KR101585935B1 - Apparatus of heat treatment of microporous membrane - Google Patents

Abstract

We propose an apparatus for heat treatment of microporous membranes with low shrinkage and high porosity by using infrared ray and uniformly forming pores in the thickness direction and machine direction. The apparatus includes an infrared ray generating unit for generating infrared rays and a normal temperature roll having a heat absorbing layer formed on a surface thereof which is spatially separated from the infrared ray generating unit and brought into contact with the microporous membrane.

Description

[0001] Apparatus for heat treatment of microporous membrane [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an apparatus for manufacturing a microporous film, and more particularly, to a device for a heat treatment for forming pores in a microporous film by using infrared rays.

Microporous membranes are used for precise filtration membranes, separators for batteries, separators for capacitors, and the like. Among them, when used as a separator for a lithium ion battery, generally required characteristics such as mechanical strength and electrolyte permeability should be good. The battery separator is manufactured through a heat treatment process so as to have a low shrinkage ratio and a high porosity. Heat treatment is carried out by irradiation with hot air, hot air, low-humidity air, infrared rays, electron beams, and the like. Recently, however, the use of infrared rays is increasing. When the infrared ray is irradiated on the porous film and subjected to heat treatment, crystallization occurs in the separation film, and pores are formed when the film is stretched. Accordingly, a device for performing a heat treatment is very important in order to manufacture a separation membrane which has uniformity, high porosity and does not shrink easily.

On the other hand, it is preferable that the pores are uniformly formed in the thickness direction and the machine direction of the microporous membrane. Japanese Laid-Open Patent Application No. 2012-0091028 discloses a method of applying infrared rays or the like for drying a microporous membrane. However, the above patent does not specifically disclose a process in which heat generated from infrared rays acts on a microporous membrane to form pores, and a method of uniformly forming pores of the microporous membrane in the thickness direction and the machine direction. Accordingly, there is a demand for a heat treatment apparatus and a heat treatment method therefor that use a infrared ray to make a microporous film have a low shrinkage ratio and a high porosity.

SUMMARY OF THE INVENTION An object of the present invention is to provide an apparatus for heat treatment of a microporous membrane having a low shrinkage ratio and a high porosity by using infrared rays and uniformly forming pores in a thickness direction and a machine direction.

An apparatus for heat treatment of a microporous membrane for solving the problems of the present invention includes an infrared ray generating unit for generating infrared rays and a normal temperature roll having a heat absorbing layer formed on a surface thereof which is spatially separated from the infrared ray generating unit and is in contact with the microporous membrane .

In the apparatus of the present invention, the infrared ray generator may generate an infrared ray surface light source. The thickness of the heat absorbing layer is preferably 100 占 퐉 to 10,000 占 퐉. The heat absorbing layer may be made of a rubber material to which a heat absorbing material is added.

In the heat absorbing layer of the present invention, the rubber material may be at least one selected from the group consisting of fluorine rubber including Teflon, acrylic rubber, polyurethane rubber, polyamide rubber, natural rubber, polyisobutylene rubber, polyisoprene rubber, chloroprene rubber, butyl rubber, Butadiene-styrene rubber, styrene-isoprene-styrene rubber, styrene-ethylene-butadiene rubber, styrene-ethylene-butylene-styrene rubber, styrene-isoprene-propylene-styrene rubber, silicone rubber, And a chlorosulfonated polyethylene rubber, or a mixture thereof.

