WO2015080507A1 - Séparateur, son procédé de fabrication, et batterie l'utilisant - Google Patents

Séparateur, son procédé de fabrication, et batterie l'utilisant Download PDF

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Publication number
WO2015080507A1
WO2015080507A1 PCT/KR2014/011520 KR2014011520W WO2015080507A1 WO 2015080507 A1 WO2015080507 A1 WO 2015080507A1 KR 2014011520 W KR2014011520 W KR 2014011520W WO 2015080507 A1 WO2015080507 A1 WO 2015080507A1
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Prior art keywords
separator
solvent
plasticizer
extraction
porous
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PCT/KR2014/011520
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English (en)
Korean (ko)
Inventor
장정수
이상호
이정승
조재현
Original Assignee
삼성에스디아이 주식회사
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Publication of WO2015080507A1 publication Critical patent/WO2015080507A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a separator, a method for manufacturing the same, and a battery using the same.
  • a separator for an electrochemical cell refers to an interlayer membrane which maintains ionic conductivity while separating an anode and a cathode from each other in a cell, thereby allowing the battery to be charged and discharged.
  • separation membranes having excellent shape stability due to heat as well as physical properties such as strength and ventilation are required.
  • the dry method cannot control the pore size and the thickness of the membrane uniformly.However, in the wet method, the membrane is thin and uniformly controlled compared to the dry method by forming microcellular fish through the plasticizer extraction process after stretching the membrane. (Korean Patent Publication No. 10-2011-0116742). Since the plasticizer extraction process in the wet method corresponds to the bottle neck of the production rate of the membrane production process, the productivity of the membrane is determined according to the speed of the plasticizer extraction process. Efforts have been made to improve the productivity of porous membranes by the wet method as the use of the separator prepared by the wet method has been expanded. This caused a problem that the performance of the battery is reduced.
  • the problem to be solved by the present invention is to minimize the plasticizer residue in the membrane by adjusting the plasticizer extraction process of the wet method, improved air permeability, porosity, heat shrinkage, electrolyte wettability, strength, etc. of the separator prepared by the conventional wet method
  • the present invention provides a separator and a method of manufacturing the same.
  • Another problem to be solved by the present invention is to improve the performance of the battery including the separator and the shape stability of the battery through a separator having improved physical properties such as air permeability, porosity, heat shrinkage, electrolyte wetting, strength, etc. To provide.
  • the residual amount of the plasticizer in the separator according to the following formula 1 is 1.0% by weight or less based on the total weight of the membrane, the air permeability is 80 sec / 100 cc to 200 Provide a porous separator, sec / 100 cc.
  • Residual amount of plasticizer [(W1-W2) / W1] x 100
  • W1 represents the weight of the separator before the plasticizer is removed
  • W2 represents the weight of the separator after the plasticizer is removed
  • a polyolefin resin and a plasticizer are extruded to form a sheet, the sheet is stretched in a longitudinal direction (MD, machine direction) and / or transverse direction (TD, Transverse Direction), and a plurality of It is immersed in a solvent in the extraction tank, comprising extracting the plasticizer with a solvent, wherein the solvent is continuously supplied at a feed rate of 300 kg / h or more in the extraction tank, to provide a method for producing a porous membrane.
  • a separator comprising a porous heat-resistant layer formed on one side or both sides of the polyolefin resin described herein.
  • the polyolefin-based resin may be a separator described herein or a separator prepared by the method described herein.
  • the separator in the electrochemical cell including a positive electrode, a negative electrode, and an electrolyte, including a separator interposed between the positive electrode and the negative electrode, the separator is a separator according to one embodiment of the present invention To provide an electrochemical cell.
  • the separator according to the embodiments of the present invention in the preparation of the porous separator by the wet method, by minimizing the residual of the plasticizer in the separator, it is possible to prevent the degradation of the physical properties due to the plasticizer residue, thereby providing a separator having improved properties It has an effect.
  • the plasticizer extraction rate in the plasticizer extraction process by improving the plasticizer extraction rate in the plasticizer extraction process, by reducing the amount of plasticizer remaining in the membrane, the physical properties such as air permeability, uniformity of pores, heat shrinkage rate, electrolyte wetting, strength, etc. can be improved, Increasing the extraction process speed has an effect of providing a method for producing a membrane with improved productivity.
  • FIG. 1 is a process diagram schematically showing a plasticizer extraction process of the membrane manufacturing method according to an embodiment of the present invention.
  • Figure 2 is a process diagram schematically showing a plasticizer extraction process of the membrane manufacturing method according to another embodiment of the present invention.
  • FIG. 3 is a perspective view of the first extraction tank 202 of the plasticizer extraction process of FIG. 2, illustrating an example in which the solvent is re-introduced (arrow) by self-circulation of the solvent.
  • FIG. 4 is a perspective view of the first extraction tank 202 of the plasticizer extraction process of FIG. 2, and is another example showing that the solvent is reintroduced (arrow) by the self-circulation of the solvent.
  • a polyolefin-based resin and a plasticizer are extruded to form a sheet, and the sheet is stretched in a longitudinal direction (MD, machine direction) and / or in a transverse direction (TD). And it may include extracting the plasticizer.
  • a composition for forming a separator comprising a polyolefin resin and a plasticizer is injected into an extruder and extruded (extruded). At this time, the polyolefin resin and the plasticizer may be injected into the extruder simultaneously or sequentially.
  • the polyolefin resin may be composed of only one or more polyolefin resins, or may be a composition for forming a separator including one or more polyolefin resins, other resins and / or inorganic materials other than the polyolefin resin.
