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WO2015060698A1 - Procédé pour appliquer un liant adhésif sur une membrane de séparation - Google Patents

Procédé pour appliquer un liant adhésif sur une membrane de séparation Download PDF

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Publication number
WO2015060698A1
WO2015060698A1 PCT/KR2014/010139 KR2014010139W WO2015060698A1 WO 2015060698 A1 WO2015060698 A1 WO 2015060698A1 KR 2014010139 W KR2014010139 W KR 2014010139W WO 2015060698 A1 WO2015060698 A1 WO 2015060698A1
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WO
WIPO (PCT)
Prior art keywords
separator
binder
adhesive binder
layer
pattern
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/010139
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English (en)
Korean (ko)
Inventor
구용성
김준형
김석구
홍장혁
진선미
유인경
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2016526015A priority Critical patent/JP2017500688A/ja
Priority to CN201480058708.0A priority patent/CN105684190A/zh
Priority claimed from KR1020140146177A external-priority patent/KR20150048082A/ko
Publication of WO2015060698A1 publication Critical patent/WO2015060698A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • 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

Definitions

  • the present invention relates to a method of applying the adhesive binder to the separator for secondary batteries. More specifically, the present invention relates to a method of applying an adhesive binder to a separator in a predetermined pattern using printing and transfer methods.
  • a secondary battery such as a lithium secondary battery has an electrode assembly having a positive electrode, a negative electrode, and a separator, such an electrode assembly is a jelly-roll type wound around the positive electrode and the negative electrode with a separator interposed therebetween,
  • a stack type of a stack of anodes, cathodes and separators sequentially, and a mixture of these, a unit cell consisting of anodes, cathodes and separators is a long sheet-like continuous folding film (e.g. It is divided into a stack-folding type lithium secondary battery, which is bent / wound using a separator).
  • Such a stack-foldable lithium secondary battery is easy to manufacture, has a structure capable of efficiently utilizing space, and can maximize a content of an electrode active material to realize a battery of high integration.
  • Separators used in these secondary batteries are porous woven or nonwoven fabrics, or in the case of films or membranes, porous membranes in which pores are formed through a dry method or a wet method.
  • these porous separators use a binder for bonding with the electrode, which is not only coated on the surface of the porous substrate but also penetrates into the pores of the porous substrate, thereby impairing the ion channel function of the membrane. have.
  • such a porous separator is assembled with an electrode to form an electrode assembly or a battery (cell), in which case the volume of the porous separator in the electrode assembly or battery should be minimized, in order to achieve this, the thickness of the binder layer on the porous substrate It is necessary to make it as thin as possible. In addition, when the thickness of the binder layer is not kept constant, there is still a problem such as local weakness against external force.
  • the present invention has been made in order to solve the above problems, and excellent on the porosity, thickness and durability of the porous separator and the porosity, thickness and durability of the porous separator of the secondary battery on the porous separator so as to minimize It is an object to provide a novel method of applying an adhesive binder.
  • an object of the present invention is to provide an electrode assembly comprising a porous separator coated with an adhesive binder in the above method.
  • the present invention provides a method for forming an adhesive binder layer on the surface of the separator for an electrochemical device in order to solve the above technical problem.
  • the method includes (S1) preparing a binder solution by mixing a binder resin and an organic solvent; (S2) printing the binder solution in a predetermined pattern on the surface of the transfer member to form a pattern of the binder solution on the surface; (S3) removing the solvent from the printed binder solution to form a pattern of the adhesive binder; (S4) transferring the pattern of the adhesive binder to at least one side of the separator from the surface of the transfer member; And (S5) forming the adhesive binder layer on at least one side of the separator through the step (S4).
  • the step (S2) may be performed using an inkjet printer, a dispenser or a nozzle.
  • the transfer member may be one or more selected from the group consisting of a plate, a film, a frame, a roller, a cylinder, and an endless belt. Can be.