Substance to absorb the heat the metal nanoparticles, including gold, carbon black, iron _{black, VO 2, Ti 2 O 3} , NbO 2, SnO, Sb 2 O 3, Sb 2 O 4, Sb 2 O 5, NiS, CuF _{2, CuFOH, Cu (OH)} 2, Cu 3 (PO 4) 2 and _{2H 2 O, Cu 3 (PO} 4) 2, Cu 2 PO 4 (OH), Cu 3 (PO 4) 2 and Cu (OH) _{2, Cu 3 (PO 4)} (OH) 3, Cu 5 (PO 4) 3 (OH) 4, CuAl 6 (PO 4) 4 (OH) 8 and _{5H 2 O, Cu 2 P 2} O 7 and 3H ₂ O, Cu ₂ P ₂ O ₇ , Cu ₃ (P ₃ O ₉ ) ₂ , FeF ₂揃 4H ₂ O, FeF ₂ , Fe ₃ (PO ₄ ) ₂揃 8H ₂ O, LiFePO ₄ , NaFePO ₄ , Fe ₂ SiO ₄ , Fe _x Mg _{2 - x} SiO ₄ , FeCO ₃ , Ni ₃ (PO ₄ ) ₂ .8H ₂ O, TiP ₃ O ₉ . A perovskite structure in the form of Ca ₂ Fe (PO ₄ ) ₂ .4H ₂ O, MgFePO ₄ F, YbPO ₄ and A _x M _y O ₃ (where A is any one selected from metals and M is any one selected from transition metals , O is oxygen, and x and y are 0 <x? 1, 0 <y? 1).

The heat absorbing material may be selected from the group consisting of a borate salt mixture, a carbonate mixture, an alumina mixture, a nitrate mixture, a nitrite mixture, lithium borate and sodium borate, potassium borate, magnesium borate, calcium borate, strontium borate, barium borate, sodium borate, colemanite), lithium carbonate, sodium carbonate, can be at least one selected among potassium carbonate, calcium carbonate, calcite, CaCO _3, dolomite and magnesite (magnesite), material for absorbing the heat is nickel dithiol, dithiol metal complex compound, Based polymer, a cyanine-based polymer, a cyanide-based polymer, a cyanide-based polymer, a zirconium-based polymer, a croconium-based polymer, a diimmonium- Propylene-based dyes.

In the preferred apparatus of the present invention, a thermally conductive layer may further be provided between the normal temperature roll and the heat absorbing layer. The thermally conductive layer may include any one selected from gold, silver, copper, aluminum, and nickel, or an alloy thereof. The thickness of the heat conduction layer is preferably 100 m to 1,000 m.

According to the apparatus for heat treatment of the microporous membrane of the present invention, by using the normal temperature roll formed with the heat absorbing layer for allowing the heat to permeate through the porous membrane, it is possible to use the infrared ray to have a low shrinkage ratio and a high porosity, A microporous membrane having uniform pores is formed. Further, by adding a heat conductive layer between the heat absorbing layer and the normal temperature roll, the heat distribution in the porous film can be more uniform.

1 is a schematic view of a heat treatment apparatus for a microporous membrane according to the present invention.
FIG. 2 is a view for conceptually explaining the heat transfer path by the heat treatment apparatus according to the present invention.
3A is an electron micrograph of a microporous membrane produced by a conventional heat treatment apparatus without a heat absorbing layer.
3B is an electron micrograph of a microporous membrane produced by the heat treatment apparatus of the present invention having a heat absorbing layer.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

The embodiment of the present invention utilizes a normal temperature roll having a heat absorbing layer for inducing heat to be transmitted through the porous membrane by infrared rays, thereby achieving uniformity of pores in the thickness direction and the machine direction with low shrinkage ratio and high porosity An apparatus for heat treatment of microporous membranes is presented. For this purpose, the structure of the roll at room temperature capable of transmitting heat will be described in detail, and the characteristics of the microporous film thus obtained will be described in detail. Here, heat transmission means that heat passes through the thickness direction of the microporous membrane without being affected by scattering or reflection. When heat is scattered and reflected, heat loss to the outside becomes large, and heat is not evenly distributed throughout the porous film, so crystallization of the porous film does not occur uniformly. In the embodiment of the present invention, heat transmission is a main factor for crystallization of the microporous membrane of the present invention, and this will be apparent within the scope of the present invention.

