiber layer, as in the case of a conventional separator. , Low ionic resistance, high dendrite resistance, and a thin separator with a total thickness.

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

  By setting it as such a structure, it becomes possible to join easily by heating a base material layer and a 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 preferably lower than the melting point of the material constituting the base material layer.

  By adopting such a configuration, it is possible to selectively melt the bonded nanofibers by heating at a temperature between the melting point of the material constituting the base layer and the melting point of the resin having thermal bondability. Become.

[4] In the separator of the present invention, the melting point of the resin having thermal bondability is preferably 10 ° C. or more lower than the melting point of the material constituting the base material layer.

  By adopting 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 resin having thermal bondability, so that the bonded nanofibers are selectively melted by heating. Is easily possible.

[5] In the separator of the present invention, the average diameter of the bonded nanofiber is preferably in the range of 50 nm to 1000 nm.

  With such a configuration, the base material layer and the nanofiber layer are joined with sufficient strength, and the liquid permeability of the separator can be suppressed from decreasing.

  In the present invention, the average diameter of the bonded nanofibers was in the range of 50 nm to 1000 nm because the base material layer and the nanofiber layer were bonded with sufficient strength when the average diameter was smaller than 50 nm. This is because the liquid permeability of the separator may be lowered when the average diameter is larger than 1000 nm.

[6] In the separator of the present invention, it is preferable that the nanofiber layer further includes a high melting point nanofiber made of a material having a melting point higher than that of the resin having thermal bondability.

  By setting it as such a structure, it becomes possible to suppress that the structure of a nanofiber layer breaks by heating.

[7] In the separator of the present invention, the bonding nanofiber is made of a resin having solubility in a predetermined solvent, and at least a part of the base material layer and the nanofiber layer is the predetermined solvent. It is preferable to be bonded by bonded nanofibers dissolved in (1).

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

[8] In the separator of the present invention, the nanofiber layer is a low-solubility nanofiber made of a material having lower solubility in the predetermined solvent than a resin having solubility in the predetermined solvent. It is preferable that it is further included.

  By setting it as such a structure, it becomes possible to suppress that the structure of a nanofiber layer breaks with a solvent.

[9] In the separator of the present invention, the bonded nanofiber is preferably obtained by an electrospinning method.

  With such a configuration, it is possible to form a nanofiber layer having desired properties (composition, thickness, basis weight, average diameter of bonded nanofibers, melting temperature, solubility in a solvent, and the like).

[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 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 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 mixed polymer solution in which inorganic particles are mixed with a polymer solution in which a raw material for bonded nanofibers is dissolved by an electrospinning method. An electrospinning apparatus having a mechanism for forming a bonded nanofiber and a nanofiber layer containing the inorganic particles, and a bonding apparatus for bonding the base material layer and the nanofiber layer by the bonded nanofiber. And

  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 has a mechanism for forming a layer containing the bonded nanofibers on one surface of the base material layer using a polymer solution in which the raw materials of bonded nanofibers are dissolved by electrospinning. And the inorganic nanoparticle is included in the layer including the bonded nanofiber during or after the formation of the layer including the bonded nanofiber, and the layer including the bonded nanofiber is referred to as “the bonded nanofiber and the inorganic particle. An electrospinning apparatus having a mechanism of “a nanofiber layer including” and a bonding apparatus that bonds the base material layer and the nanofiber layer with the bonded nanofibers.

  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 has a mechanism for forming a layer containing the bonded nanofibers on one surface of the base material layer using a polymer solution in which the bonded nanofiber materials are dissolved by an electrospinning method. Inorganic having an electrospinning apparatus having the mechanism of further including inorganic particles in the layer including the bonded nanofibers and setting the layer including the bonded nanofibers as the “nanofiber layer including the bonded nanofibers and the inorganic particles” It is characterized by comprising a particle containing device and a bonding device for bonding the base material layer and the nanofiber layer with the bonded nanofibers.

  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 has a mechanism for forming a layer containing the bonded nanofibers on one surface of the base material layer using a polymer solution in which the bonded nanofiber raw materials are dissolved by an electrospinning method. An electrospinning apparatus, a bonding apparatus for bonding the base material layer and the layer including the bonding nanofibers by the bonding nanofibers, an inorganic particle is included in the layer including the bonding nanofibers, and the bonding nanofibers. And an inorganic particle containing device having a mechanism that makes the layer including “the nanofiber layer including the nanofiber and the inorganic particle”.

  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 includes a thermal joining device that performs thermocompression bonding in a state where the base material layer and the nanofiber layer or the layer containing the joined nanofiber are laminated. Is preferred.

  By adopting such a configuration, it is possible to bond the base material layer and the nanofiber layer by heating in the case of using bonded nanofibers made of a resin having thermal bondability.