  • the step (S3) may be performed by heating the pattern of the binder solution formed on the surface of the transfer member.
  • the transfer member may be a release treatment on the surface.
  • the pattern of the binder solution or the pattern of the adhesive binder may be patterned to include a non-coating area in which the adhesive binder is not applied to the separator surface.
  • the pattern of the binder solution or the pattern of the adhesive binder is from the group consisting of dot, circle, polygon, donut, stripe and grid It may consist of one selected subunit pattern or a combination of two or more subunit patterns.
  • the adhesive binder layer has a thickness of 0.1 to 10 ⁇ m.
  • step (S4) may be performed by pressing the contact surface of the transfer member and the separator.
  • the separator is a separator for an electrochemical device.
  • the separator may include a polyolefin porous substrate.
  • the separator is a polyolefin porous substrate and the organic / inorganic composite porous layer is formed on at least one surface of the polyolefin porous substrate, the organic / inorganic composite porous layer may include a plurality of inorganic particles and a binder resin. .
  • the present invention provides a porous substrate for an electrochemical device comprising a separator substrate comprising a polyolefin-based porous substrate and an adhesive binder layer formed on at least one side of the separator.
  • the adhesive binder layer is formed by any of the above-described methods.
  • the separator substrate is an organic / inorganic composite porous coating layer is formed on at least one side of the polyolefin-based porous substrate, the organic / inorganic composite porous coating layer may include a plurality of inorganic particles and a binder resin.
  • the binder When the adhesive binder is applied to the porous separator by the method according to the present invention, the binder is not absorbed into the porous separator and is distributed on the surface of the separator in a predetermined pattern. Therefore, the binding force between the porous separator and other electrochemical elements such as electrodes is improved.
  • the surface of the separator includes a non-coating area to which no binder is applied, and the surface of the separator is exposed to the outside, so that when the separator is bound with other electrochemical elements such as electrodes, Effects on porosity, ionic conductivity, thickness uniformity and durability are minimized.
  • FIG. 1 is a process flow diagram for the preparation of a porous separator according to an embodiment of the present invention.
  • Figure 2a briefly shows that when the binder is applied to the porous separator according to the conventional binder coating method, the binder penetrates into the porous separator and the binding force on the surface is lowered.
  • Figure 2b shows the binder distribution on the porous separator according to an embodiment of the present invention.
  • FIG 3 shows an example of a transfer process of a binder pattern using a release transfer roller having irregularities formed according to one embodiment of the present invention.
  • FIG. 4 illustrates an example of a transfer process of a binder pattern using a transfer member having irregularities formed on a surface according to one embodiment of the present invention.
  • FIG. 5 is a photograph showing a reverse transfer phenomenon of the binder pattern layer generated when a pressure in a suitable transfer process and a pressure exceeding the pressure in the transfer process according to an embodiment of the present invention is applied.
  • Example 6 is an optical micrograph on a transfer member before transfer according to Example 2 of the present invention, and an electron micrograph of a binder layer transferred from the transfer member onto a porous substrate.
  • FIG. 8 is an electron micrograph of a surface having no inorganic porous coating layer and a surface having an inorganic porous coating layer according to an embodiment of a dot in Example 1 of the present invention.
  • the present invention relates to a method of applying the adhesive binder to the surface of the separator in a predetermined pattern for binding the separator and other electrochemical devices.
  • the method includes preparing a binder solution by mixing a binder resin and an organic solvent; Printing the binder solution on a surface of a transfer member in a predetermined pattern to form a pattern of the binder solution on the surface; Removing a solvent from the printed binder solution to form a pattern of an adhesive binder; Transferring the pattern of the adhesive binder to at least one surface of the separator from the surface of the transfer member; And forming a pattern layer of the adhesive binder on at least one surface of the separator through the step.
  • the adhesive binder is finally transferred to at least one surface of the separator to form a pattern layer on the separator.