  • Non-limiting examples of the polyolefin resin include polyethylene (PE), polypropylene (PP) or poly-4-methyl-1-pentene (Poly-4-methyl-1-pentene, PMP) Can be. These may be used alone or in combination of two or more thereof, and polyolefin resin copolymers or mixtures thereof may be used.
  • Non-limiting examples of other resins except the polyolefin-based resins include polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polychlorotrifluoroethylene , PCTFE), polyoxymethylene (POM), polyvinyl fluoride (Polyvinyl fluoride, PVF), polyvinylidene fluoride (PVdF), polycarbonate (PC), polyarylate , PAR), polysulfone (PSF), polyetherimide (PEI), etc. These may be used alone or in combination of two or more thereof. Calcium carbonate, silica, barium sulfate or talc. These may be used alone or in combination of two or more thereof. have.
  • the kind of plasticizer is not particularly limited and may be any organic compound which forms a single phase with the polyolefin resin (or a mixture of polyolefin resin and other kinds of resin) at an extrusion temperature.
  • plasticizers include aliphatic or cyclic hydrocarbons such as nonan, decane, decalin, liquid paraffin (LP), liquid paraffin (or paraffin oil), paraffin wax, and the like.
  • liquid paraffin may be used in the plasticizer.
  • the liquid paraffin is harmless to the human body, has a high boiling point and little volatile components, thus making it easy to perform a membrane manufacturing process and forming uniform pores in the membrane.
  • the content of the polyolefin-based resin and the plasticizer may be appropriately adjusted according to the purpose of forming the sheet, and is not particularly limited.
  • the plasticizer may be present in an amount of about 30 wt% to about the composition for forming a separator. 80 wt%. When included in the content of the above range can not only facilitate the melting and extrusion of the polyolefin-based resin can impart appropriate porosity to the separator.
  • general additives for improving specific functions such as an oxidative stabilizer, a UV stabilizer, an antistatic agent, may be added to the composition for forming a separator according to a selection by those skilled in the art.
  • the composition for forming a separator is extruded, and then a solidified sheet is formed.
  • the polyolefin resin and the plasticizer are melt kneaded and extruded, and then cooled using a casting roll of 20 ° C. to 80 ° C., or forcibly cooled by cold air injected from an air knife to crystallize the film to form a solidified sheet. can do.
  • the temperature of the cool air injected from the air knife may be 20 °C to 80 °C.
  • the manufacturing method of the separator according to the present embodiment by stretching before the plasticizer extraction, the polyolefin-based resin is softened by the plasticizer to make the stretching operation easier, and thus the production stability can be increased, and the thickness of the sheet becomes thin due to the stretching. As a result, the plasticizer can be more easily removed from the sheet in the plasticizer extraction process after stretching.
  • the solidified sheet may be stretched in the longitudinal direction and / or in the transverse direction, and may be stretched in only one of the longitudinal or transverse directions (uniaxial stretching) or in both the longitudinal and transverse directions in both directions. Stretching can be performed (biaxial stretching). Further, when performing the biaxial stretching, the solidified sheet can be stretched simultaneously in the longitudinal direction and the transverse direction, or first in the longitudinal direction (or transverse direction), and then in the transverse direction (or longitudinal direction).
  • the stretching process may be performed by biaxial stretching, and the longitudinal stretching and transverse stretching may be performed simultaneously (simultaneously biaxial stretching), or the longitudinal (or transverse) stretching may be performed in the transverse direction (or Stretching in the longitudinal direction) (sequential biaxial stretching).
  • the sequential biaxial stretching method it may be easier to adjust the draw ratio in the longitudinal direction and the transverse direction.
  • the temperature conditions and the number of stretching may be appropriately adjusted as desired, but for example, the stretching may be performed such that the final stretching ratio is 5 to 8 times in the MD and TD directions at 100 ° C. to 120 ° C., respectively. have.
  • the plasticizer can then be extracted from the stretched sheet.
  • the stretched sheet may be immersed in a solvent in a plasticizer extractor to extract a plasticizer and then dry.
  • Plasticizer extraction may be performed using a plasticizer extractor comprising a plurality of extraction tanks.
  • the extraction tank may be 3 to 25 pieces.
  • a plurality of dipping tanks can be used to efficiently extract the plasticizer through several dipping processes.
  • the plurality of extraction tanks may be arranged in sequence in the extractor, Figure 1 shows an example using three extraction tanks, but is not limited thereto.
  • the stretched separator 20 is first immersed in a solvent in the first extraction tank 102 through a plurality of moving rolls 10 to extract a predetermined amount of plasticizer, followed by the second extraction tank 104 and the third extraction tank. It is immersed again at 106 to extract the plasticizer in the separation membrane 20 repeatedly and stepwise.
  • each extraction tank may be in an open form, and an upper portion of the third extraction tank 106 may be positioned higher than an upper portion of the remaining extraction tanks, and may be disposed in succession to the third extraction tank 106.
  • the upper portion of the extraction tank 104 may be disposed to be positioned relatively lower than the upper portion of the third extraction tank 106.
  • the extraction solvent is supplied from the solvent supply tank 160 to the third extraction tank 106, and the solvent continuously supplied from the solvent supply tank 160 to the third extraction tank 106 is supplied to the third extraction tank 106.
  • the excess solvent may be supplied and overflowed (overflow), and the overflowed solvent may be supplied to the second extraction tank 104 disposed in succession.
  • the second extraction tank 104 When the solvent is supplied from the third extraction tank 106 more than the capacity of the second extraction tank 104, the second extraction tank 104 also overflows the solvent, which is higher than the top of the second extraction tank 104 It may be supplied to the lower extraction first extraction tank 102.
