WO2015065121A1 - 역오팔 구조의 다공성 기재를 포함하는 전기화학소자용 다공성 분리막 및 이의 제조 방법 - Google Patents
역오팔 구조의 다공성 기재를 포함하는 전기화학소자용 다공성 분리막 및 이의 제조 방법 Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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- 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
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/046—Elimination of a polymeric phase
- C08J2201/0462—Elimination of a polymeric phase using organic solvents
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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Definitions
- the present invention relates to a separator for an electrochemical device and a manufacturing method thereof. More particularly, the present invention relates to a porous separator for an electrochemical device including a porous substrate having a uniform size and shape of pores, and a method of manufacturing the same.
- lithium secondary batteries developed in the early 1990s have a higher operating voltage and greater energy density than conventional batteries such as Ni-MH, Ni-Cd, and sulfuric acid-lead batteries that use an aqueous electrolyte solution. I am in the spotlight.
- lithium ion batteries have safety problems such as ignition and explosion due to the use of the organic electrolyte, and are difficult to manufacture.
- the lithium ion polymer battery has been considered as one of the next generation batteries by improving the weakness of the lithium ion battery, but the capacity of the battery is still relatively low compared to the lithium ion battery, and the discharge capacity is improved due to insufficient discharge capacity at low temperatures. This is urgently needed.
- electrochemical devices are produced by many companies, but their safety characteristics show different aspects. It is very important to evaluate the safety and secure the safety of these electrochemical devices. The most important consideration is that the electrochemical device should not cause injury to the user in case of malfunction. For this purpose, safety standards strictly regulate the ignition and smoke in the electrochemical device. In the safety characteristics of the electrochemical device, there is a high possibility that an explosion occurs when the electrochemical device is overheated to cause thermal runaway or the separator penetrates. In particular, polyolefin-based porous membranes commonly used as separators for electrochemical devices exhibit extreme heat shrinkage behavior at temperatures of 100 ° C. or higher due to material characteristics and manufacturing process characteristics including stretching, resulting in a short circuit between the anode and the cathode. There is a problem that causes.
- 2008-0109237 discloses a method of manufacturing an electrode that prevents penetration of a binder polymer by first applying a solvent to a surface of an active material layer before forming a porous coating layer, but a packing density according to application of a solvent. There is still a problem of deterioration and rough surface formation.
- an object of the present invention is to provide a porous separator for an electrochemical device having excellent porosity and ionic conductivity.
- Another object of the present invention is to provide an environmentally friendly reverse opal structure manufacturing process that does not require hydrofluoric acid treatment and a membrane manufacturing process using the same, unlike a conventional process using silica or titania.
- the present invention provides a porous substrate for an electrochemical device and a method of manufacturing the same for solving the above technical problem.
- the porous substrate according to the present invention has a reverse opal structure, and a method for preparing the same includes preparing a colloidal solution including polymer particles (S10); Coating the colloidal solution on a substrate to form a coating layer of polymer particles having an opal structure (S20); Preparing a polymer resin dispersion in which the polymer resin is dispersed in a first organic solvent (S30); Filling the opal structure of the polymer particles with the polymer resin dispersion (S40); And dissolving the polymer particles using the second organic solvent (S50). It includes.
- the polymer particles may be a non-crosslinked polymer
- the polymer resin may be a crosslinked polymer
- the polymer particles are styrene-butadiene rubber (SBR), polybutadiene rubber, polyfluoroprene (neoprene), nitrile rubber, acrylic rubber, fluorine-based rubber (FKM), PVC, polystyrene, polystyrene, polymethyl methacrylate
- SBR styrene-butadiene rubber
- PMMA polybutadiene rubber
- FKM fluorine-based rubber
- PVC polystyrene
- polystyrene polystyrene
- polymethyl methacrylate One selected from the group consisting of latex (PMMA), acrylonitrile-butadiene-styrene (ABS), polyvinylidene fluoride, polyvinyl fluoride, PTFE, polyvinyl acetate or copolymers thereof, and vinyl acetate-ethylene copolymers Or two or more kinds.
- PMMA latex
- ABS acrylonitrile-
- the diameter of the polymer particles may be 0.1 ⁇ m to 1 ⁇ m.
- the polymer resin may be a high heat resistance plastic engineering resin.
