[go: up one dir, main page]

WO2016110894A1 - Séparateur pour une batterie rechargeable non aqueuse, son procédé de fabrication et batterie rechargeable non aqueuse - Google Patents

Séparateur pour une batterie rechargeable non aqueuse, son procédé de fabrication et batterie rechargeable non aqueuse Download PDF

Info

Publication number
WO2016110894A1
WO2016110894A1 PCT/JP2015/006032 JP2015006032W WO2016110894A1 WO 2016110894 A1 WO2016110894 A1 WO 2016110894A1 JP 2015006032 W JP2015006032 W JP 2015006032W WO 2016110894 A1 WO2016110894 A1 WO 2016110894A1
Authority
WO
WIPO (PCT)
Prior art keywords
functional layer
separator
secondary battery
polymer
aqueous secondary
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/JP2015/006032
Other languages
English (en)
Japanese (ja)
Inventor
純之介 秋池
慶 大浦
一輝 浅井
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.)
Zeon Corp
Original Assignee
Zeon Corp
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 Zeon Corp filed Critical Zeon Corp
Priority to CN201580071472.9A priority Critical patent/CN107112480B/zh
Priority to JP2016568172A priority patent/JP6750506B2/ja
Priority to KR1020177017829A priority patent/KR102477891B1/ko
Publication of WO2016110894A1 publication Critical patent/WO2016110894A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M50/443—Particulate material
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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 for a non-aqueous secondary battery, a method for producing a separator for a non-aqueous secondary battery, and a non-aqueous secondary battery.
  • Non-aqueous secondary batteries such as lithium ion secondary batteries (hereinafter sometimes simply referred to as “secondary batteries”) have the characteristics of being small and light, having high energy density, and capable of repeated charge and discharge. Yes, it is used for a wide range of purposes.
  • the non-aqueous secondary battery generally includes a battery member such as a positive electrode, a negative electrode, and a separator that separates the positive electrode and the negative electrode and prevents a short circuit between the positive electrode and the negative electrode.
  • a porous film layer for improving heat resistance and strength, an adhesive layer for bonding battery members, and the like (hereinafter, these are collectively referred to as “functional layer”).
  • battery members are used.
  • a separator formed by forming a functional layer on a separator base material is used as a battery member.
  • thermoplastic polymer having a predetermined glass transition temperature is used for a separator formed by forming an adhesive layer made of a thermoplastic polymer coating layer on a separator substrate made of a polyolefin microporous film.
  • a technique for improving adhesiveness and ionic conductivity has been proposed by adopting a thermoplastic polymer coating layer having a configuration in which a portion including a portion and a portion not including a thermoplastic polymer are present in a sea-island shape.
  • adhesion to an electrode can be improved by using a thermoplastic polymer having a predetermined glass transition temperature, and a portion containing the thermoplastic polymer and the thermoplastic polymer Ion conductivity can be improved by making the part which does not contain be present in the shape of a sea island.
  • the conventional separator described above did not have sufficient adhesion of the adhesive layer (functional layer) in the electrolytic solution. Therefore, the above conventional separator further improves the adhesion of the functional layer in the electrolyte while ensuring ionic conductivity, and the battery characteristics (high temperature cycle characteristics and low temperature output characteristics) of the nonaqueous secondary battery including the separator. There was room for improvement in terms of further improvement.
  • an object of this invention is to provide the separator excellent in the adhesiveness and ionic conductivity in electrolyte solution.
  • Another object of the present invention is to provide a non-aqueous secondary battery that is excellent in high-temperature cycle characteristics and low-temperature output characteristics.
  • this separator which forms this functional layer on a separator base material
  • this inventor has the specific core shell structure provided with the core part and shell part which have the specific electrolyte solution swelling degree about the structure of a functional layer, respectively.
  • the present inventor applied the functional layer composition containing the organic particles on the separator substrate, and when the functional layer composition was dried to form the functional layer on the separator substrate, By setting the water droplet contact angle on the surface of the separator substrate on which the functional layer is formed and the surface tension of the composition for the functional layer within a specific range, a functional layer having the specific configuration described above can be easily formed. Found to get. And this inventor completed this invention based on the new knowledge mentioned above.
  • the separator for non-aqueous secondary batteries of this invention is on a separator base material and at least one surface of the said separator base material.
  • a functional layer formed, and the functional layer has a structure in which a phase of an organic particle having a core-shell structure including a core portion and a shell portion that partially covers an outer surface of the core portion is present in an irregular shape.
  • the core part is made of a polymer having an electrolyte solution swelling degree of 5 times or more and 30 times or less
  • the shell part is made of a polymer having an electrolyte solution swelling degree of more than 1 time and 4 times or less.
  • the ratio of the area of the portion where the organic particle phase is present to the area of the functional layer forming surface of the material is 20% or more and 80% or less.
  • the functional layer including the organic particle phase having the predetermined core-shell structure and properties described above is provided, and the area ratio of the portion where the organic particle phase exists in the functional layer forming surface is 20% or more.
  • the adhesiveness of the functional layer in electrolyte solution can be improved, and the separator excellent in adhesiveness can be provided.
  • the organic particle phase having the predetermined core-shell structure and properties described above is present in an irregular shape, and the area ratio of the portion where the organic particle phase is present in the functional layer forming surface is 80% or less.
  • the separator excellent in ion conductivity can be provided, improving the adhesiveness of the functional layer in electrolyte solution.
  • the “electrolyte swelling degree” of the polymer constituting the core part of the organic particles and the polymer constituting the shell part should be measured using the measuring method described in the examples of the present specification. Can do.
  • “the ratio of the area of the portion where the organic particle phase is present” is determined by observing the functional layer of the separator using a scanning electron microscope (SEM) and in the observation field of view using image analysis software. Can be obtained by calculating the ratio of the area of the portion where the organic particle phase exists.
  • the glass transition temperature of the polymer of the core part is ⁇ 50 ° C. or more and 150 ° C. or less, and the glass transition temperature of the polymer of the shell part is 50 ° C.
  • the temperature is preferably 200 ° C. or lower. If the glass transition temperature of the polymer constituting the core part of the organic particle and the polymer constituting the shell part are within the above-mentioned ranges, respectively, the strength of the organic particle in the electrolytic solution and the adhesion of the functional layer are improved. This is because the handling properties of the separator can be improved.
  • the “glass transition temperature” of the polymer constituting the core part of the organic particles and the polymer constituting the shell part can be measured using the measuring method described in the examples of the present specification. it can.
  • the manufacturing method of the separator for non-aqueous secondary batteries of this invention is the manufacturing method of the separator for non-aqueous secondary batteries mentioned above.
  • the layer composition is moderately repelled on the surface of the separator substrate, a functional layer having a configuration in which the phase of the organic particles exists in an irregular shape can be easily formed. Therefore, the above-described separator having excellent adhesion and ionic conductivity in the electrolytic solution can be easily produced.
  • the “water droplet contact angle” can be determined by dropping 1 ⁇ L of ion-exchanged water on the separator substrate and measuring the contact angle 60 seconds after landing.
  • the “surface tension” of the composition for a non-aqueous secondary battery functional layer can be measured using a plate method.
  • the non-aqueous secondary battery of this invention is equipped with either of the separators for non-aqueous secondary batteries mentioned above, It is characterized by the above-mentioned. To do. As described above, when the above-described separator for non-aqueous secondary battery having excellent adhesion and ionic conductivity in the electrolytic solution is used, a non-aqueous secondary battery having excellent high-temperature cycle characteristics and low-temperature output characteristics can be obtained.
  • the separator excellent in the adhesiveness and ionic conductivity in electrolyte solution can be provided.
  • the separator for a non-aqueous secondary battery of the present invention is used as a separator for a non-aqueous secondary battery such as a lithium ion secondary battery.
  • a non-aqueous secondary battery of the present invention is used.
  • the non-aqueous secondary battery of this invention is equipped with the separator for non-aqueous secondary batteries of this invention.
  • the separator for non-aqueous secondary batteries of this invention is equipped with the separator base material and the functional layer formed on the at least one surface (functional layer formation surface) of a separator base material.
  • the functional layer of the separator for non-aqueous secondary batteries of this invention contains the organic particle which has a specific core-shell structure provided with the core part and shell part which have specific electrolyte solution swelling degree.
  • the organic particles form a phase of organic particles singly or in combination in the functional layer.
  • the phase of the organic particles exists in an irregular shape as shown in, for example, an SEM image of an example of the functional layer in FIG. 1, and exists in a specific area ratio in the functional layer forming surface. .
  • the organic particles are observed as spherical dots having a diameter of about 0.3 to 0.7 ⁇ m.
  • the separator for non-aqueous secondary batteries of this invention since the functional layer containing a specific organic particle is provided, the adhesiveness of the functional layer in electrolyte solution can be improved. Therefore, the separator for non-aqueous secondary batteries of the present invention can exhibit excellent adhesiveness in the electrolytic solution.
  • the organic particle phase is present in an irregular shape, and the ratio of the area of the portion where the organic particle phase exists in the functional layer forming surface is specified. Since it is within the range, good ion conductivity can be ensured while sufficiently enhancing the adhesion of the functional layer in the electrolytic solution.
  • the separator base material on which the functional layer is formed on at least one surface is not particularly limited, and is a known one such as a microporous film described in JP2012-204303A.
  • a separator substrate can be used. Among these, the film thickness of the entire separator can be reduced, thereby increasing the ratio of the electrode active material in the secondary battery and increasing the capacity per volume.
  • a microporous membrane (organic separator substrate) made of a resin of polyethylene, polypropylene, polybutene, or polyvinyl chloride is preferable.
  • a separator base material can be made into arbitrary thickness, Usually, 0.5 micrometer or more, Preferably it is 5 micrometers or more, Usually, 40 micrometers or less, Preferably it is 30 micrometers or less, More preferably, it is 20 micrometers or less.