  • the binder is coated on the surface of the separator substrate by the above method, when the porous substrate is used as the separator, the bonding properties of the separator and other electrochemical elements are maintained, but the porosity of the separator substrate and the conductivity of lithium ions are not impaired.
  • the binder solution is directly applied to the separator, particularly in the case of the porous separator, the binder solution penetrates through the pores, so that the amount of binder required for binding to the surface is insufficient, and the pores of the separator are blocked by the binder solution. .
  • 2A and 2B schematically illustrate a method of forming a binder layer on a surface of a porous separator.
  • 2a illustrates a method of forming a binder layer according to the prior art.
  • the binder solution is directly applied to the surface of the porous separator to form a binder layer.
  • the binder solution penetrates into pores in the separator before the binder solution is dried. There is a problem that the air permeability of the separator is lowered.
  • the present invention solves this problem, the binder solution is not directly applied to the separator, but the pattern layer of the adhesive binder in the solvent removed state is transferred to the surface of the separator, the pore closure of the separator by the binder solvent does not occur, the separation membrane
  • the air permeability of is excellent and the binding force with other electrochemical elements, such as an electrode, is given (refer FIG. 2B).
  • the adhesive binder is formed in a pattern including the non-coating portion, the separator surface of the non-coating portion is exposed to the outside to provide excellent ventilation.
  • FIG. 1 is a flow chart briefly explaining a method of applying an adhesive binder on the surface of the separator of the present invention.
  • a binder solution is prepared (S1).
  • the binder solution may be prepared in the form of a mixture of a binder resin and a solvent in which the binder resin is dispersed in an organic solvent.
  • the content of the binder resin may vary depending on the thickness of the binder pattern layer formed in a later step.
  • the binder resin may be included in a ratio of about 1 to about 30 parts by weight, preferably about 5 to about 20 parts by weight, based on 100 parts by weight of the binder solution.
  • the binder resin may be a polyvinylidene fluoride (PVdF, polyvinylidene fluoride) resin, styrene-butadiene rubber (SBR, styrene-butadiene rubber), polytetrafluoroethylene (PTFE, polytetrafluoroethylene), polyethylene glycol (PEG, polyethylene glycol) ), Polypropylene glycol (PPG), toluene diisocyanate (TDI), polymethylmethacrylate (polymethylmethacrylate), polyacrylonitrile, polyvinylpyrrolidone (polyvinylpyrrolidone), polyvinyl Acetate (polyvinylacetate), ethylene-co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate cellulose acetate propionate, cyanoethylpullulan, cyanoe Polyvinyl alcohol (cyanoeth
  • PVDF polyvinylidene fluoride
  • polyvinylidene fluoride-co-hexafluoropropylene polyvinylidene fluoride-co-trichloroethylene
  • a solvent having a similar solubility index to the binder resin used so that the solvent can be uniformly mixed with the binder resin used.
  • a solvent having a high boiling point in order to prevent the nozzle from being blocked when the binder solution is sprayed through a nozzle such as an ink jet printer in the following steps.
  • the boiling point is too high in order to effectively remove the organic solvent.
  • the solvent has a boiling point of 80 ° C to 180 ° C, or 100 ° C to 165 ° C.
  • non-limiting examples of the solvent are cyclohexane, mesitylene, dimethylacetamide, dimethylsulfone, dimethylcarbonate, acetone, tetra Tetrahydrofuran, methylene chloride, chloroform, dimethylformamide, N-methyl-2-pyrrolidone (NMP), water, methylethyl It may be one or a mixture of two or more selected from the group consisting of ketone (methyl ethyl ketone), methyl acetate (methyl acetate), cyclohexanone (cyclohexanone).
  • the solvent may be one, or a mixture of two or more selected from cyclohexane, mesitylene, dimethylacetamide, dimethylsulfone, and dimethylcarbonate.
  • the binder solution is printed on the surface of the transfer member in a predetermined pattern to form a pattern of the binder solution on the surface of the transfer member (S2).