[17] The separator manufacturing method of the present invention uses a mixed polymer solution in which inorganic particles are mixed into a polymer solution in which a raw material of bonded nanofibers is dissolved by a base layer preparing step for preparing a base layer and an electrospinning method. Then, an electrospinning step of forming “the nanofiber layer including the bonded nanofibers and the inorganic particles” on one surface of the base layer, and the base layer and the nanofiber layer by the bonded nanofibers. And a joining step of joining the layers 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 bonded nanofibers is dissolved by an electrospinning method. Forming a layer containing the bonded nanofibers on the surface, and including or bonding inorganic particles to the layer including the bonded nanofibers during or after the formation of the layer including the bonded nanofibers. Including an electrospinning step of “the bonded nanofiber and the nanofiber layer including the inorganic particles” and a bonding step of bonding the base material layer and the nanofiber layer by the bonded nanofiber in this order. Features.

  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 for preparing a base material layer, and a polymer solution in which a raw material of bonded nanofibers is dissolved by an electrospinning method. An electrospinning step of forming a layer including the bonded nanofiber on the surface of the substrate, and further including inorganic particles in the layer including the bonded nanofiber, and the layer including the bonded nanofiber is referred to as “the bonded nanofiber and the inorganic particle”. Inorganic particle containing step of “containing nanofiber layer” and a bonding step of bonding the base material layer and the nanofiber layer with the bonded nanofibers 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] A base material layer preparing step for preparing a base material layer and a polymer solution in which a raw material of the joint nanofiber is dissolved by an electrospinning method, and the joint nanofiber is included on one surface of the base material layer. An electrospinning step of forming a layer, a bonding step of bonding the base material layer and the layer containing the bonded nanofibers by the bonded nanofibers, the layer including the bonded nanofibers including inorganic particles, and the bonding And an inorganic particle-containing step in which the nanofiber-containing layer is “the nanofiber layer containing the bonded nanofiber and the inorganic particle” 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, the joining step is a thermal joining step of thermocompression bonding in a state where the base material layer and the nanofiber layer or the layer containing the joined nanofiber are laminated. It is preferable that at least a part of the bonded nanofibers is melted by heat in the thermal bonding step, and the base material layer and the nanofiber layer or the layer containing the bonded nanofibers are bonded by the bonded nanofibers.

  By adopting such a method, it is possible to bond the base material layer and the nanofiber layer by heating in the case of using bonded nanofibers made of a resin having thermal bondability.

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 S3 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 electrospinning process S12 and inorganic particle containing process S13 which concern on Embodiment 2. FIG. 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 figure for demonstrating the separator 2 which concerns on Embodiment 4. FIG. It is a front view of the separator manufacturing apparatus 106 which concerns on Embodiment 5. FIG. 10 is a flowchart of a separator manufacturing method according to Embodiment 5. 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 shown in FIG. 1, the separator 1 according to Embodiment 1 includes a base material layer 10 and a nanofiber layer 20. In the separator 1, the base material layer 10 and the nanofiber layer 20 are bonded by bonded nanofibers 22. Specifically, as shown in FIG. 1C, the base material layer 10 and the nanofiber layer 20 are bonded by bonded 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 nanofiber layer 20 includes nanofibers 22 and inorganic particles 26. In addition, the nanofiber layer should just contain joining nanofiber and inorganic particle, and if it is on it, it may contain substances other than joining nanofiber and inorganic particle. The bonded nanofiber 22 is made of a resin having thermal bondability. The average diameter of the bonding nanofiber 22 is in the range of 50 nm to 1000 nm, for example, 100 nm. The bonded nanofiber 22 can be obtained by an electrospinning method as described later.
The average diameter of the inorganic particles 26 is in the range of 5 nm to 1000 nm, for example, 50 nm. The inorganic particles 26 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 lower than the melting point of the material (base material fiber 12) constituting the base material layer 10, and more specifically, 10 or more.

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, an electrospinning device 120, and a joining device 130. The separator manufacturing apparatus 100 includes one electrospinning apparatus 120.

  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 electrospinning apparatus 120 uses a mixed polymer solution in which inorganic particles 26 are mixed with a polymer solution in which the raw materials of the bonded nanofibers 22 are dissolved by an electrospinning method, and uses one side of the base material layer 10 (in the first embodiment). It has a mechanism for forming a nanofiber layer 20 ′ including bonded nanofibers 22 and inorganic particles 26 on the lower surface (see FIG. 4B described later).
As shown in FIG. 2, the 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 electrospinning apparatus 120 discharges the polymer solution from the discharge ports of a plurality of upward nozzles 220, which will be described later, to form the 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 discharges “a mixed polymer solution in which inorganic particles 26 are mixed with a polymer solution in which the raw materials of the bonding nanofibers 22 are dissolved (a polymer solution of a resin having thermal bonding properties)” supplied from the polymer solution supply unit 230. It is a nozzle that discharges from the outlet. 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).
The upward nozzle 220 in the first embodiment uses a mixed polymer solution in which inorganic particles 26 are mixed with a polymer solution in which the raw materials of the bonding nanofibers 22 are dissolved in the electrospinning apparatus 100, One of the mechanisms for forming the “nanofiber layer 20 ′ including the bonded nanofibers 22 and the inorganic particles 26” has a diameter larger than that of the inorganic particles 26. Specifically, the particle diameter of the inorganic particles 26 is preferably 100 times or more.