  • the separator base material may contain an arbitrary layer that can exhibit an intended function other than the functional layer.
  • the surface on the side which forms a functional layer Is preferably 80 ° or more, more preferably 85 ° or more, still more preferably 90 ° or more, and preferably 130 ° or less, more preferably 120 ° or less, still more preferably 110 ° or less. It is preferable to use a microporous membrane. This is because if a separator substrate having a surface with a water droplet contact angle of 80 ° to 130 ° is used, an organic particle phase having an irregular shape and a specific area ratio can be easily formed.
  • the water droplet contact angle on the surface of the separator substrate can be adjusted by using a known method such as, for example, changing the composition of the resin used for forming the microporous film or treating the surface of the microporous film.
  • a resin for example, polyethylene, polypropylene, etc.
  • the contact angle is preferably adjusted by surface treatment of the microporous membrane.
  • the microporous membrane is subjected to surface treatment using dry treatment such as plasma treatment, corona discharge treatment, and UV treatment. It is preferable to perform surface treatment using corona discharge treatment.
  • the treatment strength can be preferably 20 W ⁇ min / m 2 or more, more preferably 30 W ⁇ min / m 2 or more, still more preferably 40 W ⁇ min / m 2 or more, further, preferably 80W ⁇ min / m 2 or less, more preferably 70W ⁇ min / m 2 or less, more preferably be a 60W ⁇ min / m 2 or less.
  • the treatment strength is too high, the water droplet contact angle may be too low.
  • the functional layer formed on the separator substrate may be a porous film layer for improving the heat resistance and strength of the separator, or the separator and the electrode are bonded.
  • the adhesive layer may be a layer that exhibits both functions of the porous membrane layer and the adhesive layer.
  • the functional layer of the separator for a non-aqueous secondary battery according to the present invention includes a core portion made of a polymer having an electrolyte solution swelling degree of 5 times or more and 30 times or less, and an electrolyte solution swelling degree of more than 1 time and less than 4 times. It has a configuration in which a phase of organic particles having a core-shell structure, which is made of a polymer and has a shell part partially covering the outer surface of the core part, exists in an irregular shape.
  • the ratio of the area where the organic particle phase is present is 20% or more and 80% or less with respect to the area of the functional layer forming surface.
  • the functional layer exhibits excellent adhesiveness in the electrolyte and has good ionic conductivity.
  • the separator for a non-aqueous secondary battery of the present invention includes a functional layer having the above-described configuration on one surface and a functional layer having no above-described configuration on the other surface (for example, a function not containing organic particles). Layer or a functional layer in which the area ratio of the phase of the organic particles does not satisfy the above range).
  • the functional layer optionally contains a functional layer binder, non-conductive particles (except those corresponding to organic particles and functional layer binders), and other components. May be.
  • the content of the organic particles in the functional layer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the organic particles contained in the functional layer have a function of exhibiting excellent adhesiveness in the functional layer in the electrolytic solution.
  • the organic particles have a core-shell structure including a core portion and a shell portion that partially covers the outer surface of the core portion.
  • the core portion has an electrolyte swelling degree of 5 times or more and 30 times or less. It is made of a polymer, and the shell part is made of a polymer having an electrolyte solution swelling degree of more than 1 time and 4 times or less.
  • the organic particles having the above structure and properties exhibit excellent adhesiveness in the electrolytic solution, and further, the elution of components into the electrolytic solution is small, and excellent adhesiveness can be maintained for a long time.
  • the functional layer containing an organic particle can improve the battery characteristic of a secondary battery favorably.
  • a separator having a functional layer containing organic particles is less likely to cause blocking (separation between separators via the functional layer). Also, handling is excellent.
  • the polymer constituting the shell portion of the organic particles swells to some extent with respect to the electrolytic solution.
  • the functional group of the polymer in the swollen shell part is activated, and the functional group is formed on the surface of the separator substrate on which the functional layer is formed or on the surface of the electrode or the like bonded to the separator having the functional layer. Due to factors such as causing chemical or electrical interaction with the group, the shell portion can be firmly bonded to the separator substrate, electrodes, and the like.
  • the shell portion does not exhibit a large adhesive force before it swells in the electrolytic solution. Therefore, it is assumed that the functional layer containing the organic particles can strongly bond the separator and the electrode in the electrolytic solution while suppressing the occurrence of blocking.
  • the polymer of the shell part and the polymer of the core part both have an electrolyte solution swelling degree set to a predetermined value or less, and do not swell excessively with respect to the electrolyte solution. Therefore, for example, it is speculated that the excellent adhesiveness described above can be sufficiently exhibited even after the secondary battery is operated for a long time.
  • the functional layer containing the organic particles since the functional layer can exert a strong adhesive force in the electrolyte solution as described above, in the secondary battery including the functional layer, the functional layer is It is difficult to generate a gap between the separator and the electrode bonded via the electrode. Therefore, in a secondary battery using a separator having a functional layer containing the organic particles, the distance between the positive electrode and the negative electrode is difficult to increase in the secondary battery, the internal resistance of the secondary battery can be reduced, and the electric power in the electrode can be reduced. The reaction field for chemical reactions is unlikely to be uneven. Furthermore, in the secondary battery, even if charging and discharging are repeated, it is difficult to form a gap between the separator and the electrode, and the battery capacity is unlikely to decrease.
  • the secondary battery which is excellent in high temperature cycling characteristics etc. can be provided.
  • the polymer constituting the core part of the organic particles swells greatly with respect to the electrolytic solution.
  • the gap between the molecules of the polymer becomes large, and ions easily pass between the molecules.
  • the polymer in the core part of the organic particles is not completely covered by the shell part. Therefore, ions easily pass through the core portion in the electrolytic solution, so that the organic particles can exhibit high ion diffusibility. Therefore, if the organic particles are used, it is possible to suppress an increase in resistance due to the functional layer and to suppress a decrease in battery characteristics such as low-temperature output characteristics.
  • an organic particle exhibits the outstanding adhesiveness by swelling to electrolyte solution, and does not exhibit big adhesive force before being immersed in electrolyte solution.
  • the organic particles do not exhibit adhesiveness unless they are swollen in the electrolytic solution, and are heated to a certain temperature or higher (for example, 50 ° C. or higher) even if they are not swollen in the electrolytic solution. Therefore, adhesiveness can be expressed.
  • the organic particles have a core-shell structure including a core part and a shell part that covers the outer surface of the core part.
  • the shell portion partially covers the outer surface of the core portion. That is, the shell part of the organic particles covers the outer surface of the core part, but does not cover the entire outer surface of the core part. Even if it appears that the outer surface of the core part is completely covered by the shell part, the shell part is outside the core part as long as a hole that communicates the inside and outside of the shell part is formed.
  • a shell part that partially covers the surface Therefore, for example, organic particles including a shell portion having pores communicating from the outer surface of the shell portion (that is, the peripheral surface of the organic particle) to the outer surface of the core portion are included in the organic particles.
  • the organic particle 100 has a core-shell structure including a core part 110 and a shell part 120, as shown in FIG.
  • the core part 110 is a part which is inside the shell part 120 in the organic particle 100.
  • the shell part 120 is a part that covers the outer surface 110 ⁇ / b> S of the core part 110, and is usually the outermost part of the organic particles 100.
  • the shell portion 120 does not cover the entire outer surface 110S of the core portion 110, but partially covers the outer surface 110S of the core portion 110.
  • the average ratio (coverage) at which the outer surface of the core part is covered by the shell part is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more, preferably It is 95% or less, more preferably 90% or less, and still more preferably 80% or less.
  • the coverage is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more, preferably It is 95% or less, more preferably 90% or less, and still more preferably 80% or less.
  • the volume average particle diameter D50 of the organic particles is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 0.2 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and further preferably Is 1 ⁇ m or less.
  • the adhesiveness in electrolyte solution can be improved and the high temperature cycling characteristic of a secondary battery can be improved by making the volume average particle diameter D50 of an organic particle below the upper limit of the said range.
  • the “volume average particle diameter D50” of the organic particles can be measured using the measuring method described in the examples of the present specification.
  • the shell part preferably has an average thickness that falls within a predetermined range with respect to the volume average particle diameter D50 of the organic particles.
  • the average thickness (core-shell ratio) of the shell part with respect to the volume average particle diameter D50 of the organic particles is preferably 1.5% or more, more preferably 3% or more, and even more preferably 5% or more. Is 30% or less, more preferably 25% or less, and still more preferably 20% or less.
  • the organic particles may include arbitrary constituent elements other than the above-described core part and shell part as long as the intended effect is not significantly impaired.
  • the organic particles may have a portion formed of a polymer different from the core portion inside the core portion.
  • the seed particles used when the organic particles are produced by the seed polymerization method may remain inside the core portion.
  • the organic particles include only the core part and the shell part from the viewpoint of remarkably exhibiting the intended effect.
  • the core part of the organic particle is made of a polymer having a predetermined degree of swelling with respect to the electrolytic solution.
  • the electrolyte swelling degree of the polymer of the core part needs to be 5 times or more, preferably 7 times or more, more preferably 8 times or more, and 30 It is necessary that it is not more than twice, preferably not more than 28 times, and more preferably not more than 25 times.
  • the adhesiveness of the functional layer in electrolyte solution can be improved, and the high temperature cycling characteristic of a secondary battery can be improved by making electrolyte solution swelling degree of the polymer of a core part below the upper limit of the said range.