  • each extraction tank eg, the first to third extraction tanks
  • the solvent supply tank 160 As the flow of solvent in each extraction tank is generated by the continuously supplied solvent and the overflowed solvent, the plasticizer is extracted in the extraction solvent and the concentration gradient formed near the immersed separator is eliminated, thereby making the plasticizer extraction process more efficient. You can do that.
  • the solvent overflowed from the first extraction tank 102 flows to the solvent recovery tank 120 located at a lower altitude than the first extraction tank 102, and the recovered solvent is subsequently supplied to the purification tank 140. And can be purified for reuse. Thereafter, the purified solvent is recycled back to the solvent supply tank 160 in such a manner that an efficient and economical plasticizer extraction process can be achieved.
  • the method of circulating the solvent is not particularly limited so long as it is a method of recovering the overflowed solvent sequentially generated from each extraction tank to be reusable, and then supplying it to each extraction tank, for example, from each tank to another tank.
  • a moving passage (eg, a pipe, a pipe, etc.) 180 may be connected to each tank to allow the movement and / or supply of the solvent.
  • the shape and size of each extraction tank can be appropriately selected by those skilled in the art, the concentration of the solvent in each extraction tank by the overflow can be kept constant, due to the continuous flow of solvent, each extraction tank The concentration of the solvent in the solvent may be maintained in the range of 90 to 99% by weight.
  • the stretched sheet 20 is sequentially immersed in the first extraction tank 102, the second extraction tank 104 and the third extraction tank 106 to perform a plasticizer extraction process
  • the first extraction tank As the separation membrane 20 moves from the 102 through the second extraction tank 104 to the third extraction tank 106, the plasticizer content in the separation membrane can be lowered, and the continuous supply of the solvent and the top of each extraction tank opening type By overflowing the solvent formed by the high difference, the extraction rate of the plasticizer is improved, thereby improving the productivity of the membrane manufacturing process.
  • the present embodiment can extract the plasticizer by immersing the stretched sheet in a solvent at 15 ° C to 30 ° C, for example 19 ° C to 26 ° C, each 20 to 100 seconds in a plurality of extraction tanks,
  • the plasticizer may be extracted by soaking for 20 to 60 seconds.
  • plasticizer extraction process After the plasticizer extraction process, it may be dried for more than 30 seconds at 15 °C to 30 °C, specifically 15 °C to 25 °C, specifically for 30 seconds to 3 minutes.
  • the first extraction tank 102 For example, it was immersed in about 5 L methylene chloride in the first extraction tank 102 for 20 seconds at 20 ° C., followed by subsequent immersion under the same conditions in the second extraction tank 104 and the third extraction tank 106. Then, it can be dried for 30 seconds at room temperature (25 °C) in a ventilated space. Increase in shrinkage in the transverse direction within the temperature and time range can be prevented, and the plasticizer can be sufficiently extracted. It is also possible to inject dry air from the outside in order to increase the drying efficiency.
  • the supply rate of the solvent supplied from the solvent supply tank 160 into the third extraction tank 106 may be adjusted to 300 kg / h or more, specifically 300 kg / h to 1500 It can be adjusted in kg / h. It is possible to improve the extraction rate decrease due to the high plasticizer concentration formed near the membrane surface in the above range.
  • the solvent used for the extraction is not particularly limited, and any solvent can be used as long as the solvent can extract the plasticizer.
  • Non-limiting examples of the solvent include halogenated hydrocarbons such as methylene chloride, 1,1,1-trichloroethane, and fluorocarbon, which have high extraction efficiency and are easy to dry; hydrocarbons such as n-hexane and cyclohexane; Alcohols such as ethanol and isopropanol; Ketones such as acetone and 2-butanone; and the like, and methylene chloride may be used when using liquid paraffin as a plasticizer.
  • the heat setting process may be performed after the plasticizer extraction and drying process.
  • the heat setting process is to reduce the heat shrinkage rate of the final sheet by removing residual stresses of the dried sheet, and may adjust the air permeability, heat shrinkage rate, strength, and the like of the separator according to the temperature and the fixed rate during the process.
  • the heat setting process may be a process of stretching and / or relaxing (shrinking) the extracted and dried sheets in at least one axis direction, and may be performed on both axes in the lateral direction and the longitudinal direction.
  • the process may be performed to stretch or relax all in the axial direction, to stretch and relax both in the axial direction, or to stretch and relax in one axial direction and to draw or relax only in the other axial direction.
  • the heat setting may be a process of stretching and relaxing (shrink) in the transverse direction, and the order of stretching and relaxing is not particularly limited. Specifically, after performing the transverse stretching, the transversely stretched sheet may be performed in a manner of alleviating again in the transverse direction.
  • the strength of the separator can be improved, and the heat shrinkage rate of the separator can be improved to enhance heat resistance.
  • the film may be stretched at a predetermined magnification in the horizontal direction while being heat-set at a temperature below the melting point of the dried separator or may not be stretched if necessary.
  • the dried separator may be heat-fixed at 110 ° C to 130 ° C.
  • the thermal conditions at the time of heat setting may be appropriately adjusted to various temperature ranges, and the transverse stretching and / or transverse relaxation is repeatedly performed at an appropriate number of times one or more times according to the strength, thermal contraction rate of the desired separator, the use of the film
  • the draw ratio can be adjusted arbitrarily according to the invention.
  • the separation membrane production method of the present embodiment includes self-circulating the solvent during plasticizer extraction.
  • the solvent can be self-circulated to achieve more efficient plasticizer extraction.
  • Processes that are not specifically mentioned, such as extrusion and film forming processes and stretching processes, are substantially the same as the method for preparing a separator according to an embodiment of the present invention described above, and hereinafter, focusing on the self-circulation of the solvent in the plasticizer extraction process Explain.