  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. In the raw material tank 232 of the electrospinning apparatus 120, a mixed polymer solution in which the inorganic particles 26 are mixed with a polymer solution in which the raw material of the bonding nanofibers 22 is dissolved is contained.

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 bonding device 130 is a device that bonds the base material layer 10 and the nanofiber layer 20 using the bonded nanofibers 22. The bonding apparatus 130 is a thermal bonding apparatus that performs thermocompression bonding in a state where the base material layer 10 and the nanofiber layer 20 ′ are stacked. 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 addition, in FIG. 2, although the calender roll illustrated the thing of the structure which pinches | interposes the nanofiber laminated body 30 with an upper and lower roller one by one, it is not restricted to such a structure, Upper and lower two each 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. 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 nanofiber laminate 30 after the electrospinning step S2.
FIG. 5 is a view for explaining the joining step S3 in the first embodiment. FIG. 5A is an enlarged schematic diagram before the joining step S3, and FIG. 5B is an enlarged schematic diagram after the joining step S3.

  As shown in FIG. 3, the separator manufacturing method according to Embodiment 1 includes a base material layer preparation step S1, an electrospinning step S2, and a joining step S3 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. Electrospinning process S2
As shown in FIG. 4B, the electrospinning step S2 is performed by using a mixed polymer solution in which inorganic particles 26 are mixed with a polymer solution in which a raw material of the bonded nanofiber 22 is dissolved by an electrospinning method. This is a step of forming “a nanofiber layer 20 ′ including bonded nanofibers 22 and inorganic particles 26” on one (lower surface) of the base material layer 10 using a polymer solution in which the raw material is dissolved.
The electrospinning step S2 is performed using the electrospinning apparatus 120 described above. Specifically, first, the mixed polymer solution is supplied to the nozzle unit 210 through the polymer solution supply unit 230 in the 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, thereby forming the nanofiber layer 20 ′ on the lower surface of the base material layer 10 that is a long sheet. In this case, the nanofiber laminate 30 is used.

3. Joining step S3
The joining step S3 is a step of joining the base material layer 10 and the nanofiber layer 20 using the joined nanofibers 22 as shown in FIG. The joining step S3 is a thermal joining step in which the base material layer 10 and the nanofiber layer 20 are laminated and thermocompression bonded, and at least a part of the joined nanofibers 22 is melted by heat in the thermal joining step. The base material layer 10 and the nanofiber layer 20 are bonded with the bonded nanofibers 22.
The joining step S3 is performed using the joining device 130 described above.

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

  As a material of the bonding nanofiber 22, a resin having thermal bonding properties, for example, polyvinylidene fluoride (PVDF), polylactic acid (PLA), polypropylene (PP), polyethylene (PE), polyvinyl acetate (PVAc), 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.

  As a solvent for producing the polymer solution, 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 base material layer has the nanofiber layer 20 including the bonded nanofibers 22, and the base material layer 10 and the nanofiber layer 20 are bonded by the bonded nanofibers 22. And the nanofiber layer can be prevented from peeling off, and as a result, the nanofiber layer can be prevented from peeling off and being damaged in the manufacturing process of the separator.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since it has the nanofiber layer 20 containing the inorganic particle 26, it is the separator which has high thermal stability and high affinity with respect to electrolyte solution similarly to the conventional separator. It becomes possible.

  Moreover, according to the separator 1 which concerns on Embodiment 1, it can be set as the separator which has various properties like the conventional separator by using the base material layer 10 and the nanofiber layer 20 which have a respectively different property. It becomes possible.

  Moreover, according to the separator 1 which concerns on Embodiment 1, by adding the property (a large surface area, a fine space | gap, etc.) which the nanofiber layer 20 has to the property which the base material layer 10 has, similarly to the conventional separator, A separator having more various properties can be obtained.

  Further, according to the separator 1 according to the first embodiment, since the average fiber diameter and voids are provided with the nanofiber layer 20, compared with a separator having a general fiber layer, as in the conventional separator, It is possible to obtain a separator having a high total electrolyte absorption, 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 joining nanofiber 22 consists of resin which has heat bondability, it can be easily joined by heating a base material layer and a nanofiber layer. Become.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since melting | fusing point of resin which has thermal bondability is lower than melting | fusing point of the material which comprises the base material layer 10, melting | fusing point and thermal bondability of the material which comprises a base material layer It becomes possible to selectively melt the bonded nanofibers by heating at a temperature between the melting point of the resin having the.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since melting | fusing point of resin which has heat bondability is 10 degreeC or more lower than melting | fusing point of the material which comprises the base material layer 10, it is melting | fusing point of the material which comprises a base material layer, Since there is a sufficient difference in the melting point of the resin having thermal bondability, it becomes easy to selectively melt the bonded nanofibers by heating.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the average diameter of joining nanofiber 22 exists in the range of 50 nm-1000 nm, it will be in the state where the base material layer and the nanofiber layer were joined with sufficient intensity, And it becomes possible to suppress that the liquid permeability of a separator falls.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the joining nanofiber 22 was obtained by the electrospinning method, desired properties (composition, thickness, basis weight, average diameter of joining nanofiber, melting temperature) It is possible to form a nanofiber layer having solubility in a solvent.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the average diameter of the inorganic particle 26 exists in the range of 5 nm-1000 nm, it becomes possible to make handling of an inorganic particle easy, and a nanofiber layer It is possible to suppress the collapse of the spatial structure.