  • the “electrolyte swelling degree” of the polymer of the core part can be measured using the measuring method described in the examples of the present specification.
  • the kind and amount of the monomer used for preparing the polymer of the core part Is appropriately selected.
  • the SP value of a polymer is close to the SP value of an electrolytic solution, the polymer tends to swell in the electrolytic solution.
  • the SP value of the polymer is far from the SP value of the electrolytic solution, the polymer tends to hardly swell in the electrolytic solution.
  • the SP value means a solubility parameter.
  • the SP value can be calculated using the method introduced in Hansen Solubility Parameters A User's Handbook, 2nd Ed (CRCPless). Further, the SP value of an organic compound can be estimated from the molecular structure of the organic compound. Specifically, it can be calculated by using simulation software (for example, “HSPiP” (http://www.hansen-solution.com)) that can calculate the SP value from the SMILE equation. In this simulation software, Hansen SOLUBILITY PARAMETERS A User's Handbook Second Edition, Charles M. et al. The SP value is obtained based on the theory described in Hansen.
  • the glass transition temperature of the polymer constituting the core part of the organic particles is preferably ⁇ 50 ° C. or higher, more preferably 0 ° C. or higher, further preferably 20 ° C. or higher, It is preferable that it is 150 degrees C or less, It is more preferable that it is 120 degrees C or less, It is more preferable that it is 100 degrees C or less.
  • the glass transition temperature of the polymer in the core part is equal to or higher than the lower limit of the above range, the strength and blocking resistance of the functional layer can be further improved.
  • the adhesiveness in the electrolyte solution of a functional layer and the high temperature cycling characteristic of a secondary battery can be improved by making the glass transition temperature of the polymer of a core part below into the upper limit of the said range.
  • the type and amount of the monomer used for preparing the polymer of the core part are the same as the homopolymer glass of the monomer. Appropriate selection is considered in consideration of the transition temperature.
  • the transition temperature of the glass tends to be low.
  • (meth) acryl means acryl and / or methacryl.
  • a monomer having an electrolyte solution swelling degree within the above range can be appropriately selected and used.
  • monomers include vinyl chloride monomers such as vinyl chloride and vinylidene chloride; vinyl acetate monomers such as vinyl acetate; styrene, ⁇ -methylstyrene, styrenesulfonic acid, butoxystyrene, Aromatic vinyl monomers such as vinylnaphthalene; vinylamine monomers such as vinylamine; vinylamide monomers such as N-vinylformamide and N-vinylacetamide; methyl acrylate, ethyl acrylate, butyl acrylate, methacryl (Meth) acrylic acid ester monomers such as methyl acrylate, ethyl methacrylate and 2-ethylhexyl acrylate; (meth) acrylamide monomers such as acrylamide and methacrylamide;
  • (meth) acrylate means acrylate and / or methacrylate
  • (meth) acrylonitrile means acrylonitrile and / or methacrylonitrile
  • the polymer of the core part preferably contains a (meth) acrylate monomer unit, and more preferably contains a monomer unit derived from methyl methacrylate and / or butyl acrylate.
  • the polymer of the core part may include an acid group-containing monomer unit.
  • the acid group-containing monomer a monomer having an acid group, for example, a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, a monomer having a phosphoric acid group, and And monomers having a hydroxyl group.
  • Examples of the monomer having a carboxylic acid group include monocarboxylic acid and dicarboxylic acid.
  • Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
  • Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
  • Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamido-2-methyl. Examples thereof include propanesulfonic acid and 3-allyloxy-2-hydroxypropanesulfonic acid.
  • examples of the monomer having a phosphoric acid group include phosphoric acid-2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, and ethyl phosphate- (meth) acryloyloxyethyl phosphate.
  • examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate.
  • (meth) allyl means allyl and / or methallyl
  • (meth) acryloyl means acryloyl and / or methacryloyl.
  • an acid group-containing monomer a monomer having a carboxylic acid group is preferable, among which monocarboxylic acid is preferable, and (meth) acrylic acid is more preferable.
  • an acid group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the ratio of the acid group content body unit in the polymer of the core part is preferably 0.1% by mass or more, more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass. Hereinafter, it is more preferably 7% by mass or less.
  • the polymer of the core part preferably contains a crosslinkable monomer unit in addition to the monomer unit.
  • a crosslinkable monomer is a monomer that can form a crosslinked structure during or after polymerization by heating or irradiation with energy rays. By including a crosslinkable monomer unit, the electrolyte solution swelling degree of the polymer can be easily kept within the above range.
  • crosslinkable monomer examples include polyfunctional monomers having two or more polymerization reactive groups in the monomer.
  • polyfunctional monomers include divinyl compounds such as divinylbenzene; di (meta) such as ethylene dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and 1,3-butylene glycol diacrylate.
  • Acrylic acid ester compounds Tri (meth) acrylic acid ester compounds such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate; Ethylenically unsaturated monomers containing epoxy groups such as allyl glycidyl ether and glycidyl methacrylate; Is mentioned.
  • an ethylenically unsaturated monomer containing a dimethacrylic acid ester compound and an epoxy group is preferred, and a dimethacrylic acid ester compound is more preferred. preferable.
  • these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the ratio of the crosslinkable monomer unit is preferably determined in consideration of the type and amount of the monomer used.
  • the specific ratio of the crosslinkable monomer unit in the polymer of the core part is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.5% by mass or more. Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less.
  • the shell part of the organic particle is made of a polymer having a predetermined electrolyte solution swelling degree smaller than the electrolyte solution swelling degree of the core part.
  • the electrolyte solution swelling degree of the polymer of the shell portion needs to be more than 1 time, preferably 1.1 times or more, more preferably 1.2 times or more. In addition, it is necessary to be 4 times or less, 3.5 times or less is preferable, and 3 times or less is more preferable.
  • the electrolyte solution swelling degree of the polymer of the shell part exceed the lower limit value of the above range, the low-temperature output characteristics of the secondary battery can be improved by expressing high ion diffusibility in the functional layer.
  • the electrolyte swelling degree of the polymer of the shell part below the upper limit of the above range, it is possible to improve the adhesion of the functional layer in the electrolyte and improve the high-temperature cycle characteristics of the secondary battery.
  • the "electrolyte swelling degree" of the polymer of a shell part can be measured using the measuring method as described in the Example of this specification.
  • the kind and amount of the monomer for producing the polymer of the shell part are determined. Appropriate selection can be mentioned.
  • the glass transition temperature of the polymer constituting the shell part of the organic particles is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and 200 It is preferably not higher than ° C., more preferably not higher than 180 ° C., and further preferably not higher than 150 ° C.
  • the glass transition temperature of the polymer of the shell part is preferably 50 ° C. or higher, it is possible to improve the low temperature output characteristics of the secondary battery in addition to suppressing the occurrence of blocking.
  • the adhesiveness of a functional layer can further be improved by making the glass transition temperature of the polymer of a shell part into 200 degrees C or less.
  • the type and amount of the monomer used for preparing the polymer of the shell part are the same as the homopolymer glass of the monomer. Appropriate selection is considered in consideration of the transition temperature.
  • a monomer having an electrolyte solution swelling degree within the above range can be appropriately selected and used.
  • examples of such a monomer include the same monomers as those exemplified as monomers that can be used to produce the core polymer.
  • such a monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the polymer of the shell part preferably includes an aromatic vinyl monomer unit.
  • aromatic vinyl monomers styrene derivatives such as styrene and styrene sulfonic acid are more preferable. If an aromatic vinyl monomer is used, it is easy to control the degree of electrolyte swelling of the polymer. Moreover, the adhesiveness of the functional layer can be further enhanced.
  • the ratio of the aromatic vinyl monomer unit in the polymer of the shell part is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and still more preferably 60% by mass or more. Especially preferably, it is 80 mass% or more, Preferably it is 100 mass% or less, More preferably, it is 99.5 mass% or less, More preferably, it is 99 mass% or less.
  • the polymer of the shell part may contain an acid group-containing monomer unit in addition to the aromatic vinyl monomer unit.
  • the acid group-containing monomer a monomer having an acid group, for example, a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, a monomer having a phosphoric acid group, and And monomers having a hydroxyl group.
  • examples of the acid group-containing monomer include monomers similar to the acid group-containing monomer that can be contained in the core portion.
  • the acid group-containing monomer is preferably a monomer having a carboxylic acid group, more preferably a monocarboxylic acid, and even more preferably (meth) acrylic acid.
  • an acid group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the ratio of the acid group-containing monomer unit in the polymer of the shell part is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and preferably 20% by mass. Hereinafter, it is more preferably 10% by mass or less, and further preferably 7% by mass or less.
  • the polymer of the shell part may contain a crosslinkable monomer unit.
  • the crosslinkable monomer include monomers similar to those exemplified as the crosslinkable monomer that can be used in the core polymer.
  • crosslinked monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the ratio of the crosslinkable monomer unit in the polymer of the shell part is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, preferably Is 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less.
  • the form of the shell part is not particularly limited, but the shell part is preferably composed of polymer particles.
  • the shell part is composed of polymer particles, a plurality of particles constituting the shell part may overlap in the radial direction of the organic particles. However, in the radial direction of the organic particles, it is preferable that the particles constituting the shell portion do not overlap each other, and those polymer particles constitute the shell portion as a single layer.
  • the organic particles having the core-shell structure described above use, for example, a polymer monomer in the core part and a polymer monomer in the shell part, and change the ratio of these monomers over time.
  • the organic particles can be prepared by a continuous multi-stage emulsion polymerization method and a multi-stage suspension polymerization method in which the polymer of the previous stage is sequentially coated with the polymer of the subsequent stage.
  • an emulsifier for example, an anionic surfactant such as sodium dodecylbenzenesulfonate and sodium dodecylsulfate, a nonionic surfactant such as polyoxyethylene nonylphenyl ether and sorbitan monolaurate, or Cationic surfactants such as octadecylamine acetate can be used.
  • anionic surfactant such as sodium dodecylbenzenesulfonate and sodium dodecylsulfate