  • the self-circulation of the solvent may be formed through one inlet of the extraction tank and the inlet through which the solvent flows out and the inlet through which the solvent flows back into the extraction tank.
  • the extraction tank of this embodiment can self circulate the solvent in at least one extraction tank for plasticizer extraction through more effective circulation of the solvent.
  • Each end of the pipe is not particularly limited as long as it can recirculate the solvent flowing out of the extraction tank, and the length, shape, angle, etc. of the pipe may be selected by those skilled in the art according to the location of the separation membrane in the extraction tank. You can decide accordingly.
  • the pipe for self-circulation of the solvent in the extraction tank may be formed in at least one of the plurality of extraction tanks, forming a hole on the surface of the pipe, or by attaching a tip or the like to re-extract the solvent flowing out of the extraction tank
  • the solvent flows into the space between the separation membranes to form a flow of the solvent, thereby facilitating self-circulation of the solvent.
  • pressure may be applied from the outside for injection of the solvent when the solvent is reflowed from the extraction tank.
  • Supply of the solvent for the self-circulation of the solvent in the extraction tank can be made at a rate of 300 kg / h to 500 kg / h, as described above through the overflow and the self-circulation of the solvent using a pipe,
  • the extraction efficiency can be improved even with the same amount of solvent, Accordingly, there is an advantage that can reduce the total amount of solvent used.
  • a heat setting process may be performed to finally form a separator, and the heat setting process may be performed by the same method as the above-described embodiment of the present invention.
  • the membrane production method of the present embodiment may include self-circulating the solvent at the time of plasticizer extraction.
  • the solvent can be self-circulated to extract the plasticizer efficiently.
  • FIG. 4 shows the first extraction tank 202 of FIG. 2, which is similar to the structure of the extraction tank for self-circulation of the solvent described with reference to FIG. 3, but differs in shape and location of the outlet and the inlet. Therefore, the self-circulation of the solvent will be described in more detail based on the above difference.
  • a plurality of inlets 310 are provided at both sides of the first extraction tank 202 to allow the solvent to be introduced at the same time. This can further reduce the variation in the concentration gradient of the solvent in the extraction tank.
  • the solvent may flow out through the solvent outlet 320 formed at the bottom of the first extraction tank, and may be re-introduced into the extraction tank through the pipe 308.
  • the first extraction tank 202 and the inlet 310 of the pipe 308 for the re-introduction of the solvent is formed in the first extraction tank 202 in a form attached to the side surface of the first extraction tank 202.
  • Each end of the pipe 308 attached to the first extraction tank 202 is not particularly limited as long as it is a position to recirculate and circulate the solvent discharged in the extraction tank, the length of the pipe, The shape, angle, and the like may also be appropriately determined by a person skilled in the art according to the position of the separator in the extraction tank.
  • three or more inlets 310 connecting the pipe and the first extraction tank to each side for recycling of the solvent may be formed, more specifically, the first extraction tank 202 by forming three to six Solvent may be self-circulated by reflowing the solvent.
  • the plasticizer concentration gradient in the solvent can be more effectively reduced.
  • the inlet 310 may be formed to flow in the vertical direction of the direction in which the separation membrane moves, so that pressure may not be applied to the separation membrane when the solvent is re-introduced by the self-circulation of the solvent.
  • the separator according to an embodiment of the present invention is a porous separator including a polyolefin-based resin, and the residual amount of the plasticizer in the separator according to Formula 1 may be 1.0 wt% or less based on the total weight of the separator.
  • Residual amount of plasticizer [(W1-W2) / W1] x 100
  • W1 represents the weight of the separator before the plasticizer is removed
  • W2 represents the weight of the separator after the plasticizer is removed.
  • the separator of this embodiment may be prepared by the method of manufacturing a separator according to the embodiments of the present invention described above.
  • the residual amount of the plasticizer in the separator is within the above range, it is possible to improve the decrease in air permeability, porosity, thermal shrinkage, electrolyte wettability, tensile strength and puncture strength due to the residual plasticizer.
  • the method of measuring the residual amount of the plasticizer is not particularly limited, and any method can be used as long as it can measure the residual amount of the plasticizer in the separator, and a non-limiting example is as follows: 500 mm (W) ⁇ 600 mm (L After sampling the separation membrane (about 2g) in size and store in 105 °C oven for 10 minutes to measure the moisture removal weight (W1). Methylene chloride was heated at 120 ° C.
  • Residual amount of plasticizer [(W1-W2) / W1] x 100
  • the air permeability may be 80 sec / 100 cc to 200 sec / 100 cc, specifically 100 sec / 100 cc to 200 sec / 100 cc, more specifically 100 sec / 100 cc to 180 sec / 100 cc.
  • the method of measuring the airflow is not particularly limited, but a non-limiting example of the airflow is as follows: after making 10 specimens cut at 10 different points, the airflow measuring device EG01-55-1MR (Asahi Seiko) G) is used to measure air permeability by measuring the average time (sec) five times for each of the specimens having a circular area of 1 inch diameter to permeate 100 cc of air, and then calculating the average value.
  • Separation membrane according to an embodiment of the present invention may exhibit a porosity (porosity) of 30% to 60%, the porosity may be specifically 40% to 50%, more specifically may be 43% to 47% have.
  • the electrolyte may be sufficiently impregnated to improve battery performance, and maintain the strength of the separator.
  • the method of measuring the porosity is not particularly limited, but may be performed by, for example, the following method:
  • the membrane is cut into 10 cm ⁇ 10 cm to obtain the volume (cm 3) and mass (g) of each sample. From the volume and mass and the density (g / cm 3) of the separator, the porosity is calculated using Equation 2 below.