- the high heat resistance plastic engineering resin is polysulfone (PSF), polyether sulfone (PES), polyetherimide (PEI), polyphenylene sulfide (PPS), polyether ether ketone (PEEK), polyarylate (PA) and polyamideimide (PAI), polyimide (PI) may be one or two or more selected from the group consisting of.
- the first organic solvent may be a chlorine-based organic solvent.
- the second organic solvent may be one capable of selectively dissolving the polymer particles.
- the present invention also provides an electrode assembly comprising a cathode, an anode, and a separator interposed between the cathode and the anode, and an electrochemical device comprising the electrode assembly, wherein the separator is a method according to the present invention described above. It includes a porous substrate prepared by.
- the present invention provides a porous substrate for an electrochemical device having a reverse opal structure, a plurality of pores are present on the surface and the inside of the porous substrate and the standard deviation of the pore diameter is 1% to 35%. .
- the pores are those having a diameter of 0.1 ⁇ m to 1 ⁇ m.
- the porous substrate may include a high heat resistance plastic engineering resin.
- the high heat resistance plastic engineering resin is polysulfone (PSF), polyether sulfone (PES), polyetherimide (PEI), polyphenylene sulfide (PPS), polyether ether ketone (PEEK), polyarylate (PA) and polyamideimide (PAI), polyimide (PI) may be one or two or more selected from the group consisting of.
- the high heat resistance plastic engineering resin may have a molecular weight of 100,000 Da to 10,000,000 Da.
- the high heat resistance plastic engineering resin may be a linear polyimide or an aromatic heterocyclic polyimide containing an imide group in the main chain.
- the porous substrate may include a crosslinked polymer resin.
- the separator according to the present invention is formed by the manufacturing process of the reverse opal structure, the size and shape of the pores is uniform and has a high porosity. In addition, the separator has excellent porosity, ionic conductivity and air permeability without problems of pore closure and thickness reduction. Finally, the manufacturing method of the reverse opal structure according to the present invention is environmentally friendly and not harmful to the human body because hydrofluoric acid treatment is not required unlike the prior art.
- FIG. 1 is a flowchart schematically illustrating a process for preparing a separator having an inverse opal structure according to the present invention.
- FIG. 2 schematically illustrates a process of forming a conventional inverse opal structure.
- Figure 3 schematically shows a process for producing a membrane of the reverse opal structure according to the present invention.
- Figure 4 shows the template of the opal structure prepared in the membrane manufacturing process of the present invention.
- the present invention relates to a porous substrate having a reverse opal structure and a method of manufacturing the same.
- the present invention provides a separator comprising the porous substrate and an electrochemical device including the separator.
- a first aspect of the invention is directed to a method of making a porous substrate having an inverse opal structure.
- the porous substrate having an inverse opal structure according to the present invention is obtained by forming a template of an opal structure using polymer particles, filling a polymer resin into the template, and then dissolving and removing the polymer particles using an organic solvent. Can lose.
- FIG. 1 is a flow chart of the procedure for producing a porous substrate of the reverse opal structure of the present invention. Next, the present invention will be described in detail with reference to FIG. 1.
- a colloidal solution containing polymer particles is prepared.
- the polymer particles preferably have a crosslinking degree (or gel fraction) of less than 10%, or less than 5%, or less than 3%, or less than 1%, or an uncrosslinked polymer.
- a crosslinking degree or gel fraction of less than 10%, or less than 5%, or less than 3%, or less than 1%, or an uncrosslinked polymer.
- Highly crosslinked polymers swell when contacted with a solvent but do not dissolve well. Therefore, in the steps to be described later, the polymer particles are not crosslinked with the polymer particles in order to dissolve the polymer particles by the solvent to remove the template of the opal structure and form the reverse opal structure.
- the degree of crosslinking (or gel fraction) may be calculated by the following general formula (1).
- A is the mass of the polymer used as the polymer particles
- B is the insoluble fraction collected after 72 hours of immersion in ethyl acetate at room temperature in a 200-mesh mesh.
- the gel fraction of the polymer particles is less than 10%, or less than 5%, or less than 3%, or less than 1%, or 0% or by using uncrosslinked particles to facilitate removal by dissolution in the steps described below. can do.