  • the printing method is not particularly limited as long as it is a printing process capable of forming a pattern of a binder solution on the surface of the transfer member.
  • the printing may be performed using an inkjet printer, a dispenser or a nozzle.
  • the transfer member is not particularly limited as long as it can serve to transfer the pattern formed on the surface of the transfer member to another surface such as the surface of the separator substrate in a later step.
  • the transfer member may be, for example, in the form of a plate, film, frame, roller, cylinder, endless belt, or the like (FIG. 3). And FIG. 4). Specifically, a transfer roller, a roll liner or a plate liner can be used. The transfer member may then be heated to remove the organic solvent from the printed binder solution. Therefore, the transfer member may be made of a metal or ceramic having heat resistance.
  • the transfer member may include a support member made of metal or ceramic and an elastic member formed of a chemical or heat resistant resin such as silicone, polyurethane, polydimethylsiloxane (PDMS), and Teflon on the surface of the support member.
  • a support member made of metal or ceramic
  • an elastic member formed of a chemical or heat resistant resin such as silicone, polyurethane, polydimethylsiloxane (PDMS), and Teflon on the surface of the support member.
  • the surface of the transfer member may be provided with a release layer that has been released.
  • the surface of the transfer member may be directly released.
  • a release film or film may be provided on the surface of the transfer member.
  • the transfer member is a film transfer member having a release treated surface. More specifically, it is a PDMS release film.
  • the release layer lowers the surface energy of the transfer member so that an adhesive material such as an adhesive is attached to the surface, and then the adhesive material can be easily moved (transferred) to the surface of another object.
  • the release treatment may be, for example, irregularities are formed on the surface.
  • the shape of the irregularities, the interval between the irregularities, the width or height of the irregularities may be appropriately modified according to the shape and material of the pattern to be transferred.
  • the solvent is removed from the binder solution printed on the surface of the transfer member (S3). Removal of the solvent may be performed by heating the pattern of the binder solution.
  • the heating may be typically performed through a heating process such as a heater, an oven, resistance heating, electric induction heating, hot air heating, infrared heating, or the like.
  • the transfer member may have a function as a support for printing a binder solution as well as a means for removing the organic solvent included in the binder solution by drying the binder solution. Therefore, the heating may be performed by a method of heating the transfer member by providing the transfer member with a heating means as described above.
  • the heating may be performed at a temperature range of about 40 ° C to about 200 ° C, preferably at a temperature of about 60 ° C to about 150 ° C, more preferably about 80 ° C to about 120 ° C. In addition, the heating may be performed for about 3 to about 180 seconds, preferably about 1 to about 60 seconds.
  • the solvent remains in a range of 10 parts by weight or less, preferably 5 parts by weight or less, most preferably 1 parts by weight or less, relative to 100 parts by weight of the binder solution. Can be removed.
  • the solvent is removed in the above-described content range in the binder solution, the adhesiveness of the binder pattern is increased, so that the initial print pattern is well maintained during the transfer of the binder solution, thereby enabling the transfer of the pattern at the ⁇ m level. It is also advantageous to achieve high transfer rates of the dried binder solution to the separator surface.
  • the resultant in which the adhesive is removed from the binder solution to increase the adhesiveness is referred to as an adhesive binder to distinguish it from the binder solution.
  • the binder layer has a predetermined pattern according to the pattern of the adhesive binder printed on the transfer member.
  • the pattern is one pattern subunit selected from the group consisting of pattern subunits such as dot, circle, polygon, donut, stripe and grid. Or it may be composed of a combination of two or more pattern subunits, but is not limited thereto.
  • the pattern can be appropriately modified according to the proportion of the plain portion to be formed on the surface of the separator substrate.
  • the binder layer includes a non-coating area, that is, a portion where the adhesive binder between the pattern subunits is not applied.
  • the plain area is from about 1% to about 50% of the surface area of the separator on which the binder layer is formed.