  • Porosity (%) (volume-mass / sample density) / volume ⁇ 100
  • the heat shrinkage measured after leaving the separator according to an embodiment of the present invention at 120 ° C. for 1 hour may be 7% or less in the longitudinal direction and 4% or less in the transverse direction, and specifically, 6% or less in the longitudinal direction. And 3% or less in the transverse direction.
  • the method for measuring the thermal contraction rate of the separator is not particularly limited, it may be used a method commonly used in the art.
  • a non-limiting example of the method of measuring the heat shrinkage rate is as follows: The prepared separator is cut to about 5 cm in length (MD) about 5 cm in length (TD), which is cut in a chamber at 120 ° C. After storage for 1 hour, the shrinkage in the longitudinal and transverse directions of the separator may be measured to calculate the heat shrinkage rate.
  • the separator according to an embodiment of the present invention may have a wettability of the electrolyte when the separator is immersed in the electrolyte at 18 ° C. for 60 minutes, 10 mg / g or more, and specifically 15 mg / g to 40 mg / g or more. May be from 15 mg / g to 35 mg / g.
  • Absorption rate of the electrolyte may be improved in the above range, thereby improving performance of a battery including the separator having the above physical properties.
  • the method of measuring the wettability is not particularly limited as long as it is a method of measuring the weight of the electrolyte per 1 g of the separator, and a non-limiting example of the method is as follows: an electrolyte in which each separator is kept at 18 ° C. (electrolyte: LiBF 4 , Electrolyte concentration: 1 mo1 / L, solvent: propylene carbonate), and immersed for 1 hour, and the increase in mass was investigated to calculate the electrolyte wettability represented by Equation 3 below.
  • the tensile strength of the separator according to an embodiment of the present invention may be 1000 kgf / cm 2 or more in the longitudinal direction and transverse direction, specifically 1100 kgf / cm 2 or more in the longitudinal direction and transverse direction, 1200 kgf / cm 2 or more.
  • the strength can be controlled in the above range.
  • Method for measuring the tensile strength of the separator is not particularly limited, it can be used a method commonly used in the art.
  • a non-limiting example of a method for measuring the tensile strength of the separator is as follows: 10 prepared by cutting the membrane at 10 different points in the shape of a rectangle (MD) 10 mm ⁇ length (TD) 50 mm After the specimens were prepared, each specimen was mounted in a UTM (tension tester), and the bite was measured to have a measuring length of 20 mm, and then the specimens were pulled to measure average tensile strength in the longitudinal and transverse directions.
  • the puncture strength of the separator according to an embodiment of the present invention may be 400 gf or more, specifically 400 gf to 600 gf, may be 400 gf to 550 gf. In the above range, the sticking strength can be easily controlled.
  • a method of measuring the sticking strength a method commonly used in the art may be used, and a non-limiting example of a method of measuring the sticking strength of the separator is as follows: ) 10 specimens cut from 10 different points 50 mm ⁇ 50 mm (TD) were fabricated, and then placed on a 10 cm hole using a KATO Tech G5 instrument and drilled with a 1 mm probe. The force is measured, and the puncture strength of each specimen is measured three times, and then the average value is calculated.
  • the separator according to the present embodiment includes a polyolefin-based resin and a porous heat-resistant layer formed on one or both sides of the polyolefin-based resin.
  • the polyolefin resin is a porous membrane formed by the manufacturing method according to the embodiments of the present invention described above, the residual amount of the plasticizer in the polyolefin resin may be 1.0% by weight or less based on the total weight of the polyolefin resin.
  • the porous heat resistant layer may be formed of a porous heat resistant layer composition, and the porous heat resistant layer composition may include an organic binder, inorganic particles, and a solvent.
  • the organic binder used in the present invention is specifically, polyvinylidene fluoride (PVdF) homopolymer, polyvinylidene fluoride-hexaxafluoropropylene copolymer (Polyvinylidene fluoride-Hexafluoropropylene copolymer, PVdF-HFP), poly Methyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, polyethylene oxide, cellulose acetate, cellulose acetate butylate (cellulose acetate butyrate), cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose ), Pullulan (p ullulan), carboxyl methyl cellulose, and acrylonitrilestyrene-butadiene copolymers alone or mixtures thereof.
  • a PVdF-based binder may be used, and the PVdF-based binder may have a weight average molecular weight (Mw) of 500,000 g / mol to 1,500,000 g / mol and may be used by mixing two or more kinds having different weight average molecular weights.
  • Mw weight average molecular weight
  • one or more types of weight average molecular weights of 1,000,000 g / mol or less and one or more types of 1,000,000 g / mol or more can be mixed and used.
  • PVdF-based binder within the above molecular weight range enhances the adhesion between the porous heat-resistant layer and the separator polyolefin resin, thereby effectively suppressing shrinkage of heat-sensitive separator polyolefin resin by heat, and further improving the electrolyte impregnation properties.
  • Separation membrane can be prepared and by using this has the advantage that can produce a battery with efficient electrical output.
  • the inorganic particles used in the present invention are not particularly limited and may be inorganic particles commonly used in the art.
  • Non-limiting examples of the inorganic particles usable in the present invention include Al 2 O 3 , SiO 2 , B 2 O 3 , Ga 2 O 3 , TiO 2 , SnO 2 , and the like. These can be used individually or in mixture of 2 or more types.
  • Al 2 O 3 (alumina) can be used as the inorganic particles used in the present invention.
  • the size of the inorganic particles used in the present invention is not particularly limited, but the average particle diameter may be 1 nm to 2,000 nm, for example, 100 nm to 1,000 nm.
  • the inorganic particles in the size range it is possible to prevent the dispersion and fairness of the inorganic particles in the porous heat-resistant layer to be lowered and the thickness of the porous heat-resistant layer is appropriately adjusted to decrease the mechanical properties and increase the electrical resistance Can be prevented.