- the polymer particles are styrene-butadiene rubber (SBR), polybutadiene rubber, polyfluoroprene (neoprene), nitrile rubber, acrylic rubber, fluorine-based rubber (FKM), PVC, polystyrene (PS), polymethyl methacrylate ( PMMA), acrylonitrile-butadiene-styrene (ABS), polyvinylidene fluoride, polyvinyl fluoride, PTFE, polyvinyl acetate or copolymers thereof, or vinylacetate-ethylene copolymers It is However, the present invention is not limited thereto, and the polymer particles are not particularly limited as long as they produce stable particles by emulsion polymerization or suspension polymerization.
- SBR styrene-butadiene rubber
- polyfluoroprene neoprene
- nitrile rubber acrylic rubber, fluorine-based rubber (FKM), PVC, polystyrene (PS
- the polymer particles of SBR can be obtained by low temperature emulsion polymerization while stirring monomers such as 1,3 butadiene and styrene, and additives such as emulsifiers, polymerization initiators, electrolytes, and molecular weight regulators in water at a temperature of about 30 ° C. have.
- the manufacturing method of the polymer particles is not limited thereto, and an appropriate method may be selected according to the type of the polymer particles.
- the polymer particles may have an average particle diameter of 0.1 ⁇ m to 1 ⁇ m, or 0.1 ⁇ m to 0.7 ⁇ m, or 0.2 ⁇ m to 0.5 ⁇ m in consideration of the air permeability of the separator. If the average particle diameter of the polymer particles is out of the above-mentioned range, pores may be formed in the porous substrate having an inverse opal structure obtained in the last step, too small or large, so that the air permeability and ionic conductivity when applied to the separator for an electrochemical device There are disadvantages to this.
- the size of the polymer particles may be appropriately changed according to a predetermined use or characteristics of the porous substrate and the separator including the same.
- the size of the polymer particles may be appropriately adjusted in consideration of characteristics such as air permeability of the porous substrate, ionic conductivity, diameter of the pores or porosity.
- the particle diameter of the polymer particles has a monomodal distribution.
- the standard deviation of the particle size of the polymer particles is 1% to 35% or 1% to 35%.
- the concentration of the polymer particles in the colloidal solution is 10 to 50% by weight, but is not limited thereto. Since the aqueous medium such as water in the colloidal solution is removed in the drying step described later, it can be appropriately adjusted within a range where excessive drying time or heating temperature is not required.
- the colloidal solution is applied onto a substrate and dried to form a coating layer of polymer particles.
- the coating layer serves as a template for forming a porous substrate in a step to be described later as the polymer particles are formed by forming an opal structure.
- the substrate is not particularly limited to serve as a support for forming the coating layer.
- a glass or silicon wafer can be used as the substrate.
- the coating method of the colloidal solution is not particularly limited.
- Non-limiting examples of the coating method are knife coating, roll coating, curtain coating, cast coating, engraved roll coating, spray coating ( spary coating, foam coating, reverse roll coating, calendar coating, extrusion coating, dip coating or air-knife coating coating) can be performed by selecting one of the methods.
- the coating method according to one specific embodiment of the present invention is preferably carried out by a method of dip coating in which the substrate is immersed in a colloidal solution.
- the colloidal solution may be dried under atmospheric pressure or pressurized conditions, and may be dried by applying heat or hot air to the substrate as necessary.
- the drying may be performed using an oven, a gas furnace or an electric furnace.
- the drying may be performed at a temperature condition of 25 ° C. to 100 ° C., preferably 50 ° C. to 80 ° C., but is not limited thereto.
- the drying temperature or drying time may be appropriately selected depending on the process conditions such as the concentration of the colloidal solution or the type of the polymer particles.
- FIG. 3 schematically shows a process diagram of the production of the reverse opal structure of the present invention, schematically showing an example of the polymer particle aggregate of the reverse opal structure obtained after the aqueous medium is dried.
- the aggregate of the opal structure includes a plurality of pores formed between the polymer particles and is used as a template for forming a porous substrate having an inverse opal structure made of a polymer resin in a step to be described later.
- the polymer resin is dispersed in a first organic solvent to prepare a polymer resin dispersion.
- the polymer particles comprise a crosslinked polymer polymer. Since the polymer resin is used as a porous substrate of a separator having an inverse opal structure, it is preferable that the polymer resin is crosslinked to prevent dissolution in a polar solvent or an organic solvent such as an electrolyte after battery assembly. According to one specific embodiment of the present invention, the polymer resin has a crosslinking degree (or gel fraction) of 40% or more, or 50% or more, or 70% or more, or 80% or more, or 90% or more. The measurement of the degree of crosslinking is as described above.