  Moreover, according to the separator 1 which concerns on Embodiment 1, since the inorganic particle 26 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 electrospinning apparatus 120 and the joining apparatus 130 are provided, the separator 1 according to the first embodiment as described above can be manufactured.

  Moreover, according to the separator manufacturing apparatus 100 which concerns on Embodiment 1, since the joining apparatus 130 consists of a thermobonding apparatus thermocompression-bonded in the state which laminated | stacked the base material layer 10 and the nanofiber layer 20, it has thermal bondability. In the case of using bonded nanofibers made of resin, it is possible to bond the base material layer and the nanofiber layer by heating.

  According to the separator manufacturing method according to the first embodiment, the base material layer preparation step S1, the electrospinning step S2, and the joining step S3 are included in this order, and thus the separator 1 according to the first embodiment as described above is manufactured. It becomes possible to do.

  Moreover, according to the separator manufacturing method which concerns on Embodiment 1, joining process S3 is a thermal joining process of thermocompression bonding in the state which laminated | stacked the base material layer 10 and the nanofiber layer 20, Comprising: By the said thermal joining process In the case of using bonded nanofibers made of a resin having thermal bondability, at least a part of the bonded nanofibers 22 is melted by heat to bond the base layer 10 and the nanofiber layer 20 with the bonded nanofibers 22. The base material layer and the nanofiber layer can be bonded 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 electrospinning step S12 and the inorganic particle containing step S13 according to the second embodiment. FIG. 8A is an enlarged schematic view after the electrospinning step S12, and FIG. 8B is an enlarged schematic view after the inorganic particle containing step S13.

  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 has basically the same configuration as the separator manufacturing apparatus 100 according to the first embodiment, but may further include an electrospinning apparatus and an inorganic particle containing apparatus. This 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 electrospinning device 122 in the separator manufacturing apparatus 102 has basically the same configuration as the electrospinning device 120 in Embodiment 1, but uses a polymer solution in which the raw materials of the bonded nanofibers 22 are dissolved. Thus, the difference is that it has a mechanism for forming the layer 21 including the bonded nanofibers 22 on one surface (the lower surface in the second embodiment) of the base material layer 10.

Although the detailed description of the electrospinning device 122 is omitted, although the basic mechanical configuration is the same as that of the electrospinning device 120, the detailed structure is different in order to form the layer 21 including the bonded nanofibers 22. In FIG. 6, for simplicity of explanation, the same reference numerals are given to the components of the electrospinning device 122 that have the same basic configuration and role as the corresponding components in the electrospinning device 120. .
Note that a polymer solution in which the raw material of the bonded nanofibers 22 is dissolved enters the raw material tank 232 of the electrospinning device 122.

  The inorganic particle containing apparatus 140 further includes the inorganic particles 26 in the layer 21 including the bonded nanofibers 22, and the layer 21 including the bonded nanofibers 22 is changed to “the nanofiber layer 20 ′ including the bonded nanofibers 22 and the inorganic particles 26 ′. Is a device having a mechanism of “see FIG. 8”. Specifically, the inorganic particle containing device 140 is a device that is disposed between the electrospinning device 122 and the bonding device 130 and injects the inorganic particles 26 together with the solvent toward the layer 21 including the bonded nanofibers 22. is there. As the solvent, a solvent that does not damage the bonded nanofibers 22 can be used. Although the solvent which can be used changes with kinds of joining 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 Embodiment 2 is basically the same method as the separator manufacturing method according to Embodiment 1, except that the contents of the electrospinning step and the inorganic particle-containing step are further included in Embodiment 1. This is different from the case of the separator manufacturing method. Details will be described below.

As shown in FIG. 7, the separator manufacturing method according to Embodiment 2 includes a base material layer preparation step S11, an electrospinning step S12, an inorganic particle inclusion step S13, and a joining step S14 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. Moreover, joining process S14 is the same process as joining process S3 in Embodiment 1. FIG. Therefore, description of these steps is omitted.

The electrospinning step S12 is a step of forming the layer 21 including the bonded nanofibers 22 on one surface of the base material layer 10 using a polymer solution in which the raw materials of the bonded nanofibers 22 are dissolved by an electrospinning method ( (See FIG. 8.)
In the second embodiment, the layer 21 including the bonded nanofibers 22 is formed using the above-described electrospinning device 122.

In the inorganic particle inclusion step S <b> 13, the layer 21 including the bonded nanofiber 22 further includes the inorganic particle 26, and the layer 21 including the bonded nanofiber 22 is changed to “nanofiber layer 20 ′ including the bonded nanofiber 22 and the inorganic particle 26 ′. It is a process to make.
The inorganic particle containing step S13 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, since the electrospinning apparatus 122, the inorganic particle containing apparatus 140, and the bonding apparatus 130 are provided, the separator 1 can be manufactured. .