  • the adhesive binder layer may have a thickness of about 0.1 ⁇ m to about 10 ⁇ m, preferably about 0.1 to about 5 ⁇ m.
  • the binder layer of the present invention may maintain the porosity of the porous substrate in an optimal state together with excellent bonding force between the porous separator and the electrode.
  • FIG. 3 illustrates an example of transferring an adhesive binder to a separator using a transfer roller according to one embodiment of the present invention.
  • 4 illustrates an embodiment of transferring an adhesive binder to a separator using a film transfer member according to one embodiment of the present invention.
  • the transfer step (S4) may be performed by applying a pressure of about 10 to about 100 kgf, preferably about 20 to about 80 kgf. If pressurized beyond the pressure range, the adhesive binder may be transferred to the separator and then transferred back to the transfer member (reverse transfer). Referring to FIG. 5, it can be seen that the adhesive binder was not transferred to the separator but reversely transferred to the transfer member. On the contrary, when the pressure applied is less than the above-mentioned range, the transfer rate of the adhesive binder may be lowered.
  • the pattern of the binder layer is formed such that the subunit patterns are regularly arranged on the surface of the separator at regular intervals.
  • the dot-shaped binder pattern subunits may be distributed on the surface of the separator spaced apart at regular intervals.
  • This arrangement can be used in the case of assembly of the cell, deformation of the cell itself, etc., such as winding, unwinding, folding and compression of the electrode assembly, expansion of the cell components, and the like.
  • the force is uniformly applied to the separator and avoided locally, thereby reducing the possibility of damage such as deformation and tearing.
  • ions are directly passed through the porous separator (pores in the separator) to regions of the porous substrate where the binder is not coated, and thus the ion conductivity and the performance of the battery are improved. Greatly improved.
  • the present invention provides a porous separator for a secondary battery including the adhesive binder layer prepared by the method described above.
  • the separator includes a porous separator base layer and an adhesive binder layer formed on at least one side of the porous base layer.
  • the adhesive binder layer is formed by the above-described method.
  • the porous membrane base layer is a porous membrane, a polymer membrane made of one or more polymer resins, or a multilayer, a woven fabric, a nonwoven fabric, a single film, or a multilayer film in which two or more layers of the polymer membrane are laminated. It may include.
  • the film may have a porous structure by forming pores by a dry method or a wet method known in the art.
  • the separator base layer may include a polyolefin-based porous film.
  • the porous substrate layer has a plurality of pores so as to have a desired porosity and breathability. These pores basically act as a channel of ions in the cell, but when the temperature rises over a certain range due to internal factors such as external factors or short circuits, the inside of the membrane forming the pores melts and collapses to open the passage of the membrane. This prevents further temperature rise of the battery (shutdown).
  • the binder layer according to the present invention maintains a constant thickness of the binder layer on the surface of the transferred separator. Such a constant thickness of the binder layer is then applied to the external separator due to no local biased force on the surface of the binder layer when forming the electrode assembly, cell or battery through the combination of the porous separator (substrate) and the electrode The durability of the separator and the battery can be improved.
  • the porous separator may be an organic / inorganic composite porous layer on at least one side of the porous base layer.
  • the porous separator includes a composite porous layer
  • the binder layer is transferred to the surface of the composite porous layer.
  • the composite porous layer includes a plurality of inorganic particles and a polymer resin.
  • the porous coating layer has a porous property by the pores formed by the interstitial volume between the inorganic particles.
  • the interstitial volume means a space defined by the inorganic particles substantially interviewed in the filling structure of the inorganic particles.
  • the inorganic particles are not particularly limited as long as they are electrochemically stable.
  • the inorganic particles that can be used in the present invention are not particularly limited as long as the oxidation and / or reduction reactions do not occur in the operating voltage range of the battery to be applied (for example, 0 to 5 V on the basis of Li / Li +).
  • the inorganic particles may be, for example, inorganic particles having a dielectric constant of about 5 or more, or inorganic particles having a lithium ion transfer ability (for a lithium secondary battery), alone or in combination thereof.