1 is a view schematically showing an apparatus for heat treating a microporous film according to an embodiment of the present invention. Of course, additional devices for operating the heat treatment apparatus may be variously installed within the scope of the present invention. For convenience of explanation, the microporous membrane 30 before the heat treatment is the pre-crystallization microporous membrane 30, and the microporous membrane 31 after the heat treatment is divided into the crystallized microporous membrane 31. The crystallized microporous membrane 30 is subsequently subjected to a drawing process or the like to form pores. The microporous membrane 30 can be expressed collectively as a pre-crystallization microporous membrane 30 and a crystallized microporous membrane 31. When the heat is directed to the center of the normal temperature roll 10, it is defined as the thickness direction, and when it is directed to the rotating direction of the normal temperature roll 10, it is defined as the machine direction.

Referring to FIG. 1, the thermal processing apparatus of the present invention includes an infrared ray generator 40 and a room temperature roll 10 spatially separated by a predetermined interval. The pre-crystallization microporous film 30 is supplied from the supply roll 20 and heat-treated on the room temperature roll 10, and the crystallized microporous film 31 is wound by the winding roll 22. [ The crystallized microporous membrane 31 will be formed into fine pores inside the membrane after the drawing step, the heat fixing step, and the like, and is used for a filtration membrane, a separator for a battery, a separator for a condenser, and the like. The infrared ray corresponds to a wavelength band of 700 nm to 2500 nm, and particularly preferably a wavelength band corresponding to a band of 800 nm to 1500 nm.

The heat generated by the light energy is transmitted directly to the microporous membrane 30 instead of the thermal flow system. The infrared ray generator 40 may take various forms, but an infrared ray heater equipped with a lamp (not shown) for generating infrared rays is preferable. The infrared rays of the infrared ray generator 40 adjust the arrangement of the lamps so that the heat is uniformly irradiated to the microporous film 30 across the machine direction. The distribution of heat in the machine direction can be more precisely controlled by the infrared ray generator 40.

The room temperature roll 10 is preferably in the form of a cylinder, and the heat absorbing layer 16 according to the embodiment of the present invention is formed around the roll. The temperature of the normal-temperature roll 10 is preferably maintained at a temperature of 100 ° C to 150 ° C, and the fruit passage 12 can be fed with the fruit. The normal temperature roll 10 may be made of a metal such as stainless steel which is resistant to thermal shock and corrosion. The microporous membrane 30 moves while contacting the heat absorbing layer 16 of the normal temperature roll 10. In the course of the heat treatment of the microporous membrane 30, it is preferable that the normal-temperature roll 10 be rotated in the direction in which the microporous membrane 30 is conveyed. When the microporous membrane 30 is subjected to heat treatment, crystallization occurs inside. It is preferable that the crystallization is a form in which the orientation of crystallization is not constant, that is, no orientation. The microporous film 31 crystallized in the non-oriented state according to the embodiment of the present invention forms pores in the region between the crystals after the drawing step, the heat fixing step, and the like. The amorphous part between crystals has a relatively weak bonding force.

Generally, the crystallized microporous membrane 31 has molecules arranged in the machine direction. If the crystallized microporous membrane 31 is exposed to heat for a certain period of time, the molecules of the microporous membrane 31 crystallized by the residual stress tend to return to the opposite direction of the machine direction, resulting in heat shrinkage. As in the embodiment of the present invention, when the microporous membrane 31 crystallized in the orientation by the heat treatment is formed, the residual stress of the arranged molecules can be removed and the heat shrinkage can be prevented. This is because the orientation of the crystals is anisotropic and the residual stress is not localized in a particular direction.

The heat treatment region (a) is a place where the microporous membrane (30) is heat-treated by the infrared rays irradiated from the infrared ray generator (40) and occupies a part of the normal temperature roll (10). The heat treatment region (a) is a portion that allows the heat treatment of the microporous membrane 30 to occur sufficiently within the scope of the present invention. The heat treatment zone a is set in advance in consideration of the moving speed of the microporous membrane 30, the size of the room temperature roll 10, the infrared intensity, the distance between the infrared ray generator 40 and the room temperature roll 10, . The infrared ray generator 40 may include at least one infrared ray heater, and may form a planar light source as the case may be. In order to ensure the uniformity of the heat treatment, the infrared ray generator 40 can maintain uniform spacing from the normal temperature rolls 10 throughout.