  • a nonionic surfactant such as polyoxyethylene nonylphenyl ether and sorbitan monolaurate
  • Cationic surfactants such as octadecylamine acetate
  • polymerization initiator examples include peroxides such as t-butylperoxy-2-ethylhexanoate, potassium persulfate, cumene peroxide, 2,2′-azobis (2-methyl-N- (2 An azo compound such as -hydroxyethyl) -propionamide) or 2,2'-azobis (2-amidinopropane) hydrochloride can be used.
  • a monomer and an emulsifier that form a core part are mixed, and emulsion polymerization is performed at once to obtain a particulate polymer constituting the core part.
  • the organic particle which has the core shell structure mentioned above can be obtained by superposing
  • the monomer that forms the polymer of the shell portion is divided into a plurality of times or continuously supplied to the polymerization system.
  • the monomer that forms the polymer of the shell part is divided into a polymerization system or continuously supplied, whereby the polymer constituting the shell part is formed into particles, and these particles are bonded to the core part. Thereby, the shell part which covers a core part partially can be formed.
  • the monomer for forming the polymer of the shell part is divided and supplied in a plurality of times, it is possible to control the average thickness of the shell part according to the ratio of dividing the monomer.
  • the monomer that forms the polymer of the shell part it is possible to control the average thickness of the shell part by adjusting the monomer supply amount per unit time. is there.
  • the volume average particle diameter D50 of the organic particles after forming the shell portion can be set to a desired range by adjusting the amount of the emulsifier, the amount of the monomer, and the like. Furthermore, the average ratio (coverage) by which the outer surface of the core part is covered by the shell part is adjusted by, for example, adjusting the amount of the emulsifier and the amount of the monomer that forms the polymer of the shell part. Can range.
  • the organic particles usually do not swell in the electrolytic solution and do not exhibit great adhesion in a state where they are not heated. Therefore, from the viewpoint of suppressing the organic particles from dropping off from the functional layer immediately after the formation of the functional layer (before heating or immersion in the electrolytic solution), the functional layer is not swollen in the electrolytic solution, and It is preferable that the binder for functional layers which exhibits adhesiveness also in the state which is not heated is included.
  • the functional layer binder components such as organic particles can be prevented from falling off from the functional layer even in a state where the electrolyte is not swollen and heated.
  • a binder for functional layers which can be used together with the said organic particle a known binder, for example, a thermoplastic elastomer, is mentioned.
  • a thermoplastic elastomer a conjugated diene polymer and an acrylic polymer are preferable, and an acrylic polymer is more preferable.
  • the conjugated diene polymer refers to a polymer containing a conjugated diene monomer unit.
  • Specific examples of the conjugated diene polymer include aromatic vinyl such as styrene-butadiene copolymer (SBR).
  • Examples thereof include a polymer containing a monomer unit and an aliphatic conjugated diene monomer unit, and an acrylic rubber (NBR) (a polymer containing an acrylonitrile unit and a butadiene unit).
  • an acrylic polymer refers to the polymer containing a (meth) acrylic acid ester monomer unit.
  • the (meth) acrylate monomer that can form a (meth) acrylate monomer unit is the same as the monomer used to prepare the polymer of the core part of the organic particles.
  • These functional layer binders may be used alone or in combination of two or more.
  • the polymer as the functional layer binding material is an organic particle having a core-shell structure made of the predetermined polymer described above. Be different.
  • the acrylic polymer as the binder for the functional layer includes a (meth) acrylonitrile monomer unit. Thereby, the intensity
  • the amount of the (meth) acrylonitrile monomer unit relative to the total amount of the (meth) acrylonitrile monomer unit and the (meth) acrylic acid ester monomer unit is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less.
  • the acrylic polymer as the binder for the functional layer is appropriately swollen with respect to the electrolytic solution by setting the ratio to be not more than the upper limit of the above range, the ion conductivity of the functional layer is reduced. A decrease in the low-temperature output characteristics of the secondary battery can be suppressed.
  • the glass transition temperature of the binder for the functional layer is usually lower than the glass transition temperature of the polymer of the core part of the organic particles and the glass transition temperature of the polymer of the shell part, and preferably ⁇ 100 ° C. or higher. More preferably, it is ⁇ 90 ° C. or more, more preferably ⁇ 80 ° C. or more, preferably 0 ° C. or less, more preferably ⁇ 5 ° C. or less, and further preferably ⁇ 10 ° C. or less. .
  • the glass transition temperature of the functional layer binder higher than the lower limit of the above range, the adhesiveness and strength of the functional layer binder can be enhanced. Moreover, the softness
  • the binder for the functional layer having a low glass transition temperature is usually fluidized by heating at the time of forming the functional layer, for example, it is widely dispersed in the functional layer so that it is difficult to grasp the shape by SEM or the like. To do.
  • the content of the functional layer binder in the functional layer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of the organic particles described above.
  • the amount is more preferably at least part by mass, more preferably at most 30 parts by mass, even more preferably at most 25 parts by mass, even more preferably at most 20 parts by mass.
  • Examples of the method for producing the functional layer binder include a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
  • the emulsion polymerization method and the suspension polymerization method are preferable because the polymerization can be performed in water and the aqueous dispersion containing the particulate functional layer binder can be suitably used for forming the functional layer as it is.
  • the reaction system contains a dispersing agent.
  • the functional layer binder is usually formed of a polymer substantially constituting the functional layer binder, but may be accompanied by optional components such as additives used in the polymerization.
  • the functional layer when the functional layer also functions as a porous membrane layer, the functional layer may contain non-conductive particles.
  • the non-conductive particles to be blended in the functional layer are not particularly limited, and known non-conductive particles used for non-aqueous secondary batteries can be exemplified.
  • the non-conductive particles both inorganic fine particles and organic fine particles other than the organic particles and the functional layer binder described above can be used, but inorganic fine particles are usually used.
  • a material of nonelectroconductive particle the material which exists stably in the use environment of a non-aqueous secondary battery and is electrochemically stable is preferable.
  • non-conductive particle material examples include aluminum oxide (alumina), hydrated aluminum oxide (boehmite), silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania).
  • Oxide particles such as BaTiO 3 , ZrO, alumina-silica composite oxide; nitride particles such as aluminum nitride and boron nitride; covalently bonded crystal particles such as silicon and diamond; barium sulfate, calcium fluoride, barium fluoride Insoluble ion crystal particles such as; clay fine particles such as talc and montmorillonite;
  • these particles may be subjected to element substitution, surface treatment, solid solution, and the like as necessary.
  • the nonelectroconductive particle mentioned above may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the functional layer may contain arbitrary other components besides the component mentioned above.
  • the other components are not particularly limited as long as they do not affect the battery reaction, and known components can be used. Moreover, these other components may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the other components include known additives used at the time of forming a functional layer, such as a wetting agent such as an ethylene oxide-propylene oxide copolymer, a viscosity modifier, and an electrolytic solution additive.
  • the functional layer formed on the functional layer forming surface of the separator substrate is composed of a single organic particle or a plurality of assembled organic particles, as shown in FIG.
  • the organic particle phase that is, the portion where the organic particles are present
  • the portion where the organic particles are not present for example, the portion where only components other than the organic particles such as the binder for the functional layer are present
  • phase of the organic particles needs to be present in a ratio of 20% to 80% with respect to the area of the functional layer forming surface without covering the entire functional layer forming surface.
  • the organic particles exhibit a certain degree of high ionic conductivity
  • the portion where the organic particles are present has a lower ionic conductivity than the portion where the organic particles are not present. Therefore, from the viewpoint of improving the ion conductivity of the functional layer in the electrolyte and enhancing the low-temperature output characteristics of the secondary battery using the separator, it exists on the functional layer forming surface with respect to the area of the functional layer forming surface.
  • the ratio of the area of the phase of the organic particles to be performed needs to be 80% or less.
  • the area of the portion where the organic particle phase is present relative to the area of the functional layer forming surface The ratio is preferably 25% or more, more preferably 30% or more, and further preferably 35% or more.
  • the proportion of the area of the part is preferably 70% or less, more preferably 60% or less, and further preferably 45% or less.
  • the phase of the organic particles exists in an irregular shape.
  • a plurality of phases composed of single organic particles or aggregated organic particles are present in an irregular shape rather than a fixed repetitive pattern shape (for example, a stripe shape or a lattice shape). is doing.
  • the adhesiveness in electrolyte solution can be improved because the phase of an organic particle exists in an irregular shape.
  • the configuration in which the phase of the organic particles is present in an irregular shape is not particularly limited, and for example, an island-like phase composed of a single organic particle or an aggregate of 10 or less organic particles
  • a configuration in which a continental phase composed of an aggregate of 11 or more organic particles is mixed with a portion where no organic particles exist is included.
  • the area of the part in which the phase of the organic particles exists and the shape of the phase of the organic particles are, for example, the type of the material used for forming the separator base material and the functional layer (composition for the non-aqueous secondary battery functional layer), and It can be adjusted by changing the method of forming the functional layer.
  • the method for producing a separator for a non-aqueous secondary battery according to the present invention includes a step of preparing a separator base material having a water droplet contact angle of 80 ° to 130 ° on the functional layer forming surface (base material preparation step), A step of preparing a composition for a non-aqueous secondary battery functional layer containing a component constituting the functional layer and a dispersion medium such as water and having a surface tension of 33 mN / m to 39 mN / m (composition preparation) Step) and a non-aqueous secondary battery functional layer composition applied on the functional layer-forming surface of the separator base material, and the applied non-aqueous secondary battery functional layer composition is dried to function on the separator base material.