  According to the separator manufacturing method according to the second embodiment, as described above, since the base layer preparation step S11, the electrospinning step S12, the inorganic particle inclusion step S13, and the joining step S14 are 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 basically has the same configuration as the separator manufacturing apparatus 100 according to the first embodiment, except that the configuration of the electrospinning apparatus is the separator manufacturing apparatus 100 according to the first embodiment. Is different. Details will be described below.

  As shown in FIG. 9, the electrospinning device 124 in the separator manufacturing apparatus 104 has basically the same configuration as the electrospinning device 120 in the first embodiment, but uses a polymer solution in which the raw materials of the bonded nanofibers 22 are dissolved. The base layer 10 has a mechanism for forming the layer 21 including the bonded nanofibers 22 on one surface (the lower surface in the third embodiment), and the layer 21 including the bonded nanofibers 22 is formed. The layer 21 including the bonded nanofibers 22 includes inorganic particles 26 later, and the layer 21 including the bonded nanofibers 22 has a mechanism of “a nanofiber layer 20 ′ including the bonded nanofibers 22 and the inorganic particles 26”. Different.

Although the detailed description of the electrospinning device 124 is omitted, although the basic mechanical configuration is the same as that of the electrospinning device 120, the electrospinning device 124 further includes an inorganic particle containing device 142 at the subsequent stage of the nozzle unit 210. In FIG. 9, in order to simplify the explanation, the same reference numerals are given to the components of the electrospinning device 124 that have the same basic configuration and role as the corresponding components in the electrospinning device 120. .
A polymer solution in which the raw material of the bonding nanofibers 22 is dissolved enters the raw material tank 232 of the electrospinning device 124.

  The inorganic particle inclusion device 142 includes the layer 21 including the bonded nanofibers 22 to include the inorganic particles 26, and the layer 21 including the bonded nanofibers 22 is changed to “the nanofiber layer 20 ′ including the bonded nanofibers 22 and the inorganic particles 26”. It is an apparatus having a mechanism. Except for being part of the electrospinning device 124, the inorganic particle containing device 142 has basically the same configuration as the inorganic particle containing device 140 in the second embodiment, and a detailed description thereof will be 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 electrospinning process is different from that of the separator manufacturing method according to Embodiment 1. 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, an electrospinning step S22, and a joining step S23 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, joining process S23 is a process similar to joining process S3 in Embodiment 1. FIG. Therefore, description of these steps is omitted.

In the electrospinning step S22, the layer 21 including the bonded nanofibers 22 is formed on one surface of the base material layer 10 using a polymer solution in which the raw materials of the bonded nanofibers 22 are dissolved by an electrospinning method. After the formation of the layer 21 including the nanofibers 22, the inorganic particles 26 are included in the layer 21 including the bonded nanofibers 22, and the layer 21 including the bonded nanofibers 22 is referred to as “the nanofiber layer 20 including the bonded nanofibers 22 and the inorganic particles 26. '
In the third embodiment, the nanofiber layer 20 is formed using the electrospinning device 124 described above.

  According to the separator manufacturing apparatus 104 according to the third embodiment, since the electrospinning device 124 and the bonding device 130 are provided as described above, the separator 1 can be manufactured.

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

[Embodiment 4]
FIG. 11 is a diagram for explaining the separator 2 according to the fourth embodiment. 11A is a perspective view of the separator 2 wound around a core material (not shown), FIG. 11B is an enlarged cross-sectional view of the separator 2, and FIG. It is a schematic diagram which expands further and shows the range shown by B of FIG.11 (b).

  The separator 2 according to Embodiment 4 basically has the same configuration as that of the separator 1 according to Embodiment 1, but the configuration of the nanofiber layer is different from that of the separator 1 according to Embodiment 1. That is, in the separator 2 according to Embodiment 4, as shown in FIG. 11, the nanofiber layer 40 further includes high-melting nanofibers 46 made of a material having a melting point higher than the melting point of the resin having thermal bondability. . In FIG. 11C, reference numeral 42 indicates bonded nanofibers, reference numeral 44 indicates molten bonded nanofibers, and reference numeral 48 indicates inorganic particles. The bonded nanofiber 22, the molten bonded nanofiber 24, and the inorganic particles 26 have the same configuration.

  As the material of the high melting point nanofiber 46, various materials can be used as long as the material has a melting point higher than that of the resin having thermal bondability. For example, polyvinylidene fluoride (PVDF), polylactic acid (PLA) ), Polypropylene (PP), polyethylene (PE), polyvinyl acetate (PVAc), 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 glycolic acid (PLGA), silk, cellulose, chitosan and the like can be used.

  As described above, in the separator 2 according to the fourth embodiment, the configuration of the nanofiber layer is different from that of the separator 1 according to the first embodiment, but the base material layer 10 is similar to the case of the separator 1 according to the first embodiment. Since the nanofiber layer 40 and the nanofiber layer 40 are bonded by the bonded nanofiber 42, it is possible to prevent the base material layer and the nanofiber layer from being peeled off. It is possible to suppress peeling and damage.