The heat absorbing layer 16 is made of a material which is easily contacted with the microporous membrane 30 and which absorbs heat well. The heat absorbing layer 16 according to the embodiment of the present invention is preferably a rubber material to which a heat absorbing material is added. Since the rubber material has predetermined tackiness, the microporous membrane 30 easily contacts the heat absorbing layer 16. It is possible to prevent the microporous membrane 30 from being disturbed by the environment outside the room temperature roll 10 when the microporous membrane 30 comes into contact with the heat absorbing layer 16 having adhesiveness. Here, the disturbance refers to a phenomenon in which the microporous membrane 30 is shaken by the flow of the fluid around the normal-temperature roll 10 or the microporous membrane 30 is pulled by the supply roll 20.

The rubber material may be at least one selected from the group consisting of fluorine rubber including Teflon, acrylic rubber, polyurethane rubber, polyamide rubber, natural rubber, polyisobutylene rubber, polyisoprene rubber, chloroprene rubber, butyl rubber, nitrile butyl rubber, styrene- Styrene-isoprene-butadiene rubber, styrene-isoprene-propylene-styrene rubber, silicone rubber, and chlorosulfonated polyethylene rubber, which are selected from the group consisting of styrene-butadiene-styrene rubber, styrene-isoprene-styrene rubber, styrene- One or a mixture thereof.

The heat absorbing material serves to absorb heat in the microporous membrane 30. The material may be selected from the group consisting of metal nanoparticles including gold, carbon black, iron oxide, VO ₂ , Ti ₂ O ₃ , NbO ₂ , SnO, Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₅ , NiS, CuF ₂ , CuFOH, _{Cu (OH) 2, Cu 3} (PO 4) 2 and _{2H 2 O, Cu 3 (PO} 4) 2, Cu 2 PO 4 (OH), Cu 3 (PO 4) 2 and Cu (OH) _2, Cu _{3 (PO 4) (OH) 3} , Cu 5 (PO 4) 3 (OH) 4, CuAl 6 (PO 4) 4 (OH) 8 and _{5H 2 O, Cu 2 P 2} O 7 and 3H ₂ O, Cu _{2 P 2 O 7, Cu 3 (} P 3 O 9) 2, FeF 2 and _{4H 2 O, FeF 2, Fe} 3 (PO 4) 2 and _{8H 2 O, LiFePO 4, NaFePO} 4, Fe 2 SiO 4, Fe x _{Mg 2 -xSiO 4, FeCO 3,} Ni 3 (PO 4) 2 and _{8H 2 O, TiP 3 O 9} . A perovskite structure in the form of Ca ₂ Fe (PO ₄ ) ₂ .4H ₂ O, MgFePO ₄ F, YbPO ₄ and A _x M _y O ₃ (where A is any one selected from metals and M is any one selected from transition metals , O is oxygen, and x and y are 0 <x? 1, 0 <y? 1).

The heat absorbing substance may also be selected from the group consisting of a borate salt mixture, a carbonate mixture, an alumina mixture, a nitrate mixture, a nitrite mixture, lithium borate and sodium borate, potassium borate, magnesium borate, calcium borate, strontium borate, barium borate, and may be at least one selected from colemanite, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, calcite, CaCO ₃ , dolomite and magnesite. Further, the material may be at least one selected from the group consisting of a nickel dithiol system, a dithiol-based metal complex compound, a cyanine system, a squarite system, a croconium system, a diimonium system, an aminium system, an ammonium system, a phthalocyanine system, a naphthalocyanine system and an aminium system, , Naphthoquinone type, polymer condensation azo type pyrrole, polymethine type, and propylene type.