  • base material preparation step A step of preparing a composition for a non-aqueous secondary battery functional layer containing a component constituting the functional layer and a dispersion medium such as water and having a surface tension of 33 mN / m to 39 mN
  • the composition for non-aqueous secondary battery functional layers was apply
  • a separator substrate having a water droplet contact angle of 80 ° to 130 ° on the functional layer forming surface is used, and the surface tension is 33 mN /
  • the functional layer having the above-described configuration can be easily formed.
  • a separator base material having a water droplet contact angle on at least one surface (functional layer forming surface) of 80 ° or more and 130 ° or less is prepared.
  • the water droplet contact angle on the functional layer forming surface is less than 80 °, the ratio of the area of the portion where the organic particle phase exists in the formed functional layer becomes too large.
  • the water droplet contact angle on the functional layer forming surface is more than 130 °, the ratio of the area of the formed functional layer where the organic particle phase exists is too small.
  • the water droplet contact angle of the functional layer forming surface is preferably 85 ° or more, and preferably 90 ° or more. More preferably, it is preferably 120 ° or less, and more preferably 110 ° or less.
  • the separator substrate having a water droplet contact angle of 80 ° to 130 ° is not particularly limited, and may be prepared by purchasing a commercially available separator substrate having a surface with a water droplet contact angle within the above range. It is good to adjust the size of the contact angle of water droplets on the surface of the microporous membrane that can be used as a separator substrate by using a surface treatment such as corona discharge treatment as described in the section ⁇ Separator substrate>. You may prepare by.
  • composition preparation step it is a slurry composition containing at least the organic particles described above, optionally containing a binder for functional layers, non-conductive particles, and other components, using water as a dispersion medium, And the composition for non-aqueous secondary battery functional layers whose surface tension is 33 mN / m or more and 39 mN / m or less is prepared.
  • the surface tension of the functional layer composition is less than 33 mN / m, the ratio of the area of the portion where the organic particle phase is present in the formed functional layer becomes too large.
  • the surface tension of the functional layer composition is preferably 34 mN / m or more, and more preferably 35 mN / m or more. More preferably, it is preferably 38 mN / m or less, and more preferably 37 mN / m or less.
  • the method for preparing the functional layer composition is not particularly limited, but usually, organic particles, water as a dispersion medium, and functional layer binder, non-conductive particles and A functional layer composition is prepared by mixing with other components.
  • the mixing method is not particularly limited, in order to disperse each component efficiently, mixing is usually performed using a disperser as a mixing device.
  • the disperser it is preferable to use an apparatus capable of uniformly dispersing and mixing the above components. Examples of the disperser include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, and a planetary mixer. From the viewpoint that a high dispersion share can be added, it is also preferable to use a high dispersion apparatus such as a bead mill, a roll mill, or a fill mix.
  • size of the surface tension of the composition for functional layers is not specifically limited, It can adjust by adding a wetting agent to the composition for functional layers, for example, increasing the addition amount of a wetting agent. Thereby, the surface tension of the composition for functional layers can be made small.
  • the wetting agent is not particularly limited, and a known surfactant such as a nonionic surfactant or an ionic surfactant can be used.
  • a nonionic surfactant is preferably used, a polyether copolymer is more preferably used, and an ethylene oxide-propylene oxide copolymer is further preferably used.
  • the compounding quantity of a wetting agent will not be specifically limited if the surface tension of the composition for functional layers can be made into the range mentioned above, for example, shall be 0.1 mass part or more per 100 mass parts of organic particles. It is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, particularly preferably 1.5 parts by mass or more, and 5.0 parts by mass or less. Preferably, it is 3.0 mass parts or less, More preferably, it is 2.5 mass parts or less, It is especially preferable to set it as 2.2 mass parts or less. When the amount of the wetting agent is too small, the surface tension of the functional layer composition may not be sufficiently reduced.
  • the amount of the wetting agent is too large, the surface tension of the functional layer composition may be too small.
  • the adhesiveness of a functional layer may fall or the high temperature cycling characteristic of a secondary battery may fall.
  • the functional layer forming step includes a step of applying the functional layer composition to the functional layer forming surface of the separator base material (application step), and drying the functional layer composition applied on the separator base material to form a functional layer.
  • a process of forming (drying process) is included.
  • the functional layer forming step when the functional layer composition having the surface tension described above is applied onto the functional layer forming surface having the water droplet contact angle, the functional layer composition is appropriately repelled and functions. Disperse non-uniformly without covering the entire surface of the layer formation.
  • the functional layer formed by drying the composition for the functional layer has the above-described specific shape and phase of organic particles having a specific area ratio.
  • the method for coating the functional layer composition on the separator substrate is not particularly limited.
  • Examples include the rouge method and the brush painting method.
  • the gravure method and the spray coating method are preferable from the viewpoint of forming a thinner functional layer.
  • the method for drying the composition for the functional layer on the separator substrate is not particularly limited, and a known method can be used. For example, a drying method using hot air, hot air, low-humidity air, or a vacuum drying method. And a drying method by irradiation with infrared rays or electron beams.
  • the drying conditions are not particularly limited, but the drying temperature is preferably 30 to 80 ° C., and the drying time is preferably 30 seconds to 10 minutes.
  • the thickness of the functional layer formed on the separator substrate is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 0.5 ⁇ m or more, preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less. More preferably, it is 5 ⁇ m or less.
  • the thickness of the functional layer is not less than the lower limit of the above range, the strength of the functional layer can be sufficiently secured.
  • the thickness of the functional layer is less than or equal to the upper limit of the above range, the ion diffusibility of the functional layer can be secured and the low-temperature output characteristics of the secondary battery can be further improved.
  • the non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolyte, and uses a separator for a non-aqueous secondary battery including the functional layer described above as a separator. And in the non-aqueous secondary battery of this invention, when the said functional layer functions as an adhesive layer, a positive electrode and a separator and / or a negative electrode and a separator are adhere
  • non-aqueous secondary battery of the present invention includes the separator of the present invention having a functional layer that is excellent in both adhesion and ionic conductivity in an electrolytic solution, high temperature cycle characteristics, low temperature output characteristics, etc. Excellent battery characteristics.
  • nonaqueous secondary battery known positive electrodes and negative electrodes used in nonaqueous secondary batteries can be used as the positive electrode and the negative electrode.
  • electrolytic solution a known electrolytic solution used in a non-aqueous secondary battery can be used.
  • the electrode positive electrode and negative electrode
  • an electrode in which an electrode mixture layer is formed on a current collector can be used.
  • the current collector, the components in the electrode mixture layer for example, the electrode active material (positive electrode active material, negative electrode active material) and the electrode mixture layer binder (positive electrode mixture layer binder, negative electrode composite)
  • a known material can be used. Specifically, for example, those described in JP2013-145663A can be used.
  • an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
  • a lithium salt is used as the supporting electrolyte.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable, and LiPF 6 is particularly preferable because it is easily soluble in a solvent and exhibits a high degree of dissociation.
  • electrolyte may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Usually, the lithium ion conductivity tends to increase as the supporting electrolyte having a higher degree of dissociation is used, so that the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
  • the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
  • dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC) ), Carbonates such as butylene carbonate (BC) and ethyl methyl carbonate (EMC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; Sulfur compounds; etc. are preferably used.
  • the concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate.
  • the concentration is preferably 0.5 to 15% by mass, more preferably 2 to 13% by mass, and more preferably 5 to 10% by mass. More preferably.
  • known additives such as fluoroethylene carbonate and ethyl methyl sulfone may be added to the electrolytic solution.
  • a non-aqueous secondary battery is, for example, a stack of a positive electrode and a negative electrode sandwiched between separators, wound in accordance with the battery shape as needed, folded into a battery container, and an electrolyte solution in the battery container. It can be manufactured by pouring and sealing. In order to prevent the occurrence of pressure rise inside the non-aqueous secondary battery, overcharge / discharge, etc., an overcurrent prevention element such as a fuse or a PTC element, an expanded metal, a lead plate, etc. may be provided as necessary. .
  • the shape of the non-aqueous secondary battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like, for example.
  • the high-temperature cycle characteristics and low-temperature output characteristics of the secondary battery were measured and evaluated by the following methods.
  • ⁇ Swelling degree of electrolyte solution of polymer of core part and polymer of shell part Using the monomers and various additives used for the formation of the core part and shell part of the organic particles, under the same polymerization conditions as the polymerization conditions for the core part and shell part, the polymer of the core part and the shell part An aqueous dispersion containing the polymer was prepared. This aqueous dispersion was put in a petri dish made of polytetrafluoroethylene and dried under conditions of 110 ° C. and 10 hours to obtain a film having a thickness of 0.5 mm. And the obtained film was cut
  • test piece was immersed in an electrolytic solution at 60 ° C. for 72 hours. Then, the test piece was taken out from the electrolytic solution, the electrolytic solution on the surface of the test piece was wiped off, and the mass W1 of the test piece after the immersion test was measured. And using these mass W0 and W1, electrolyte solution swelling degree S (times) was calculated
  • required by S W1 / W0.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • VC vinylene carbonate
  • ⁇ Glass transition temperature of core polymer, shell polymer and functional layer binder> A polymer (core part) to be a measurement sample under the same polymerization conditions as the polymerization conditions of the core part and the shell part using the monomers and various additives used for forming the core part and shell part of the organic particles Water dispersions containing the polymer and the shell polymer).