  • the size of the pores generated in the separator is appropriately adjusted, there is an advantage that can lower the probability of the internal short circuit occurs during the charge and discharge of the battery.
  • the inorganic particles may be used in the form of an inorganic dispersion in which it is dispersed in a suitable solvent.
  • the appropriate solvent is not particularly limited and may be a solvent commonly used in the art.
  • Acetone can be used as a suitable solvent for dispersing the inorganic particles, for example.
  • the inorganic particles in the porous heat-resistant layer may be included in 70 to 95% by weight, specifically 75 to 90% by weight, more specifically 80 to 90% by weight based on the total weight of the porous heat-resistant layer.
  • the inorganic particles are contained within the above range, the heat dissipation characteristics of the inorganic particles may be sufficiently exhibited, and when the separator is coated using the inorganic particles, heat shrinkage of the separator may be effectively suppressed.
  • Non-limiting examples of the solvent that can be used in the present invention is dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, dimethyl carbonate or N-methylpyrrolidone (N-methylpyrrolydone) etc. are mentioned.
  • the content of the solvent may be 20 wt% to 99 wt%, specifically 50 wt% to 95 wt%, and more specifically 70 wt% to 95 wt%, based on the weight of the porous heat-resistant layer composition. .
  • the porous heat resistant layer may be easily manufactured, and the drying process of the porous heat resistant layer may be performed smoothly.
  • Method for producing a separator according to another embodiment of the present invention is an organic binder; Inorganic particles; And forming a porous heat resistant layer composition comprising a solvent, and forming the porous heat resistant layer with the porous heat resistant layer composition on one or both surfaces of the separator polyolefin resin described herein.
  • forming the porous heat-resistant layer composition may include mixing the organic binder, the solvent, and the inorganic particles and stirring for 30 minutes to 5 hours at 10 °C to 40 °C.
  • the content of the solid content may be 10 parts by weight to 20 parts by weight with respect to the porous heat-resistant layer composition
  • the weight ratio of the binder and the inorganic particles in the solid content may be 3: 7 to 0.5: 9.5.
  • a porous heat resistant layer composition may be prepared by preparing an inorganic dispersion in which the inorganic particles are dispersed in a dispersion medium and mixing the same with a polymer solution containing an organic binder and a solvent.
  • the inorganic dispersion is prepared separately as described above, the dispersibility and crude liquid stability of the inorganic particles and the binder may be improved.
  • the binder component and the inorganic particles may each be prepared and mixed in a dissolved or dispersed state in a suitable solvent.
  • the porous heat-resistant layer composition may be prepared by preparing a solution in which an organic binder is dissolved in a suitable solvent and an inorganic dispersion in which inorganic particles are dispersed, and then mixing them with a suitable solvent.
  • a ball mill, a beads mill, a screw mixer, or the like may be used for the mixing.
  • porous heat resistant layer is formed on the one or both surfaces of the porous polyolefin resin after plasticizer extraction using the porous heat resistant layer composition.
  • the method of forming the porous heat-resistant layer on the polyolefin resin using the porous heat-resistant layer composition is not particularly limited, methods commonly used in the technical field of the present invention, for example, coating method, lamination, ball Extrusion or the like can be used.
  • Non-limiting examples of the coating method may include a dip coating method, a die coating method, a roll coating method, or a comma coating method. These may be applied alone or in combination of two or more methods.
  • the porous heat resistant layer of the separator of the present invention may be formed by, for example, a dip coating method.
  • the thickness of the porous heat resistant layer of the present invention may be 0.01 ⁇ m to 20 ⁇ m, specifically 1 ⁇ m to 10 ⁇ m, and more specifically 1 ⁇ m to 5 ⁇ m. Within the thickness range, an excellent thermal stability and adhesion can be obtained by forming a porous heat resistant layer having an appropriate thickness, and the thickness of the entire separator can be prevented from becoming too thick to suppress an increase in the internal resistance of the battery.
  • Drying the porous heat-resistant layer in the present invention may be a method of irradiating with dry or vacuum drying or far-infrared rays or electron beams by hot air, hot air, low humidity.
  • the drying temperature is different depending on the type of the solvent, but can be dried at a temperature of approximately 60 °C to 120 °C.
  • the drying time also varies depending on the type of solvent, but may generally be dried for 1 minute to 1 hour. For example, it may be dried for 1 minute to 30 minutes, or 1 minute to 10 minutes at a temperature of 90 °C to 120 °C.
  • the type of the secondary battery is not particularly limited and may be a battery of a kind known in the art.
  • the secondary battery may be a lithium secondary battery such as a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • the method for manufacturing the secondary battery is not particularly limited, and a method commonly used in the technical field of the present invention may be used.
  • a non-limiting example of a method for manufacturing the secondary battery is as follows: The separator comprising the heat resistant layer of the present invention is placed between the positive electrode and the negative electrode of the battery, and then the battery is prepared by filling the electrolyte therein. Can be.
  • Secondary battery according to an embodiment is described as an example of the square, but the present invention is not limited thereto, and may be applied to various types of batteries such as lithium polymer battery, cylindrical battery.
  • a secondary battery includes an electrode assembly wound through a separator between a positive electrode and a negative electrode, and a case in which the electrode assembly is embedded.
  • the positive electrode, the negative electrode and the separator are impregnated with an electrolyte.
  • the separator is as described above.
  • the positive electrode may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
  • the positive electrode active material layer may include a positive electrode active material, a binder, and optionally a conductive material.