The heat absorbing layer 16 absorbs the heat generated by the infrared rays introduced into the microporous membrane 30 while the microporous membrane 30 is in contact. The heat treatment of the microporous membrane 30 according to the embodiment of the present invention is performed under the condition that the infrared rays are uniformly irradiated in the machine direction. Since the heat due to the infrared rays uniformly irradiated is absorbed by the heat absorbing layer 16, the heat treatment of the microporous membrane 30 can occur uniformly in the thickness direction and the machine direction. The heat absorbing layer 16 may be formed by attaching a film containing the heat absorbing material to the normal temperature roll 10 or by applying a mixture of the material and the binder to the normal temperature roll 10. The thickness of the heat absorbing layer 16 can be adjusted in consideration of the thermal conductivity of the rubber material, heat absorption of the heat absorbing material, and the like.

On the other hand, it is most preferable that the heat treatment using the infrared ray proceeds with the microporous membrane 30 being separated from the normal temperature roll 10 by a predetermined distance. However, if the microporous membrane 30 is separated from the normal-temperature roll 10, the microporous membrane 30 may be stretched and deformed. The microporous film 30 spaced apart from the normal temperature roll 10 may be stretched by the tension of the supply roll 20 and the winding roll 22 or may be stretched due to the flow of the fluid around the microporous film 30 The sclera 30 may be shaken. The embodiment of the present invention solves the above problem by using the heat absorbing layer 16. When the heat absorbing layer 16 is placed, the effect of making the microporous membrane 30 spatially separated from the normal temperature roll 10 by the thickness of the heat absorbing layer 16 is obtained.

In the embodiment of the present invention, the thickness of the heat absorbing layer 16 is preferably 100 占 퐉 to 10,000 占 퐉. If the thickness of the heat absorbing layer 16 is smaller than 100 mu m, the effect of causing the microporous membrane 30 to be detached from the normal temperature roll 10 is insignificant. If the thickness is larger than 10,000 m, the cost of forming the heat absorbing layer 16 increases and it is thicker than necessary to realize the desired properties in the present invention. If the thickness is too large, it takes a long time to transfer the heat absorbed by the heat absorbing layer 16, which hinders absorption of the heat of the microporous membrane 30 uniformly.

Alternatively, the embodiment of the present invention may further form the heat conduction layer 14 between the heat absorbing layer 16 and the room temperature roll 10. [ The thermally conductive layer 14 provides a path through which the heat absorbed by the heat absorbing layer 16 can easily escape to the normal temperature roll 10. The heat conduction layer 14 allows the heat to be more effectively transferred in the thickness direction and the machine direction. The heat conduction layer 14 allows the absorbed heat to diffuse and distribute uniformly, so that the heat is easily transferred to the room temperature roll 10. The thermally conductive layer 14 prevents the localized regions of the normal-temperature rolls and the heat-absorbing layer from being heated, thereby helping to uniformly transfer the heat. The heat conduction layer 14 is preferably made of a metal material having a good thermal conductivity, and may be attached in a film form or formed through deposition or the like.

The heat conduction layer 14 may be made of any one selected from metals such as gold, silver, copper, aluminum, and nickel, an alloy of the metal, or a material in which an insulating binder is mixed with the metal and the alloy. The binder may be any one or a combination of silicon polymer, epoxy, polyimide, polyethylene, polypropylene, polyphenylene oxide, polysulfone, silicon dioxide, aluminum oxide, zirconia and other metal oxides. The thickness of the heat conduction layer 14 is preferably 100 占 퐉 to 1,000 占 퐉. If the thickness of the heat conduction layer 14 is less than 100 mu m, the heat conduction effect does not occur properly. If the thickness is larger than 1,000 占 퐉, the cost of forming the thermally conductive layer 14 is excessively increased and is thicker than necessary to realize the desired properties in the present invention.

FIG. 2 is a view for conceptually explaining the heat transfer path by the heat treatment apparatus according to the embodiment of the present invention. At this time, the heat transfer path represents only the main transfer path, and the auxiliary path that may actually occur is omitted for convenience of explanation.