  Moreover, according to the separator 2 which concerns on Embodiment 4, since the nanofiber layer 40 further contains the high melting point nanofiber 46 which consists of material which has melting | fusing point higher than melting | fusing point of the resin which has heat bondability, the structure of a nanofiber layer Can be prevented from being broken by heating.

  In addition, since the separator 2 which concerns on Embodiment 4 has the structure similar to the separator 1 which concerns on Embodiment 1 except the structure of a nanofiber layer, the effect applicable among the effects which the separator 1 which concerns on Embodiment 1 has as it is. Have.

[Embodiment 5]
FIG. 12 is a front view of the separator manufacturing apparatus 106 according to the fifth embodiment.
FIG. 13 is a flowchart of the separator manufacturing method according to the fifth embodiment.

  In the fifth 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 106 according to the fifth embodiment has basically the same configuration as the separator manufacturing apparatus 102 according to the second embodiment, but the position of the inorganic particle containing apparatus and the joining apparatus is 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. 12, 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 fifth embodiment, the bonding device 130 is a device that bonds the base material layer 10 and the layer 21 including the bonding nanofibers 22 with the bonding nanofibers 22, and the inorganic particle containing device 140 is a bonding nanofiber. In this apparatus, inorganic particles are further included in the layer including the fibers 22, and the layer including the bonded nanofibers 22 is the “nanofiber layer 20 including the bonded nanofibers 22 and the inorganic particles 26”. In the fifth embodiment, the bonding apparatus 130 includes a thermal bonding apparatus that performs thermocompression bonding in a state where the base material layer 10 and the layer 21 including bonded nanofibers are stacked.

  The separator manufacturing method according to the fifth 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. 13, the separator manufacturing method according to Embodiment 5 includes a base material layer preparation step S31, an electrospinning step S32, a joining step S33, and an inorganic particle inclusion S34 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 electrospinning step S32 is the same step as the electrospinning step S12 in the second embodiment. Therefore, description of these steps is omitted.
The separator manufacturing method according to Embodiment 5 is performed using the separator manufacturing apparatus 106 described above.

The joining step S33 is a step of joining the base material layer 10 and the layer 21 containing the joined nanofibers with the joined nanofibers 22. The joining step S33 is a thermal joining step in which thermocompression bonding is performed in a state where the base material layer 10 and the layer 21 containing joined nanofibers are laminated, and at least a part of the joined nanofibers 22 is heated by the thermal joining step. The base material layer 10 and the layer 21 containing the bonded nanofibers are melted and bonded with the bonded nanofibers 22.
The joining step S33 is performed using the joining device 130 described above.
In the inorganic particle inclusion step S34, the layer including the bonded nanofibers 22 further includes the inorganic particles 26, and the layer including the bonded nanofibers 22 is referred to as “the nanofiber layer 20 including the bonded nanofibers 22 and the inorganic particles 26”. It is a process.
The inorganic particle containing step S34 is performed using the inorganic particle containing device 140 described above.

  According to the separator manufacturing apparatus 106 according to the fifth embodiment, as described above, since the electrospinning apparatus 122, the bonding 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 the fifth embodiment, as described above, since the base layer preparation step S31, the electrospinning step S32, the joining step S33, and the inorganic particle inclusion step S34 are 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 and the nanofiber layer 20 as an example, but the present invention is not limited to this. For example, it is good also as a separator further provided with components (reinforcing member etc.) other than a base material layer and a nanofiber layer.

(3) Although the separator 1 which concerns on the said Embodiments 1-3 shall be manufactured using the separator manufacturing apparatus which concerns on each of Embodiment 1-3, 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 the electrospinning apparatus and the bonding apparatus are separate bodies. Thus, the separator of this invention can be manufactured using various separator manufacturing apparatuses.

(4) Although the separator 1 which concerns on the said Embodiments 1-3 shall be manufactured with the separator manufacturing method which concerns on each of Embodiment 1-3, 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 a step of manufacturing a base material layer and an electrospinning step 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 of the first to third embodiments is performed using the separator manufacturing apparatus according to each of the first to third embodiments, 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 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) In Embodiment 3 described above, the nanostructure has a mechanism for forming the layer 21 including the bonded nanofibers 22 on one surface of the base material layer 10, and the bonded nanostructures are formed after the formation of the layer 21 including the bonded nanofibers 22. An electrospinning device 124 having a mechanism in which inorganic particles 26 are included in the layer 21 including the fibers 22 and the layer 21 including the bonded nanofibers 22 is “a nanofiber layer 20 ′ including the bonded nanofibers 22 and the inorganic particles 26”. Although used, the present invention is not limited to this. The base material layer has a mechanism for forming a layer containing bonded nanofibers on one surface, and the inorganic nanoparticle is included in the layer including bonded nanofibers during the formation of the layer including bonded nanofibers. An electrospinning apparatus having a mechanism that makes a layer containing a “nanofiber layer containing bonded nanofibers and inorganic particles” may be used. As such an electrospinning device, for example, an electrospinning device in which an inorganic particle-containing device is disposed between nozzles in a plurality of nozzles, or an electric field in which an inorganic particle-containing device is disposed on the side surface side of a nozzle unit. A spinning device or the like can be used.