  • the binder resin is not particularly limited as long as it can provide a binding force between the inorganic particles and a binding force between the inorganic particles and the separator base layer.
  • the content of the inorganic particles in the composite porous layer is 50% to 99% by weight relative to 100% by weight of the composite porous layer.
  • the composite porous layer is prepared by mixing an inorganic particle and a binder resin with a suitable solvent to prepare a slurry for the composite porous layer, which is then known as a dip coating method or a doctor blade coating method on the surface of the porous base layer. It can be formed by applying the slurry in the method of and drying it.
  • the present invention provides an electrode assembly including a porous separator in which the binder layer is formed and an electrochemical device including the electrode assembly.
  • the electrode assembly may be formed by forming an aggregate by placing two counter electrodes, that is, an anode and a cathode on both sides of the separator, and compressing the assembly.
  • the formed aggregate is carried out through a pressing step using two or more oppositely rotating rolls or the like.
  • This compacting step may consist of hot rolling, cold rolling or a combination thereof.
  • Hot rolling is a method of rolling by passing between two rotating rolls at or above the recrystallization temperature of the object, and the hot rolling roll used is a method of rolling an object at a temperature of about 1/2 or more of the melting point (absolute temperature) of the object. It is advantageous for processing.
  • hot rolling may have a low rolling power and has an advantage of easily inducing large deformation. Therefore, the temperature of hot rolling, the rotational speed of the roll, and the like can be adjusted according to the state of the object, that is, the aggregate of the present invention.
  • Cold rolling is a method of rolling using a roll below the recrystallization temperature of the object, and the cold rolling roll used does not need to be different from the hot rolling roll in particular, so that hot rolling or cold rolling may be performed by heating the roll depending on the situation. It can be used as a roll for it.
  • the surface condition of the roll may be reflected in the object without any change to the surface of the object. Therefore, cold rolling can correct defects caused by unevenness, wrinkles, scratches, etc. on the surface of an object (eg, an assembly) that can occur in hot rolling, and can process the thickness of the object thinly, and the dimensional accuracy of the object during processing is high. It is preferable to obtain a desired object (eg, electrode assembly) having a surface that is largely smooth depending on the surface of the cold rolled roll used.
  • the pressing step is carried out under a temperature and a pressure at which the binding force of the binder layer and the object in contact with the separator (ie, the porous separator and the electrode) can be expressed to the maximum, the temperature is about 80 to about 150 °C, preferably Is about 90 to about 110 ° C. and the pressure may be about 30 to about 200 kgf, or about 50 to about 180 kgf.
  • the bonding force of the resulting electrode assembly is greatly increased, and this high bonding force maintains excellent air permeability of the porous separator and the performance of the battery together with the thin thickness of the binder layer. And it can contribute greatly to the improvement of durability.
  • the hot rolling and the cold rolling may be used in combination with each other to make the best use of the advantages.
  • the electrochemical device includes all devices that undergo an electrochemical reaction, and specific examples thereof include all kinds of capacitors such as primary cells, secondary batteries, fuel cells, solar cells, or super capacitor devices.
  • a lithium secondary battery such as a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery is preferable among the secondary batteries.
  • a binder solution 92.5 parts by weight of mesitylene and 7.5 parts by weight of acrylic polymer (Toyo) were dissolved to form a binder solution.
  • the binder solution was printed on a polydimethylsiloxane (PDMS) release film such that a dot pattern having a diameter of about 80 ⁇ m was arranged at intervals of about 500 ⁇ m on the x axis and about 100 ⁇ m on the y axis using an inkjet head.
  • the printed pattern was then heated at a temperature of 60 ° C. for 1-5 seconds to evaporate the solvent.