  • aluminum (Al), nickel (Ni), or the like may be used, but is not limited thereto.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used. Specifically, at least one of cobalt, manganese, nickel, aluminum, iron, or a combination of metal and lithium composite oxide or phosphoric acid may be used. More specifically, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate or a combination thereof may be used.
  • the binder not only adheres the positive electrode active material particles well to each other, but also serves to adhere the positive electrode active material to the positive electrode current collector, and specific examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and polyvinyl chloride.
  • Carboxylated polyvinylchloride polyvinylfluoride, ethylene oxide containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, Acrylated styrene-butadiene rubber, epoxy resin, nylon and the like, but is not limited thereto. These can be used individually or in mixture of 2 or more types.
  • the conductive material provides conductivity to the electrode, and examples thereof include natural graphite, artificial graphite, carbon black, carbon fiber, metal powder, and metal fiber, but are not limited thereto. These can be used individually or in mixture of 2 or more types.
  • metal powder and the metal fiber metals such as copper, nickel, aluminum, and silver may be used.
  • the negative electrode may include a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector.
  • the negative electrode current collector may include copper (Cu), gold (Au), nickel (Ni), a copper alloy, or the like, but is not limited thereto.
  • the negative electrode active material layer may include a negative electrode active material, a binder, and optionally a conductive material.
  • the negative electrode active material may be a material capable of reversibly intercalating and deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and undoping lithium, a transition metal oxide, or a combination thereof. Can be used.
  • Examples of a material capable of reversibly intercalating and deintercalating the lithium ions include carbon-based materials, and examples thereof include crystalline carbon, amorphous carbon, or a combination thereof.
  • Examples of the crystalline carbon may be amorphous, plate, flake, spherical or fibrous natural graphite or artificial graphite.
  • Examples of the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, calcined coke, and the like.
  • Examples of the alloy of the lithium metal include lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn. Alloys of the metals selected may be used.
  • Examples of materials capable of doping and undoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si-C composites, Si-Y alloys, Sn, SnO 2 , Sn-C composites, Sn-Y, and the like. And at least one of these and SiO 2 may be mixed and used.
  • transition metal oxide examples include vanadium oxide and lithium vanadium oxide.
  • Kinds of the binder and the conductive material used in the negative electrode are the same as the binder and the conductive material used in the above-described positive electrode.
  • the positive electrode and the negative electrode may be prepared by mixing each active material, a binder, and optionally a conductive material in a solvent to prepare each active material composition, and applying the active material composition to each current collector.
  • N-methylpyrrolidone may be used as the solvent, but is not limited thereto. Since such an electrode manufacturing method is well known in the art, detailed description thereof will be omitted.
  • the electrolyte solution contains an organic solvent and a lithium salt.
  • the organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • Specific examples thereof may be selected from carbonate solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents and aprotic solvents.
  • the carbonate solvent examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), ethylmethyl carbonate (EMC), ethylene Carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • MPC methylpropyl carbonate
  • EPC ethylpropyl carbonate
  • EMC ethylmethyl carbonate
  • EMC ethylmethyl carbonate
  • EC ethylene Carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • ester solvents examples include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, decanolide, valerolactone, and meronate. Melononolactone, caprolactone, and the like.
  • ether solvent examples include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran and the like. Cyclohexanone etc. are mentioned as said ketone solvent, Ethyl alcohol, isopropyl alcohol, etc. are mentioned as said alcohol solvent.
  • the organic solvents may be used alone or in combination of two or more thereof, and the mixing ratio in the case of mixing two or more kinds may be appropriately adjusted according to the desired battery performance.
  • the lithium salt is a substance that dissolves in an organic solvent and acts as a source of lithium ions in the battery to enable operation of a basic secondary battery and to promote the movement of lithium ions between the positive electrode and the negative electrode.
  • lithium salt examples include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN (SO 3 C 2 F 5 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ) (x and y are natural numbers), LiCl, LiI, LiB (C 2 O 4 ) 2 or a combination thereof Can be mentioned.
  • the concentration of the lithium salt can be used within the range of 0.1M to 2.0M.
  • concentration of the lithium salt is within the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • Secondary battery according to another embodiment of the present invention may have a 100-cycle charge and discharge retention of 70% to 100%, specifically 80% to 100% range.
  • PE polyethylene
  • TICONA polyethylene
  • a fluid paraffin far eastern emulsion
  • the gel phase obtained through the T-die was manufactured as a sheet-type separator using a cooling roll.
  • the separator was stretched at 110 ° C. so that the draw ratios of the machine direction (Machine Direction, MD) and the transverse direction (Transverse Direction, TD) were 7 times each.
  • Plasticizers were extracted in a plasticizer extractor in which the stretched separators were arranged in order to have a high difference in the upper portions of the first extraction tank, the second extraction tank, and the third extraction tank.
  • the solvent that overflowed in the plasticizer extraction tank flowed into the solvent recovery tank and supplied to the purification tank, and the purified solvent was supplied again to the plasticizer extraction tank through the solvent supply tank to circulate the solvent.
  • the rate of the solvent supplied from the solvent supply tank to the third extraction tank was adjusted to 1000 kg / h, and after immersion for 20 seconds at 20 ° C. in about 5 L methylene chloride in the first extraction tank, followed by the second extraction It was immersed under the same conditions in the bath and the third extraction tank, neutralized, and then dried at room temperature (25 ° C.) for 30 seconds. Then, the dried film was heat-set at 130 ° C. and wound to prepare a separator having a thickness of 12 ⁇ m.
  • Example 1 the separator was prepared under the same conditions and method except that the solvent supply rate was 500 kg / h.
  • Example 1 the separator was prepared under the same conditions and method except that the solvent supply rate was 300 kg / h.