(7) In the case of (6) above, a layer containing bonded nanofibers on one surface of the substrate layer using a polymer solution in which the raw materials of bonded nanofibers are dissolved by electrospinning as the electrospinning process And forming the layer including the bonded nanofibers during the formation of the layer including the bonded nanofibers, and the layer including the bonded nanofibers is referred to as “nanofiber layer including the bonded nanofibers and the inorganic particles”. A separator can be obtained by performing the electrospinning process.

(8) In each of the embodiments described above, bonded nanofibers made of a resin having thermal bondability are used, and the base material layer and the nanofiber layer are bonded by bonded nanofibers that are at least partially melted by heat. Although the present invention has been described by taking a separator as an example, the separator of the present invention is not limited to this. FIG. 14 is a flowchart of a separator manufacturing method according to a modification. For example, a separator in which bonded nanofibers made of a resin that is soluble in a predetermined solvent are used, and at least a part of the base material layer and the nanofiber layer are bonded by bonded nanofibers dissolved in a predetermined solvent. It is good. For example, as shown in FIG. 14, such a separator is formed by immersing the nanofiber laminate in a solvent having appropriate solubility with respect to the bonded nanofibers, or through the nanofiber laminate in the vapor of the solvent. It can manufacture by performing the process (joining process (dissolution joining process) S43) which joins and a nanofiber layer. By setting it as such a structure, it becomes possible to join a base material layer and a nanofiber layer easily using a predetermined solvent.

(9) In the case of the above (8), the nanofiber layer is made of a material having a low solubility made of a material having lower solubility in a predetermined solvent than a resin having solubility in the predetermined solvent. It is preferable that a fiber is further included. By setting it as such a structure, it becomes possible to suppress that the structure of the nanofiber layer whose fiber average diameter and space | gap are fine is broken with a solvent.

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

(11) In the second, third, and fifth embodiments, the inorganic particle 26 is sprayed to make the layer including the bonded nanofibers “the nanofiber layer including the bonded nanofibers and the inorganic particles”. It is not limited to this. For example, a layer containing bonded nanofibers may be defined as a “nanofiber layer including bonded nanofibers and inorganic particles” by applying a solution containing inorganic particles.

DESCRIPTION OF SYMBOLS 1 ... Separator, 10 ... Base material layer, 12 ... Base fiber, 20, 40 ... Nanofiber layer (after joining process), 20 '... Nanofiber layer (before joining process), 21 ... Joining nanofiber Layer, 22, 42 ... bonded nanofiber, 24,44 ... melted bonded nanofiber, 26,48 ... inorganic particles, 30 ... nanofiber laminate, 100,102,104 ... separator manufacturing device, 110 ... conveying device, 111 DESCRIPTION OF SYMBOLS ... Feeding roller, 112 ... Winding roller, 113, 118 ... Tension roller, 114 ... Auxiliary roller, 120, 122, 124 ... Electrospinning device, 130 ... Joining device, 140, 142 ... Inorganic particle containing device, 200 ... Housing Body 210... Nozzle unit 220 220 upward nozzle 250 collector 252 insulating member 260 power supply 270 auxiliary belt device 27 ... auxiliary belt, 274 ... auxiliary belt rollers

Claims (21)