  • PDMS polydimethylsiloxane
  • the release film was placed on a polypropylene porous substrate having a thickness of 20 ⁇ m (about 45% porosity) such that the pattern faced and pressed using a roll laminator at a pressure of 80 kgf at a temperature of 100 ° C. Subsequently, a separator in which the adhesive binder layer was formed was removed by removing the release film.
  • PVdF-CTFE About 5% by weight of PVdF-CTFE was added to acetone, and then dissolved at a temperature of 50 ° C. for at least 12 hours to prepare a polymer solution.
  • the slurry was coated on a polypropylene substrate (thickness 18 ⁇ m, porosity 45%) to a thickness of about 3.5 ⁇ m using a dip coating method to prepare a separator in which an organic / inorganic composite porous layer was formed.
  • a binder solution 92.5 parts by weight of mesitylene and 7.5 parts by weight of acrylic polymer (Toyo) were dissolved to form a binder solution.
  • the binder solution was printed on a polydimethylsiloxane (PDMS) release film in a lattice pattern having an interval of about 500 ⁇ m ⁇ about 100 ⁇ m using an inkjet head.
  • the printed pattern was then heated at a temperature of 60 ° C. for 1-5 seconds to evaporate the solvent.
  • the release film was disposed so that the pattern faced the separator prepared above, and was pressed using a roll laminator at a pressure of 80 kgf at a temperature of 100 ° C.
  • the separator with an adhesive binder layer was obtained by removing the said release film.
  • the diameter of the dot pattern transferred to the separator is now about 105 ⁇ m compared to that before the transfer from the release film (see FIG. 6).
  • Separation membrane with an adhesive pattern layer was obtained in the same manner as in Example 2 except that the transfer pressure of the binder pattern was 100 kgf.
  • LiMnO 3 , PVdF, and Super C were mixed in a weight ratio of 93: 3: 4 and dispersed in NMP to prepare a positive electrode slurry.
  • the positive electrode slurry was applied to an aluminum current collector thin film (20 ⁇ m), dried, and pressed to prepare a positive electrode.
  • MCMB meocarbon microbead
  • super P PVdF were mixed in a weight ratio of 92: 2: 6, dispersed in NMP, and coated on copper foil to prepare a negative electrode.
  • An electrode assembly having the porous separator interposed between the positive electrode and the negative electrode by interposing the separators prepared in Examples 1 to 3 between the positive electrode and the negative electrode, and using a roll laminator at a temperature of 100 ° C. was prepared.
  • Each roll laminator pressure is as shown in Table 1 below.
  • the adhesion between the electrode and the separator was measured, and the results are summarized in Table 1 below.
  • the binder solution was applied to the surface of the porous separator in which the polypropylene porous substrate and the composite porous layer were formed such that dot patterns having a diameter of about 80 ⁇ m were arranged at intervals shown in Table 1 below using an inkjet head.
  • the porous separator in which the polypropylene porous substrate and the composite porous layer are formed is the same as used in Examples 1 to 3.
  • the binder-coated porous substrate was heated at a temperature of 60 ° C. for 1 minute to evaporate the solvent to obtain a separator.
  • the separator was placed between the positive electrode and the negative electrode and pressed using a roll laminator at a pressure of 150 kgf at a temperature of 100 ° C.
  • the cathode and anode were the same as those used in the examples.
  • the adhesion between the separator and the electrodes of the electrode assemblies of Comparative Examples 1-1 to 1-8 is summarized in Table 2 below.
  • the binder layer was transferred to the porous substrate by the same procedure as in Example 1, but was pressurized using a roll laminator at a pressure of 5 kgf at a temperature of 100 ° C.