- the polymer resin is a high heat resistance engineering plastic resin.
- the engineering plastic resin is characterized in that the heat resistance temperature is 150 °C or more, preferably 180 °C or more, most preferably 200 °C or more.
- polyolefin resins are extruded, stretched, and relaxed, and are used as separators made of a nonwoven fabric after the polyolefin resin is processed into fibers.
- a polyolefin resin has a severe heat shrinkage at a high temperature, and has a disadvantage of physically weak.
- the present inventors applied a high heat-resistant engineering plastic resin having a heat resistance temperature of 150 ° C. or higher to the separator so that it can be used stably even when the electrochemical device is overheated. Provide a separation membrane.
- the high heat-resistant engineering plastic resin has a disadvantage in processing, such as the use of a high-temperature injection process without a lot of solvent to dissolve in producing a porous membrane by a conventional method.
- the present invention provides a novel method for producing a porous separator having excellent ion conductivity and air permeability by applying a method for preparing an inverse opal structure to a high heat resistant engineering plastic resin.
- the high heat resistance engineering plastic resin is not limited thereto, but according to one preferred embodiment of the present invention, polysulfone (PSF), polyethersulfone (PES), polyetherimide (PEI), polyphenylene sulfide (PPS) ), Polyether ether ketone (PEEK), polyarylate (PA) and polyamideimide (PAI), one or a mixture of two or more selected from the group consisting of polyimide (PI).
- PSF polysulfone
- PES polyethersulfone
- PEI polyetherimide
- PPS polyphenylene sulfide
- PEEK Polyether ether ketone
- PA polyarylate
- PAI polyamideimide
- PI polyamideimide
- the high heat resistance engineering plastic resin has a molecular weight of 100,000 Da to 10,000,000 Da, preferably 500,000 Da or more.
- the high heat resistance engineering plastic resin is a linear polyimide or an aromatic heterocyclic polyimide having an imide group in its main chain. Or a copolymer resin including a monomer including the imide group.
- the first organic solvent may be a chlorine-based organic solvent.
- the chlorine-based organic solvent one or a mixture of two or more selected from the group consisting of chloroform, methylene chloride, carbon tetrachloride, carbon dichloride, ethane trichloride, vinyl chloride, ethylene dichloride, ethylene trichloride and ethylene tetrachloride can be used. Can be.
- the opal structure formed in the polymer substrate is filled with the polymer dispersion liquid obtained above.
- the filling may be performed by immersing the substrate coated with the template of the polymer particles in the polymer dispersion.
- the substrate coated with the template of the opal structure is immersed in a container containing a polymer dispersion.
- the substrate is immersed in the dispersion and left for a few minutes to several hours so that the polymer dispersion is evenly infiltrated into the interparticle pores formed in the opal structure.
- the immersion may be performed under pressurized conditions so that the penetration of the dispersion into the voids occurs effectively.
- the substrate is taken out of the dispersion and dried to cure the polymer resin dispersion.
- the drying may be performed at atmospheric pressure or pressurized conditions, and drying may be performed by applying heat or wind or hot air to the substrate as necessary. Since the polymer particles used in the template of the opal structure have high solubility, the polymer particles are not dissolved by the solvent contained in the polymer dispersion and the template is firmly maintained so that the reverse opal structure can be effectively produced. Therefore, the polymer dispersion is preferably dried quickly using heat or hot air. According to one preferred embodiment of the invention the drying may use an oven, gas furnace or electric furnace. The drying temperature may be performed at a temperature of 30 °C to 80 °C, preferably 50 °C to 80 °C. When the temperature exceeds 80 ° C, the polymer may be heated above the glass transition temperature to cause a change in shape.
- the second organic solvent is a solvent capable of dissolving only the polymer particles without dissolving the polymer resin, and a solvent having high selectivity to the polymer particles is used.
- the second organic solvent may be appropriately selected in consideration of the polymer particles or polymer resin used.
- toluene, chloroform, NMP, or the like can be used as the second organic solvent.
- dissolution of the polymer particles is performed by immersing the substrate filled with the polymer resin in a second organic solvent.
- this step can be carried out under heating conditions in order for the dissolution to be carried out effectively.
- the heating may be carried out at a temperature of 30 °C to 50 °C, preferably 30 °C to 40 °C.
- the second solvent is selective to the polymer particles, only the polymer particles are dissolved in the coating layer of the polymer particles, and the polymer resin is not dissolved. Therefore, only the polymer particles forming the opal structure are dissolved and removed to finally form a porous substrate of a polymer resin having an inverse opal structure.