A base material layer;
Having `` joining nanofibers used for joining with the base material layer '' and nanofiber layers containing inorganic particles,
The said base material layer and the said nanofiber layer are joined by the said joint nanofiber, The separator characterized by the above-mentioned. The separator according to claim 1, wherein
The bonded nanofiber is made of a resin having thermal bondability,
The separator is characterized in that the base material layer and the nanofiber layer are bonded by bonded nanofibers at least partially melted by heat. The separator according to claim 2,
The separator having a melting point of the heat-bonding resin is lower than the melting point of the material constituting the base material layer. The separator according to claim 3,
The melting point of the resin having the thermal bondability is 10 ° C. or more lower than the melting point of the material constituting the base material layer. In the separator in any one of Claims 2-4,
The bonded nanofibers have an average diameter in the range of 50 nm to 1000 nm. In the separator according to any one of claims 2 to 5,
The nanofiber layer further includes a high-melting-point nanofiber made of a material having a melting point higher than that of the resin having thermal bondability. The separator according to claim 1, wherein
The bonding nanofiber is made of a resin having solubility in a predetermined solvent,
The separator is characterized in that the base material layer and the nanofiber layer are bonded at least partially by bonded nanofibers dissolved in the predetermined solvent. The separator according to claim 7,
The nanofiber layer further includes a low-solubility nanofiber made of a material having lower solubility in the predetermined solvent than a resin having solubility in the predetermined solvent. In the separator according to any one of claims 1 to 8,
The bonded nanofiber is obtained by an electrospinning method. In the separator according to any one of claims 1 to 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. By using a mixed polymer solution in which inorganic particles are mixed with a polymer solution in which raw materials for bonded nanofibers are dissolved by an electrospinning method, on one surface of the base material layer, “nanofibers including the bonded nanofibers and the inorganic particles” An electrospinning apparatus having a mechanism for forming a layer;
A separator manufacturing apparatus comprising: a bonding device that bonds the base material layer and the nanofiber layer with the bonded nanofibers. The electrospinning method has a mechanism for forming a layer including the bonding nanofibers on one surface of the base material layer using a polymer solution in which the raw materials of the bonding nanofibers are dissolved, and includes the bonding nanofibers. An electric field having a mechanism in which inorganic particles are included in the layer including the bonded nanofibers during or after the formation of the layer, and the layer including the bonded nanofibers is referred to as “the nanofiber layer including the bonded nanofibers and the inorganic particles”. A spinning device;
A separator manufacturing apparatus comprising: a bonding device that bonds the base material layer and the nanofiber layer with the bonded nanofibers. An electrospinning apparatus having a mechanism for forming a layer containing the bonded nanofibers on one surface of the base layer using a polymer solution in which the raw materials of the bonded nanofibers are dissolved by an electrospinning method;
Inorganic particle inclusion apparatus having a mechanism that further includes inorganic particles in the layer including the bonded nanofibers, and the layer including the bonded nanofibers is referred to as “the nanofiber layer including the bonded nanofibers and the inorganic particles”.
A separator manufacturing apparatus comprising: a bonding device that bonds the base material layer and the nanofiber layer with the bonded nanofibers. An electrospinning apparatus having a mechanism for forming a layer containing the bonded nanofibers on one surface of the base layer using a polymer solution in which the raw materials of the bonded nanofibers are dissolved by an electrospinning method;
A bonding apparatus for bonding the base layer and the layer containing the bonded nanofibers by the bonded nanofibers;
An inorganic particle-containing device having a mechanism in which inorganic particles are further included in the layer including the bonded nanofibers, and the layer including the bonded nanofibers is the “nanofiber layer including the bonded nanofibers and the inorganic particles”. A separator manufacturing apparatus comprising: In the separator manufacturing apparatus in any one of Claims 12-15,
The said joining apparatus consists of a thermal joining apparatus thermocompression-bonded in the state which laminated | stacked the said base material layer and the layer containing the said nanofiber layer or the said joining nanofiber, The separator manufacturing apparatus characterized by the above-mentioned. A base material layer preparation step of preparing a base material layer;
By using a mixed polymer solution in which inorganic particles are mixed with a polymer solution in which the raw materials of bonded nanofibers are dissolved by electrospinning, the surface of the base layer is formed with “nanoparticles including the bonded nanofibers and inorganic particles”. An electrospinning process to form a fiber layer;
The separator manufacturing method characterized by including the joining process which joins the said base material layer and the said nanofiber layer with the said joining nanofiber in this order. A base material layer preparation step of preparing a base material layer;
Using electrospinning method, a layer containing the bonded nanofibers is formed on one surface of the base material layer using a polymer solution in which the raw materials of the bonded nanofibers are dissolved, and the layer including the bonded nanofibers is formed. An electrospinning step in which inorganic particles are included in the layer containing the bonded nanofibers during or after formation, and the layer including the bonded nanofibers is the “nanofiber layer including the nanofibers and the inorganic particles”;
The separator manufacturing method characterized by including the joining process which joins the said base material layer and the said nanofiber layer with the said joining nanofiber in this order. A base material layer preparation step of preparing a base material layer;
An electrospinning process in which a layer containing the bonded nanofibers is formed on one surface of the base material layer using a polymer solution in which the raw materials of bonded nanofibers are dissolved by an electrospinning method;
Inorganic particle inclusion step in which inorganic particles are further included in the layer including the bonded nanofibers, and the layer including the bonded nanofibers is the “nanofiber layer including the bonded nanofibers and the inorganic particles”;
The separator manufacturing method characterized by including the joining process which joins the said base material layer and the said nanofiber layer with the said joining nanofiber in this order. A base material layer preparation step of preparing a base material layer;
An electrospinning process in which a layer containing the bonded nanofibers is formed on one surface of the base material layer using a polymer solution in which the raw materials of bonded nanofibers are dissolved by an electrospinning method;
A bonding step of bonding the base layer and the layer containing the bonded nanofibers by the bonded nanofibers;
Inorganic particle-containing step in which inorganic particles are further included in the layer including the bonded nanofibers, and the layer including the bonded nanofibers is the “nanofiber layer including the bonded nanofibers and the inorganic particles” in this order. The separator manufacturing method characterized by including. 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 and the nanofiber layer or the layer including the bonding nanofibers are laminated, and at least the bonding nanofibers are formed by the heat bonding step. A method for producing a separator, wherein a part of the substrate layer is melted with heat to bond the base layer and the nanofiber layer or the layer containing the bonded nanofibers with the bonded nanofibers.

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