  • the binder layer formed between the electrode and the porous separator was reverse-transferred due to lack of binding force in the inorganic material, and thus did not exhibit adhesive properties.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne une membrane de séparation poreuse qui comporte une couche de liant à motifs, un ensemble électrode comportant la membrane de séparation et un procédé de fabrication de la membrane de séparation. Selon un aspect de la présente invention, une membrane de séparation poreuse est utilisée, cette dernière comportant un substrat poreux et une couche de liant à motifs qui est appliquée sur au moins une surface du substrat poreux et qui comprend une région de non enrobage, l'épaisseur selon laquelle la couche de liant est appliquée sur cette dernière étant de 0,1 à 10 µm. Selon un autre aspect de la présente invention, un procédé de fabrication d'une membrane de séparation poreuse est décrit. Le procédé comprend les étapes suivantes : la formation d'une solution de liant ; la formation d'une couche de liant à motifs ; le transfert ; le pressage. Selon un mode de réalisation de la présente invention, une membrane de séparation poreuse possède une porosité, une épaisseur uniforme et une excellente durabilité, et peut être couplée à une électrode avec une excellente force de liaison et une conductance d'ions élevée.
PCT/KR2014/010139 2013-10-25 2014-10-27 Procédé pour appliquer un liant adhésif sur une membrane de séparation Ceased WO2015060698A1 (fr)

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JP2016526015A JP2017500688A (ja) 2013-10-25 2014-10-27 分離膜に粘着性バインダーを塗布する方法
CN201480058708.0A CN105684190A (zh) 2013-10-25 2014-10-27 用于在分离膜上涂覆粘性粘结剂的方法

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KR10-2013-0127903 2013-10-25
KR20130127903 2013-10-25
KR1020140146177A KR20150048082A (ko) 2013-10-25 2014-10-27 분리막에 점착성 바인더를 도포하는 방법
KR10-2014-0146177 2014-10-27

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WO2019240500A1 (fr) 2018-06-12 2019-12-19 주식회사 엘지화학 Séparateur pour dispositif électrochimique, ayant une couche adhésive d'électrode à motifs, et procédé de fabrication de séparateur
CN110911622A (zh) * 2019-10-31 2020-03-24 东莞东阳光科研发有限公司 涂覆隔膜浆料、复合隔膜及其制备方法
CN111129406A (zh) * 2019-12-31 2020-05-08 湖北亿纬动力有限公司 一种水系高粘性涂胶隔膜、其制备方法和在电池中的应用
US20200331234A1 (en) * 2017-08-21 2020-10-22 Zeon Corporation Laminate for non-aqueous secondary battery and method of producing same, roll for non-aqueous secondary battery, and method of producing non-aqueous secondary battery component
CN115347320A (zh) * 2022-08-08 2022-11-15 珠海冠宇电池股份有限公司 一种隔膜及包括该隔膜的电池
CN119361969A (zh) * 2024-12-26 2025-01-24 港华能源创科(深圳)有限公司 一种用于水系锌基电池的复合隔膜及其制备方法和应用

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US20200331234A1 (en) * 2017-08-21 2020-10-22 Zeon Corporation Laminate for non-aqueous secondary battery and method of producing same, roll for non-aqueous secondary battery, and method of producing non-aqueous secondary battery component
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WO2019240500A1 (fr) 2018-06-12 2019-12-19 주식회사 엘지화학 Séparateur pour dispositif électrochimique, ayant une couche adhésive d'électrode à motifs, et procédé de fabrication de séparateur
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CN110911622A (zh) * 2019-10-31 2020-03-24 东莞东阳光科研发有限公司 涂覆隔膜浆料、复合隔膜及其制备方法
CN111129406A (zh) * 2019-12-31 2020-05-08 湖北亿纬动力有限公司 一种水系高粘性涂胶隔膜、其制备方法和在电池中的应用
CN115347320A (zh) * 2022-08-08 2022-11-15 珠海冠宇电池股份有限公司 一种隔膜及包括该隔膜的电池
CN119361969A (zh) * 2024-12-26 2025-01-24 港华能源创科(深圳)有限公司 一种用于水系锌基电池的复合隔膜及其制备方法和应用
CN119361969B (zh) * 2024-12-26 2025-10-14 港华能源创科(深圳)有限公司 一种用于水系锌基电池的复合隔膜及其制备方法和应用

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