- a second aspect of the present invention is a separator for an electrochemical device comprising the porous substrate and the porous substrate by the above method.
- the thickness or pore distribution must be uniform. For example, if the thickness of a specific part of the membrane is thinner than other parts, or if the porosity of the specific part of the membrane is higher than that of other parts, the ion conductivity of the part is increased and current is concentrated in that part during charging and discharging.
- the active material at the site reacts preferentially to generate a large distribution in both directions in the state of charge (SOC). This distribution accelerates the deterioration of the cell, which reduces the stability and reliability of the cell. In particular, it shows insufficient performance such as current leakage in instantaneous high current instantaneous discharge (10 seconds).
- the porous substrate for a separator according to the present invention is obtained from a template having an opal structure in which polymer particles have a predetermined rule. Therefore, the porous substrate prepared according to the method of the present invention has a considerably high uniformity in terms of the shape, size and distribution of the pores according to the regularity of the opal structure. Therefore, the battery using this as a separator has excellent resistance characteristics and high output characteristics, and even in the case of high current instantaneous discharge (10 seconds), there is an effect of preventing leakage of current.
- the separator substrate may have a pore diameter of 0.1 ⁇ m to 1 ⁇ m, or 0.1 ⁇ m to 0.7 ⁇ m, or 0.2 ⁇ m to 0.5 ⁇ m.
- the pores in the porous substrate may be defined as having a standard deviation within a range of 1% or more and less than 30%, preferably, within a range of 1% or more and 20% or less. . Since the pore diameter depends on the particle diameter of the polymer particles used as a template, the particle diameter of the polymer particles preferably exhibits a monomodal distribution so that a uniform pore distribution can be obtained.
- the porous substrate may have a breathability of 50 sec / 100 cc to 800 sec / 100 cc or 100 sec / 100 cc to 500 sec / 100. In one specific embodiment of the present invention, the porous substrate has a thickness of 10 ⁇ m to 40 ⁇ m.
- a third aspect of the present invention is a separator comprising a porous substrate prepared by the above method, an electrode assembly comprising the separator and an electrochemical device comprising the electrode assembly. That is, in the electrochemical device, the separator according to the present invention can be usefully used as the separator interposed between the cathode and the anode.
- the separator comprises a porous substrate according to the present invention.
- the separator may be one layer of the separator substrate or may be a laminate of the separator substrate in a plurality of layers.
- the porous film in which the polyolefin-based polymer resin is formed by a dry method or a wet method and the porous substrate according to the present invention may be laminated in multiple layers.
- the separator may further include an organic / inorganic composite porous coating layer formed by mixing inorganic particles and a binder resin on at least one surface of the separator.
- the composite porous coating layer is the inorganic particles are fixed to each other by the point bonding between the particles and / or surface bonding through the binder polymer resin to maintain the physical shape of the coating layer, by the interstitial volume of the inorganic particles It is a porous structure having a plurality of fine pores formed.
- the porous coating layer has a thickness of 1 ⁇ m to 30 ⁇ m or 1 to 1 ⁇ m to 20 ⁇ m or 1 ⁇ m to 15 ⁇ m.
- the size of the inorganic particles is not limited, but in order to form a uniform film thickness and proper porosity, it is preferable that the range of 0.001 ⁇ m to 10 ⁇ m, in a specific embodiment of the present invention, the content of the inorganic particles is the porous More preferably from 50% to 99% by weight or from 60% to 95% by weight per 100% by weight of the coating layer.
- An electrochemical device includes all devices that undergo an electrochemical reaction, and specific examples include capacitors such as all kinds of primary cells, secondary cells, fuel cells, solar cells, or supercapacitor elements.
- the secondary battery may include a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery.
- the electrode to be applied together with the separator according to the present invention is not particularly limited, and according to a conventional method known in the art, the electrode active material may be prepared in a form bound to the electrode current collector.
- the positive electrode active material of the electrode active material may be a conventional positive electrode active material that can be used for the positive electrode of the conventional electrochemical device, in particular lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium iron oxide or a combination thereof
- One lithium composite oxide can be used.
- Non-limiting examples of the negative electrode active material may be a conventional negative electrode active material that can be used in the negative electrode of the conventional electrochemical device, in particular lithium metal or lithium alloys, carbon, petroleum coke, activated carbon, Lithium adsorbents such as graphite or other carbons can be used.