  • Example 3 the same method and conditions except for the method of recycling the solvent by connecting pipes to the first extraction tank, the second extraction tank, and the third extraction tank to enable self-circulation of the solvent in each extraction tank.
  • a separator was prepared.
  • 'PVdF' Polyvinylidene fluoride (hereinafter referred to as 'PVdF') homopolymer (Solva) having a weight average molecular weight of 1,100,000 g / mol was added to DMF (large gold) at 10% by weight, using a stirrer at 25 ° C. Stirring for 4 hours to prepare a second polymer solution.
  • DMF Large gold
  • Alumina Japanese Light Metal
  • acetone large gold
  • a porous heat resistant layer composition was prepared by stirring at 25 ° C. for 2 hours.
  • the prepared porous heat-resistant layer composition was coated on both sides of the polyolefin-based resin of the separator prepared in Example 1 by a dip coating method and then dried to prepare a separator.
  • Example 1 the separator was prepared under the same conditions and methods except that a single extraction tank was used and the solvent feed rate was 500 kg / h.
  • Example 1 the separator was prepared under the same conditions and method except that the solvent feeding rate was 100 kg / h.
  • compositions and extraction conditions used in Examples 1 to 5 and Comparative Examples 1 and 2 are shown in Table 1 below.
  • Example / Comparative Example Solvent Feed Rate (kg / h) Extraction tank count Extraction conditions Total extraction time (seconds) Extraction temperature (°C) Example 1 1000 3 60 20 Example 2 500 3 60 20 Example 3 300 3 60 20 Example 4 300 All three 60 20 Example 5 1000 3 60 20 Comparative Example 1 500 One 60 20 Comparative Example 2 100 3 60 20
  • the separator (about 2 g) having a size of 500 mm (W) ⁇ 600 mm (L) was sampled and stored in an oven at 10O < 0 > C for 10 minutes to measure the moisture removal weight (W1). Methylene chloride was heated at 120 ° C.
  • Residual amount of plasticizer (%) [(W1-W2) / W1] x 100
  • the membranes were cut into 10 cm x 10 cm, respectively, to obtain the volume (cm 3) and mass (g) of the sample, and the porosity was calculated using the following equation 2 from the density (g / cm 3) of the membrane.
  • Porosity (%) (volume-mass / sample density) / volume ⁇ 100
  • a total of seven samples were prepared by cutting each of the separators 5 mm in length and 5 cm in length. Each sample was stored in a chamber at 120 ° C. for 1 hour, and then the shrinkage in the MD and TD directions of each sample was measured, and then the average value was calculated to determine the thermal shrinkage.
  • Each separator was immersed in an electrolyte solution (electrolyte: LiBF 4 , electrolyte concentration: 1 mo1 / L, solvent: propylene carbonate) kept at 18 ° C. for 1 hour, and the increase in mass was investigated to calculate electrolyte wettability according to the following Equation 3. It was.
  • electrolyte solution electrolyte: LiBF 4 , electrolyte concentration: 1 mo1 / L, solvent: propylene carbonate
  • Each of the separators was made of 10 specimens cut at 10 different points in the shape of a rectangle (MD) 10 mm ⁇ length (TD) 50 mm, and then each specimen was mounted on a UTM (tension tester) to measure the length. After being bitten to 20 mm, the specimens were pulled to measure average tensile strength in the MD and TD directions.
  • MD rectangle
  • TD length
  • UTM tension tester

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Abstract

La présente invention concerne un séparateur permettant d'améliorer un taux d'extraction de plastifiant en ajustant une étape d'extraction de plastifiant afin qu'une quantité de résidu d'un plastifiant à l'intérieur du séparateur soit réduite. Particulièrement, diverses propriétés de matériau du séparateur causées par un résidu de plastifiant sont améliorées en faisant circuler un solvant durant une étape d'extraction afin de réduire un gradient de concentration au voisinage d'une surface du séparateur de sorte qu'un taux d'extraction est augmenté, ce qui permet d'obtenir les performances d'une batterie et une stabilité thermique.
PCT/KR2014/011520 2013-11-29 2014-11-28 Séparateur, son procédé de fabrication, et batterie l'utilisant WO2015080507A1 (fr)

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CN107482151A (zh) * 2017-07-21 2017-12-15 苏州捷力新能源材料有限公司 锂电池隔膜的萃取穿膜方法
CN108539093A (zh) * 2017-03-03 2018-09-14 住友化学株式会社 膜制造装置及膜制造方法
CN110038319A (zh) * 2019-02-13 2019-07-23 江苏北星新材料科技有限公司 一种湿法锂离子电池隔膜萃取设备用溢流装置

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CN113471623B (zh) * 2021-05-25 2023-08-01 湖南诺邦新能源科技有限公司 一种锂电池隔膜热定型后修边处理方法

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CN106328863A (zh) * 2016-09-09 2017-01-11 深圳市星源材质科技股份有限公司 一种去除萃取溶剂的装置及方法
CN108539093A (zh) * 2017-03-03 2018-09-14 住友化学株式会社 膜制造装置及膜制造方法
CN107482151A (zh) * 2017-07-21 2017-12-15 苏州捷力新能源材料有限公司 锂电池隔膜的萃取穿膜方法
CN107482151B (zh) * 2017-07-21 2020-05-22 苏州捷力新能源材料有限公司 锂电池隔膜的萃取穿膜方法
CN110038319A (zh) * 2019-02-13 2019-07-23 江苏北星新材料科技有限公司 一种湿法锂离子电池隔膜萃取设备用溢流装置
CN110038319B (zh) * 2019-02-13 2023-12-26 江苏北星新材料科技有限公司 一种湿法锂离子电池隔膜萃取设备用溢流装置

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