  • the prepared aqueous dispersion was used as a measurement sample.
  • the aqueous dispersion containing the binder for functional layers was prepared, and it was set as the measurement sample.
  • volume average particle diameter D50 of organic particles The volume average particle size D50 of the organic particles is 50% of the cumulative volume calculated from the small diameter side in the particle size distribution measured by a laser diffraction type particle size distribution measuring device (“SALD-3100” manufactured by Shimadzu Corporation). The particle diameter was taken.
  • SALD-3100 laser diffraction type particle size distribution measuring device
  • the particle diameter was taken.
  • ⁇ Core shell ratio of organic particles The core-shell ratio of the organic particles was measured by the following procedure.
  • the prepared organic particles were sufficiently dispersed in a visible light curable resin (“D-800” manufactured by JEOL Ltd.) and then embedded to obtain a block piece containing organic particles. Next, the obtained block piece was cut into a thin piece having a thickness of 100 nm with a microtome equipped with a diamond blade to prepare a measurement sample.
  • the measurement sample was dyed using ruthenium tetroxide.
  • the dyed measurement sample was set in a transmission electron microscope (“JEM-3100F” manufactured by JEOL Ltd.), and a cross-sectional structure of organic particles was photographed at an acceleration voltage of 80 kV. The magnification of the electron microscope was set so that the cross section of one organic particle was in the visual field. Thereafter, the cross-sectional structure of the photographed organic particles was observed, and the average thickness of the shell portion of the organic particles was measured by the following procedure according to the observed configuration of the shell portion. And the core-shell ratio was calculated
  • the longest diameter of the polymer particles constituting the shell portion was measured.
  • the longest diameter of the polymer particles constituting the shell part was measured for 20 arbitrarily selected organic particles, and the average value of the longest diameters was taken as the average thickness of the shell part.
  • the maximum thickness of the shell portion was measured.
  • the maximum thickness of the shell portion was measured for 20 arbitrarily selected organic particles, and the average value of the maximum thickness was taken as the average thickness of the shell portion.
  • the cross-sectional structure of the organic particles is photographed.
  • the covering ratio Rc “AnalySIS Pro” (manufactured by Olympus Corporation) which is image analysis software was used.
  • the covering ratio Rc was measured for 20 arbitrarily selected organic particles, and the average value was defined as the average ratio (covering ratio) at which the outer surface of the core portion of the organic particles was covered by the shell portion.
  • ⁇ Surface tension of composition for non-aqueous secondary battery functional layer The prepared composition for a non-aqueous secondary battery functional layer was poured onto a glass petri dish. And the surface tension was measured by the plate method using the platinum plate. The measurement is performed twice using a fully automatic surface tension meter “CBVP-Z” manufactured by Kyowa Interface Science. The average value of the surface tension is obtained from the measured value, and the average value is used for the non-aqueous secondary battery functional layer. The surface tension of the composition was used.
  • ⁇ Water droplet contact angle of separator substrate> The separator substrate was fixed on a flat plate. Then, 1 ⁇ L of ion exchange water (surface tension 72 mN / m) was dropped on the separator substrate, and the contact angle 60 seconds after the landing was measured. The measurement was performed twice using a contact angle meter “DM-901” manufactured by Kyowa Interface Science, and the average value of the water droplet contact angles was determined from the measured values, and the average value was used as the water droplet contact angle of the separator substrate. It was.
  • DM-901 manufactured by Kyowa Interface Science
  • ⁇ Ratio of the area of the part where the phase of organic particles exists The surface of the functional layer of the separator was observed at a magnification of 5000 using a scanning electron microscope (SEM) “Hitachi S-4700” to obtain 10 SEM images. About the obtained image, the ratio of the area of the part in which the phase of an organic particle exists was computed with the following formula using image analysis software ("analysis PRO" by Olympus). And the average value of the calculated value was made into the ratio of the area of the part in which the phase of an organic particle exists with respect to the area of a functional layer formation surface.
  • SEM scanning electron microscope
  • the ratio of the area of the portion where the organic particle phase was present to the area of the functional layer forming surface was calculated from the width of the functional layer and the functional layer formation interval.
  • Ratio (%) of the area where the organic particle phase exists (area of the area where the organic particle phase exists / viewing area) ⁇ 100 ⁇ Adhesiveness between separator and electrode after immersion in electrolyte>
  • the prepared laminate including the positive electrode and the separator and the laminate including the negative electrode and the separator were each cut into a width of 10 mm to obtain test pieces. This test piece was immersed in the electrolytic solution at a temperature of 60 ° C. for 3 days.
  • EC ethylene carbonate
  • DEC / VC vinylene carbonate
  • a cellophane tape defined in JIS Z1522 was used.
  • the cellophane tape was fixed on a horizontal test bench.
  • the stress when one end of the separator base material was pulled vertically upward at a pulling speed of 50 mm / min and peeled was measured. This measurement was performed three times for each of the laminate including the positive electrode and the separator and the laminate including the negative electrode and the separator, for a total of 6 times, and the average value of the stress was obtained as the peel strength.
  • the adhesiveness was evaluated according to the following criteria. It shows that adhesiveness is so high that peel strength is large.
  • the manufactured lithium ion secondary battery of a wound type cell having a discharge capacity of 800 mAh was allowed to stand in an environment of 25 ° C. for 24 hours. Thereafter, under an environment of 25 ° C., a charge / discharge operation of charging up to 4.35 V at 0.1 C and discharging to 2.75 V at 0.1 C was performed, and the initial capacity C0 was measured.
  • Capacity maintenance ratio ⁇ C is 88% or more
  • the manufactured lithium ion secondary battery of a wound type cell having a discharge capacity of 800 mAh was allowed to stand in an environment of 25 ° C. for 24 hours. Thereafter, charging was performed for 5 hours at a charging rate of 0.1 C under an environment of 25 ° C., and the voltage V0 at that time was measured.
  • Example 1 ⁇ Preparation of organic particles having a core-shell structure>
  • 75 parts of methyl methacrylate as a (meth) acrylic acid ester monomer 75 parts of methacrylic acid as an acid group-containing monomer, 1 part of ethylene glycol dimethacrylate; 1 part of sodium dodecylbenzenesulfonate as an emulsifier; 150 parts of ion-exchanged water and 0.5 part of potassium persulfate as a polymerization initiator were added and sufficiently stirred. Then, it heated to 60 degreeC and superposition
  • Polymerization was continued until the polymerization conversion rate reached 96% to obtain an aqueous dispersion containing a particulate polymer constituting the core portion.
  • a mixture of 19 parts of styrene as an aromatic vinyl monomer and 1 part of methacrylic acid as an acid group-containing monomer was continuously added to form a shell part, and heated to 70 ° C.
  • Polymerization was continued.
  • the reaction was stopped by cooling to prepare an aqueous dispersion containing organic particles having a core-shell structure in which the outer surface of the core part was partially covered with the shell part. .
  • the obtained organic particles had a volume average particle diameter D50 of 0.45 ⁇ m.
  • aqueous dispersion containing a particulate functional layer binder (acrylic polymer).
  • the functional layer binder obtained had a glass transition temperature of ⁇ 40 ° C.
  • aqueous dispersion containing the organic particles having the core-shell structure is 100 parts in terms of solid content, and the aqueous dispersion containing the functional layer binder is 15 parts in terms of solid content.
  • Ethylene oxide as a wetting agent -Propylene oxide copolymer (solid content concentration 70% by mass, polymerization ratio: 5/5 (mass ratio)) is mixed with 1.9 parts in solid content, and ion-exchanged water is added to a solid content concentration of 15% by mass.
  • composition preparation step a slurry-like composition for a nonaqueous secondary battery functional layer was prepared (composition preparation step).
  • surface tension of the obtained composition for non-aqueous secondary battery functional layers was measured. The results are shown in Table 1.
  • ⁇ Preparation of separator substrate> A polyethylene microporous film (thickness 16 ⁇ m, Gurley value 210 s / 100 cc) was prepared.
  • the prepared microporous membrane was subjected to corona discharge treatment at a treatment strength of 50 W ⁇ min / m 2 using “Air Plasma APW-602f” manufactured by Kasuga Denki, and used as a separator base material (base material preparation step). And the water droplet contact angle of the separator base material was measured. The results are shown in Table 1.
  • ⁇ Preparation of separator> A slurry-like composition for a non-aqueous secondary battery functional layer was applied to both surfaces of the separator substrate by a gravure coating method (number of lines: 300) and dried at 50 ° C. for 1 minute (functional layer forming step).
  • a functional layer having a thickness of 0.8 ⁇ m per layer was formed on the separator base material, and a separator formed by forming the functional layers on both surfaces of the separator base material was obtained.
  • This separator includes a functional layer, a separator base material, and a functional layer in this order.
  • the functional layer of the separator was observed with SEM, and the ratio of the area of the part in which the phase of an organic particle exists was calculated
  • the obtained SEM image is shown in FIG. 1 and the results are shown in Table 1.
  • the phase of organic particles was present in an irregular shape. Moreover, only organic particles were observed as particles, and the binder for functional layers was not observed as particles by SEM.
  • a 5% aqueous sodium hydroxide solution was added to the mixture containing the particulate binder to adjust the pH to 8. Thereafter, unreacted monomers are removed from the mixture by heating under reduced pressure, and the mixture is cooled to 30 ° C. or lower to obtain an aqueous dispersion containing a desired particulate binder (binder for negative electrode mixture layer). It was.
  • MAC350HC carboxymethylcellulose sodium salt
  • ion exchange water was added to adjust the solid content concentration to 68%, and the mixture was mixed at 25 ° C. for 60 minutes. Ion exchange water was added to the liquid mixture thus obtained to adjust the solid content concentration to 62%, and the mixture was further mixed at 25 ° C. for 15 minutes.
  • 1.5 parts of the above aqueous dispersion containing the particulate binder is added in an amount corresponding to the solid content, and ion-exchanged water is further added to adjust the final solid content concentration to 52%, and further for 10 minutes. Mixed. This was defoamed under reduced pressure to obtain a negative electrode slurry composition having good fluidity.
  • the slurry composition for negative electrode was applied on a copper foil having a thickness of 20 ⁇ m, which is a current collector, with a comma coater so that the film thickness after drying was about 150 ⁇ m and dried. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a negative electrode raw material before pressing. The negative electrode raw material before pressing was rolled with a roll press to obtain a negative electrode after pressing with a negative electrode mixture layer thickness of 80 ⁇ m.