- Non-limiting examples of the positive electrode current collector is a foil made by aluminum, nickel or a combination thereof, and non-limiting examples of the negative electrode current collector by copper, gold, nickel or copper alloy or a combination thereof Foils produced.
- Electrolyte that may be used in the electrochemical device in accordance with one aspect of the present invention is A + B - A salt of the structure, such as, A + is Li +, Na +, an alkali metal cation or an ion composed of a combination thereof, such as K + It includes and B a - is PF 6 -, BF 4 -, Cl -, Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C (CF 2 SO 2) 3 - anion, or a salt containing an ion composed of a combination of propylene carbonate (PC) such as, ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC ), Dipropyl carbonate (DPC), dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran
- the electrolyte injection may be performed at an appropriate stage of the battery manufacturing process, depending on the manufacturing process and the required physical properties of the final product. That is, it may be applied before the battery assembly or at the end of battery assembly.
- a lamination (stacking) and folding (folding) process of the separator and the electrode may be performed in addition to the general winding process.
- Polystyrene (PS) particles having an average particle diameter of 300 nm were dispersed on a glass substrate, and then dried in an oven at 70 degrees Celsius to form a template film having a thickness of 30 um. Thereafter, a polyethermide-dispersed methylene chloride solution (5 wt %) was poured on and dried in the same oven for 5 min to obtain a film filled with a polymer resin. After the film was made, it was ultrasonically washed with toluene for 10 minutes to remove the PS particles and to obtain a porous membrane (porous substrate).
- PS Polystyrene
- Silica particles having an average particle diameter of 300 nm were dispersed on a glass substrate, and then dried in an oven at 70 degrees Celsius to form a template film having a thickness of 30 um. Thereafter, a polyetherimide dispersed methylene chloride solution (5 wt%) was poured thereon. Drying in the same oven for 5 min yielded a film filled with polyetherimide. Next, the film was soaked in HF solution for 1 hour and the membrane was ultrasonically washed to obtain a membrane with pores.
- Example 1 After the spherical particles were removed from Example 1 and Comparative Example 1, an inverse opal structure composed of polyetherimide was formed.
- polystyrene particles were used on the surface in Example 1, they appeared to be cleanly removed, but in Comparative Example 1, it was confirmed that the degraded particles using silica particles formed small granules.
- the shape showed a body-centered cubic structure or a face-centered cubic structure, and the porosity of the structural calculations based on the cross section is about 72% in Example 1, and about 70% in the comparative example.
- the comparative example is similar in structure to that of Example 1 but appears to be slightly less due to the aggregation of particles during hydrofluoric acid treatment.
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Abstract
Description
Claims (17)
- 고분자 입자를 포함하는 콜로이드 용액을 준비하는 단계(S10);상기 콜로이드 용액을 기재에 코팅하여 오팔 구조를 갖는 고분자 입자의 코팅층을 형성하는 단계(S20);고분자 수지를 제1 유기 용매에 분산시킨 고분자 수지 분산액을 준비하는 단계(S30);상기 고분자 수지 분산액으로 고분자 입자의 오팔 구조를 충전(filling)하는 단계 (S40); 및제2 유기 용매를 이용하여 고분자 입자를 용해하는 단계(S50);을 포함하는, 역오팔 구조를 갖는 다공성 기재의 제조 방법.
- 제1항에 있어서,상기 고분자 입자는 가교되지 않은 고분자 중합체이며, 상기 고분자 수지는 가교된 고분자 중합체인 것인, 역오팔 구조를 갖는 다공성 기재의 제조 방법.
- 제1항에 있어서,상기 고분자 입자는 스타이렌-부타디엔 러버(SBR), 폴리부타디엔 러버, 폴리플로로프렌(네오프렌), 니트릴 러버, 아크릴 러버, 불소계 고무(FKM), PVC, 폴리스티렌, 폴리스티렌, 폴리메틸메타크릴레이트(PMMA), 아크릴로니트릴-부타디엔-스티렌(ABS), 폴리비닐리덴 플루오라이드, 폴리비닐 플루오라이드, PTFE, 폴리비닐 아세테이트나 이의 공중합체, 비닐아세테이트-에틸렌 공중합체로 이루어진 그룹에서 선택된 1종 또는 2종 이상인 것인, 역오팔 구조를 갖는 다공성 기재의 제조 방법.