2, the infrared rays injected into the microporous membrane 30 are converted into heat and then absorbed by the heat absorbing layer 16. Since the heat absorbing layer 16 absorbs the heat, the heat does not remain in the microporous membrane 30. Specifically, the heat absorbing layer 16 uniformly distributes the heat across the microporous membrane 30 so that the heat is not scattered or reflected by the microporous membrane 30. When the heat absorbing layer 16 is present, the temperature gradient between the infrared ray generating part 40 and the room temperature roll 10 becomes constant, and the heat is uniformly supplied to the microporous membrane 30. When the temperature gradient becomes constant, the thermal history deviation in the thickness direction of the microporous membrane 30 is reduced. The deviation of the physical properties such as the strength, heat shrinkage, porosity and crystallinity of the microporous membrane 30 disappears due to the reduced thermal history deviation. By adding the heat conduction layer 14 thereto, the distribution of heat becomes more homogeneous and a more stable heat treatment can be performed.

If there is no heat absorbing layer 16, the heat is concentrated on the surface of the microporous membrane 30 or reflected by the normal temperature roll 10 and is distributed unevenly. In this case, the temperature gradients of the infrared ray generator 40 and the room temperature roll 10 become irregular, and thermal history deviations occur along the thickness direction of the microporous membrane 30. [ As a specific example, the surface portion or the specific portion of the microporous film 30 has a relatively large amount of crystallization so that pores are formed well, but the microporous film 30 near the normal temperature roll 10 is not crystallized properly, This does not happen properly. In the conventional heat treatment method, variations in the physical properties such as the strength, heat shrinkage, porosity and crystallinity of the microporous membrane 30 are caused by the thermal history deviation.

FIG. 3A is a photograph of a microporous membrane produced by a conventional heat treatment apparatus without a heat absorbing layer by an electron microscope, and FIG. 3B is a photograph of the microporous membrane produced by the heat treatment apparatus of the present invention having a heat absorbing layer by an electron microscope It is a photo enlarged 20,000 times. At this time, the heat treatment apparatus by reference to Figure 2 to Figure 1 b. In the heat treatment, the distance between the infrared ray generator 40 and the microporous membrane 30 was 3 cm and the time was 5 seconds. After the heat treatment, the microporous membrane was stretched by 200%.

3A and 3B, the microporous membrane 31 produced by the conventional heat treatment apparatus without the heat absorbing layer has nonuniform pore formation. This is because the heat due to infrared rays is concentrated on the surface of the microporous membrane 30 or reflected by the rolls at room temperature and is distributed unevenly. Inhomogeneous pore is formed in the microporous membrane (30) by uneven thermal history deviation. Specifically, the microporous membrane 30 shows regions (b) where pores are not formed and regions (c) where pores are formed. The regions (b, c) confirm that the heat is not uniformly distributed in the microporous membrane 30 in the heat treatment. This uneven distribution of the heat causes irregularities in the arrangement of the pores in the region (c) where the pores are formed.

On the other hand, the microporous membrane 31 produced by the heat treatment apparatus of the present invention having the heat absorbing layer was uniformly formed with pores. This is because the temperature gradient between the infrared ray generator 40 and the room temperature roll 10 is constant and the heat is uniformly supplied to the microporous membrane 30. When the temperature gradient becomes constant, the thermal history deviation in the thickness direction of the microporous membrane 30 is reduced. Uniform pores are formed in the microporous membrane 30 by a uniform thermal history deviation. Specifically, the pores were uniform throughout the entire microporous membrane 30 and maintained a constant arrangement. The pore size was uniform and constant compared with the conventional one.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but many variations and modifications may be made without departing from the scope of the present invention. It is possible.