  • ⁇ Production of positive electrode slurry composition 100 parts of LiCoO 2 having a volume average particle diameter of 12 ⁇ m as the positive electrode active material, 2 parts of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., product name “HS-100”) as the conductive material, and binder for positive electrode (positive electrode mixture layer)
  • Polyvinylidene fluoride manufactured by Kureha Co., Ltd., product name “# 7208” was mixed in an amount equivalent to the solid content, and N-methylpyrrolidone was added thereto to make the total solid content concentration 70%. These were mixed by a planetary mixer to obtain a positive electrode slurry composition.
  • the positive electrode slurry composition was applied onto a 20 ⁇ m-thick aluminum foil as a current collector by a comma coater so that the film thickness after drying was about 150 ⁇ m and dried. This drying was performed by conveying the aluminum foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a positive electrode raw material before pressing. The positive electrode raw material before pressing was rolled with a roll press to obtain a positive electrode.
  • ⁇ Manufacture of laminate of negative electrode or positive electrode and separator> The positive electrode after pressing was cut into a circle having a diameter of 13 mm to obtain a circular positive electrode.
  • the negative electrode after pressing was cut out into a circle having a diameter of 14 mm to obtain a circular negative electrode.
  • the separator was cut into a circle having a diameter of 18 mm to obtain a circular separator. Then, only the negative electrode or the positive electrode was placed on one side of the circular separator so as to be in contact with the separator on the surface on the electrode mixture layer side. Thereafter, a heat press treatment was performed at a temperature of 80 ° C. and a pressure of 0.5 MPa for 10 seconds, and the positive electrode or the negative electrode was pressure-bonded to the separator to obtain a laminate including the positive electrode and the separator, and a laminate including the negative electrode and the separator. .
  • the wound body was pressed at 60 ° C. and 0.5 MPa to obtain a flat body.
  • electrolyte LiPF 6
  • Example 2 For the preparation of organic particles and functional layers in the same manner as in Example 1 except that the amounts of methyl methacrylate, methacrylic acid and ethylene glycol dimethacrylate used for the production of the core portion were changed as shown in Table 1 when the organic particles were prepared.
  • a binder, a composition for a non-aqueous secondary battery functional layer, a separator base material, a separator, a negative electrode, a positive electrode, a laminate, and a lithium ion secondary battery were produced.
  • Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • the organic particle phase was present in an irregular shape in the functional layer.
  • only organic particles were observed as particles, and the binder for functional layers was not observed as particles by SEM.
  • Example 5 When preparing the organic particles, the amount of methyl methacrylate is changed to 43 parts and the amount of methacrylic acid is changed to 1 part for the monomer composition used for the production of the core part. Except for adding 35 parts of butyl acrylate as a body, in the same manner as in Example 1, organic particles, functional layer binder, non-aqueous secondary battery functional layer composition, separator substrate, separator, negative electrode, A positive electrode, a laminate, and a lithium ion secondary battery were produced. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. As a result of observation by SEM, the organic particle phase was present in an irregular shape in the functional layer. Moreover, only organic particles were observed as particles, and the binder for functional layers was not observed as particles by SEM.
  • Example 6 At the time of preparing the organic particles, the amount of styrene was changed to 18 parts for the monomer composition used for the production of the shell part, and 1.7 parts of acrylonitrile as a (meth) acrylonitrile monomer and a crosslinkable monomer Organic particles, binder for functional layer, functional layer for non-aqueous secondary battery, except that 0.3 part of ethylene glycol dimethacrylate as a body was added and methacrylic acid was not added Composition, separator substrate, separator, negative electrode, positive electrode, laminate, and lithium ion secondary battery were prepared. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. As a result of observation by SEM, the organic particle phase was present in an irregular shape in the functional layer. Moreover, only organic particles were observed as particles, and the binder for functional layers was not observed as particles by SEM.
  • Example 7 When preparing organic particles, the amount of styrene is changed to 15 parts for the monomer composition used in the production of the shell part, and 4.5 parts of acrylonitrile as a (meth) acrylonitrile monomer and a crosslinkable monomer Organic particles, functional layer binder, non-aqueous secondary battery functional layer in the same manner as in Example 1 except that 0.5 part of ethylene glycol dimethacrylate as a body was added and methacrylic acid was not added. Composition, separator substrate, separator, negative electrode, positive electrode, laminate, and lithium ion secondary battery were prepared. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. As a result of observation by SEM, the organic particle phase was present in an irregular shape in the functional layer. Moreover, only organic particles were observed as particles, and the binder for functional layers was not observed as particles by SEM.
  • Examples 8 to 9 In the same manner as in Example 1, except that the blending amount of the ethylene oxide-propylene oxide copolymer as the wetting agent was changed as shown in Table 1 when preparing the composition for the non-aqueous secondary battery functional layer, the organic particles Then, a functional layer binder, a non-aqueous secondary battery functional layer composition, a separator substrate, a separator, a negative electrode, a positive electrode, a laminate, and a lithium ion secondary battery were produced. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. As a result of observation by SEM, the organic particle phase was present in an irregular shape in the functional layer. Moreover, only organic particles were observed as particles, and the binder for functional layers was not observed as particles by SEM.
  • Example 10 When preparing the separator base material, the organic particles and the binder for functional layers were prepared in the same manner as in Example 1 except that the treatment strength of the corona discharge treatment for the polyethylene microporous membrane was changed as shown in Table 1. Then, a composition for a non-aqueous secondary battery functional layer, a separator substrate, a separator, a negative electrode, a positive electrode, a laminate, and a lithium ion secondary battery were produced. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. As a result of observation by SEM, the organic particle phase was present in an irregular shape in the functional layer. Moreover, only organic particles were observed as particles, and the binder for functional layers was not observed as particles by SEM.
  • Example 1 In the same manner as in Example 1 except that an ethylene oxide-propylene oxide copolymer as a wetting agent was not blended when preparing the composition for the functional layer of the non-aqueous secondary battery, the binder for organic particles and the functional layer was used. Then, a composition for a non-aqueous secondary battery functional layer, a separator substrate, a separator, a negative electrode, a positive electrode, a laminate, and a lithium ion secondary battery were produced. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. As a result of observation by SEM, the organic particle phase was present in an irregular shape in the functional layer. Moreover, only organic particles were observed as particles, and the binder for functional layers was not observed as particles by SEM.
  • Example 2 In the same manner as in Example 1, except that the blending amount of the ethylene oxide-propylene oxide copolymer as the wetting agent was changed as shown in Table 1 when preparing the composition for the non-aqueous secondary battery functional layer, the organic particles Then, a functional layer binder, a non-aqueous secondary battery functional layer composition, a separator substrate, a separator, a negative electrode, a positive electrode, a laminate, and a lithium ion secondary battery were produced. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. As a result of observation by SEM, organic particles were present uniformly over the entire surface of the separator substrate. Moreover, only organic particles were observed as particles, and the binder for functional layers was not observed as particles by SEM.
  • Example 5 At the time of preparing the composition for the non-aqueous secondary battery functional layer, the blending amount of the ethylene oxide-propylene oxide copolymer as a wetting agent was changed as shown in Table 1, and the gravure coating method was used at the time of preparing the separator.
  • the composition for the non-aqueous secondary battery functional layer was applied to the separator substrate using the wire bar coating method, the organic particles, the binder for the functional layer, and the non-aqueous system were used.
  • a composition for a secondary battery functional layer, a separator base material, a separator, a negative electrode, a positive electrode, a laminate, and a lithium ion secondary battery were produced.
  • MMA indicates methyl methacrylate
  • BA indicates butyl acrylate
  • MAA indicates methacrylic acid
  • EDMA refers to ethylene glycol dimethacrylate
  • ST indicates styrene
  • AN indicates acrylonitrile
  • NMA stands for N-methylolacrylamide
  • AAm indicates acrylamide.
  • a functional layer in which the phase of organic particles having a predetermined core-shell structure and properties exists in an irregular shape and the area ratio of the portion where the phase of organic particles exists is 20% or more and 80% or less
  • the separator having the above it is possible to obtain a secondary battery excellent in the adhesiveness between the separator and the electrode after immersion in the electrolyte, and having good battery characteristics such as high temperature cycle characteristics and low temperature output characteristics. I understand that I can do it.
  • Comparative Example 1 using a separator in which the proportion of the area where the organic particle phase is present is less than 20% the adhesion between the separator and the electrode after immersion in the electrolyte and the high-temperature cycle characteristics are It turns out that it falls.
  • the separator excellent in the adhesiveness and ionic conductivity in electrolyte solution can be provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un séparateur qui est excellent en termes d'adhésivité et de conductivité ionique dans une solution électrolytique. Ce séparateur pour une batterie rechargeable non aqueuse comprend : un substrat de séparateur ; et une couche fonctionnelle qui est formée sur au moins une surface du substrat de séparateur. La couche fonctionnelle présente une configuration dans laquelle une phase de particules organiques existe dans une forme irrégulière, les particules organiques ayant chacune une structure noyau-coque qui comprend une partie noyau et une partie coque qui recouvre partiellement une surface externe de la partie noyau. La partie noyau est composée d'un polymère qui présente un degré de gonflement dans une solution électrolytique compris entre 5 et 30 fois. La partie coque est composée d'un polymère qui présente un degré de gonflement dans une solution électrolytique compris entre 1 et 4 fois. Le rapport entre l'aire de la partie où existe la phase de particules organiques, et l'aire de la surface du substrat de séparateur sur laquelle est formée la couche fonctionnelle, est compris entre 20 et 80 %.
PCT/JP2015/006032 2015-01-09 2015-12-04 Séparateur pour une batterie rechargeable non aqueuse, son procédé de fabrication et batterie rechargeable non aqueuse Ceased WO2016110894A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201580071472.9A CN107112480B (zh) 2015-01-09 2015-12-04 非水系二次电池用间隔件及其制造方法以及非水系二次电池
JP2016568172A JP6750506B2 (ja) 2015-01-09 2015-12-04 非水系二次電池用セパレータおよびその製造方法、並びに、非水系二次電池
KR1020177017829A KR102477891B1 (ko) 2015-01-09 2015-12-04 비수계 이차 전지용 세퍼레이터 및 그 제조 방법, 그리고, 비수계 이차 전지