- 제1항에 있어서,상기 고분자 입자의 직경은 0.1㎛ 내지 1㎛인 것인, 역오팔 구조를 갖는 다공성 기재의 제조 방법.
- 제1항에 있어서,상기 고분자 수지는 고내열성 플라스틱 엔지니어링 수지인 것인, 역오팔 구조를 갖는 다공성 기재의 제조 방법.
- 제5 항에 있어서,상기 고내열성 플라스틱 엔지니어링 수지는 폴리술폰(PSF), 폴리에테르술폰(PES), 폴리에테르이미드(PEI), 폴리페닐렌술포이드(PPS), 폴리에테르에테르케튼(PEEK), 폴리아릴레이트(PA) 및 폴리아미드이미드(PAI), 폴리이미드(PI)으로 이루어진 그룹에서 선택된 1종 또는 2종 이상인 것인, 역오팔 구조를 갖는 다공성 기재의 제조 방법.
- 제1항에 있어서,상기 제1 유기 용매는 염소계 유기 용매인 것인, 역오팔 구조를 갖는 다공성 기재의 제조 방법.
- 제1항에 있어서,상기 제2 유기 용매는 고분자 입자를 선택적으로 용해할 수 있는 것인, 역오팔 구조를 갖는 다공성 기재의 제조 방법.
- 음극, 양극 및 상기 음극 및 양극 사이에 개재되는 분리막을 포함하며, 상기 분리막은 제1항 내지 제8항 중 어느 한 항에 따른 방법에 의해 제조된 다공성 기재를 포함하는 것인, 전극 조립체.
- 제9항에 따른 전극 조립체를 포함하는 전기 화학 소자.
- 전기화학소자용 다공성 기재에 있어서,상기 다공성 기재는 역오팔 구조을 갖고,상기 다공성 기재의 표면 및 내부에는 복수의 기공이 존재하며 상기 기공의 직경에 대한 표준 편차가 1% 내지 35%인 것인, 다공성 기재.
- 제11항에 있어서,상기 기공은 직경은 0.1㎛ 내지 1㎛인 것인, 다공성 기재.
- 제11항에 있어서,상기 다공성 기재는 고내열성 플라스틱 엔지니어링 수지를 갖는 것인, 다공성 기재.
- 제13항에 있어서,상기 고내열성 플라스틱 엔지니어링 수지는 폴리술폰(PSF), 폴리에테르술폰(PES), 폴리에테르이미드(PEI), 폴리페닐렌술포이드(PPS), 폴리에테르에테르케튼(PEEK), 폴리아릴레이트(PA) 및 폴리아미드이미드(PAI), 폴리이미드(PI)으로 이루어진 그룹에서 선택된 1종 또는 2종 이상인 것인, 다공성 기재.
- 제13항에 있어서,상기 고내열성 플라스틱 엔지니어링 수지는 분자량이 100,000 Da 내지 10,000,000 Da인 것인, 다공성 기재.
- 제13항에 있어서,상기 고내열성 플라스틱 엔지니어링 수지는 주쇄에 이미드(imide)기를 포함하는 선형 폴리이미드 또는 방향족 헤테로 고리 폴리이미드인 것인, 다공성 기재.
- 제11항에 있어서,상기 다공성 기재는 가교된 고분자 수지를 포함하는 것인, 다공성 기재.
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JP2016526929A JP6316417B2 (ja) | 2013-10-31 | 2014-10-31 | 逆オパール構造の多孔性基材を含む電気化学素子用多孔性分離膜及びこの製造方法 |
US14/771,720 US10115952B2 (en) | 2013-10-31 | 2014-10-31 | Porous separator having inverse opal structure for secondary battery and method for manufacturing the same |
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TW201529653A (zh) | 2015-08-01 |
EP2950367A4 (en) | 2016-08-10 |
KR20150050513A (ko) | 2015-05-08 |
EP2950367A1 (en) | 2015-12-02 |
JP6316417B2 (ja) | 2018-04-25 |
EP2950367B1 (en) | 2019-01-02 |
US20160013464A1 (en) | 2016-01-14 |
CN105051942A (zh) | 2015-11-11 |
JP2016536750A (ja) | 2016-11-24 |
KR101693778B1 (ko) | 2017-01-06 |
US10115952B2 (en) | 2018-10-30 |
TWI526484B (zh) | 2016-03-21 |
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