10; Room temperature roll 12; Fruit passage
14; A heat conduction layer 16; Heat absorbing layer
20; Feed roll 22; Winding roll
30; Microporous membrane 40; The infrared-

Claims (11)

An infrared ray generator for generating infrared rays; And
And a room temperature roll spaced apart from the infrared ray generator and having a heat absorbing layer formed on a surface contacting the microporous membrane. The apparatus of claim 1, wherein the infrared ray generator generates an infrared ray surface light source. The apparatus for heat treatment of a microporous membrane according to claim 1, wherein the heat absorbing layer is made of a rubber material to which a heat absorbing material is added. The rubber composition according to claim 3, wherein the rubber material is at least one selected from the group consisting of fluorine rubber including Teflon, acrylic rubber, polyurethane rubber, polyamide rubber, natural rubber, polyisobutylene rubber, polyisoprene rubber, chloroprene rubber, butyl rubber, Styrene-butadiene-styrene rubber, styrene-isoprene-styrene rubber, styrene-ethylene-butadiene rubber, styrene-ethylene-butylene-styrene rubber, styrene-isoprene- Wherein the polyolefin rubber is one selected from the group consisting of polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, and polyunsaturated polyethylene rubber. The method of claim 3, wherein the heat absorbing material is selected from the group consisting of metal nanoparticles including gold, carbon black, iron black, VO ₂ , Ti ₂ O ₃ , NbO ₂ , SnO, Sb ₂ O ₃ , Sb ₂ O ₄ , Sb _{2 O 5, NiS, CuF 2,} CuFOH, Cu (OH) 2, Cu 3 (PO 4) 2 and _{2H 2 O, Cu 3 (PO} 4) 2, Cu 2 PO 4 (OH), Cu 3 (PO 4) ₂ and _{Cu (OH) 2, Cu 3} (PO 4) (OH) 3, Cu 5 (PO 4) 3 (OH) 4, CuAl 6 (PO 4) 4 (OH) 8 and 5H ₂ O, Cu ₂ P ₂ O ₇ .3H ₂ O, Cu ₂ P ₂ O ₇ , Cu ₃ (P ₃ O ₉ ) ₂ , FeF ₂揃 4H ₂ O, FeF ₂ , Fe ₃ (PO ₄ ) ₂揃 8H ₂ O, LiFePO ₄ , _{NaFePO 4, Fe 2 SiO 4,} Fe x Mg 2 -xSiO 4, FeCO 3, Ni 3 (PO 4) 2 and _{8H 2 O, TiP 3 O 9} . A perovskite structure in the form of Ca ₂ Fe (PO ₄ ) ₂ .4H ₂ O, MgFePO ₄ F, YbPO ₄ and A _x M _y O ₃ (where A is any one selected from metals and M is any one selected from transition metals And O is oxygen, and x and y are at least one selected from the group consisting of 0 < x < 1 and 0 &lt; y &lt; 1. The method of claim 3 wherein the heat absorbing material is selected from the group consisting of a borate salt mixture, a carbonate mixture, an alumina mixture, a nitrate mixture, a nitrite mixture, lithium borate and sodium borate, potassium borate, magnesium borate, calcium borate, strontium borate, barium borate, Wherein the at least one selected from the group consisting of borate, colemanite, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, calcite, CaCO ₃ , dolomite and magnesite. 4. The method of claim 3, wherein the heat absorbing material is selected from the group consisting of nickel dithiol, dithiol-based metal complex compounds, cyanine, And at least one dye selected from the group consisting of aminium, anthraquinone, naphthoquinone, polymer condensation azo-based pyrrole, polymethine-based, and propylene-based dyes. The apparatus for heat treatment of a microporous membrane according to claim 1, wherein the thickness of the heat absorbing layer is 100 m to 10,000 m. The apparatus for heat treatment of a microporous membrane according to claim 1, further comprising a thermally conductive layer between the normal temperature roll and the heat absorbing layer. The apparatus of claim 9, wherein the thermally conductive layer comprises any one selected from the group consisting of gold, silver, copper, aluminum, and nickel, or an alloy thereof. The apparatus for heat-treating a microporous membrane according to claim 9, wherein the thickness of the thermally conductive layer is from 100 m to 1,000 m.

Images