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-003646 2015-01-09
JP2015003646 2015-01-09

Publications (1)

Publication Number Publication Date
WO2016110894A1 true WO2016110894A1 (fr) 2016-07-14

Family

ID=56355626

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/006032 Ceased WO2016110894A1 (fr) 2015-01-09 2015-12-04 Séparateur pour une batterie rechargeable non aqueuse, son procédé de fabrication et batterie rechargeable non aqueuse

Country Status (4)

Country Link
JP (1) JP6750506B2 (fr)
KR (1) KR102477891B1 (fr)
CN (1) CN107112480B (fr)
WO (1) WO2016110894A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017086466A1 (fr) * 2015-11-19 2017-05-26 旭化成株式会社 Séparateur pour des dispositifs de stockage d'électricité, corps d'électrode utilisant ce dernier et dispositif de stockage d'électricité
WO2018163761A1 (fr) * 2017-03-10 2018-09-13 日本ゼオン株式会社 Composition pour couches fonctionnelles de batterie secondaire non aqueuse, couche fonctionnelle pour batteries secondaires non aqueuses, et batterie secondaire non aqueuse
WO2019151118A1 (fr) * 2018-01-31 2019-08-08 日本ゼオン株式会社 Composition pour séparateur d'accumulateur au lithium-ion, composition en deux parties pour séparateur d'accumulateur au lithium-ion, procédé de fabrication d'un séparateur d'accumulateur au lithium-ion, et procédé de fabrication d'un accumulateur au lithium-ion
WO2020031614A1 (fr) 2018-08-10 2020-02-13 日本ゼオン株式会社 Composition de bouillie pour couches adhésives de batterie secondaire non aqueuse, couche adhésive pour batteries secondaires non aqueuses, séparateur pour batteries secondaires non aqueuses et batterie secondaire non aqueuse
JP2022029305A (ja) * 2020-08-04 2022-02-17 三星エスディアイ株式会社 非水電解質二次電池用バインダー組成物、非水電解質二次電池用負極、非水電解質二次電池及びこれらの製造方法
JPWO2022163591A1 (fr) * 2021-01-29 2022-08-04
JP2022125963A (ja) * 2021-02-17 2022-08-29 東レ株式会社 電気化学素子用セパレータおよび電気化学素子用セパレータの製造方法

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102647260B1 (ko) 2018-07-02 2024-03-13 에스케이이노베이션 주식회사 이차전지용 복합 분리막
EP3876304A4 (fr) * 2018-10-31 2022-08-03 Zeon Corporation Composition de couche fonctionnelle de batterie secondaire non aqueuse, couche fonctionnelle de batterie secondaire non aqueuse, séparateur pour batterie secondaire non aqueuse et batterie secondaire non aqueuse
CN110707357B (zh) * 2019-10-23 2021-05-07 北京卫蓝新能源科技有限公司 一种核壳结构的凝胶聚合物电解质及其制备方法和应用
CN112928390A (zh) * 2019-11-20 2021-06-08 北京卫蓝新能源科技有限公司 一种表面涂覆核壳结构层的隔膜及其应用
EP4102636A4 (fr) 2020-11-30 2023-05-31 Contemporary Amperex Technology Co., Limited Film séparateur, batterie secondaire le contenant, module de batterie associé, bloc-batterie et dispositif
CN119994391A (zh) 2020-11-30 2025-05-13 宁德时代新能源科技股份有限公司 一种二次电池、电池模块、电池包和装置
KR102537203B1 (ko) 2020-11-30 2023-05-26 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 분리막, 그 제조 방법 및 이와 관련된 이차 전지, 배터리 모듈, 배터리 팩 및 장치
CN113131094A (zh) * 2021-03-01 2021-07-16 东莞市溢兴新材料科技有限公司 一种高粘结力聚合物涂层隔膜及其制备方法
CN113410576B (zh) * 2021-06-17 2023-11-24 无锡恩捷新材料科技有限公司 电池隔膜及其制备方法、电池、核壳型球体的制备方法
CN116535576B (zh) * 2023-05-04 2025-12-02 浙江研一新能源科技有限公司 一种聚合物粘结剂及制备方法、陶瓷隔膜涂覆浆料、陶瓷隔膜和电池
CN116435711B (zh) * 2023-06-14 2023-08-25 中材锂膜(内蒙古)有限公司 聚合物涂覆隔膜及其制备方法和电池
KR102886432B1 (ko) 2024-11-07 2025-11-17 에스케이이노베이션 주식회사 분리막 및 이를 포함하는 전기화학소자

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011001848A1 (fr) * 2009-06-30 2011-01-06 日本ゼオン株式会社 Électrode pour batterie secondaire, et batterie secondaire
WO2013080946A1 (fr) * 2011-11-29 2013-06-06 日立マクセル株式会社 Séparateur destiné à une pile à électrolyte non aqueux et pile à électrolyte non aqueux utilisant celui-ci
WO2014017651A1 (fr) * 2012-07-26 2014-01-30 旭化成イーマテリアルズ株式会社 Séparateur destiné à un dispositif de stockage d'énergie, corps stratifié et membrane poreuse
WO2015005145A1 (fr) * 2013-07-10 2015-01-15 日本ゼオン株式会社 Batterie secondaire au lithium-ion, et adhésif ainsi que séparateur pour celle-ci

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5010817B2 (ja) * 2005-08-25 2012-08-29 日東電工株式会社 電池用セパレータのための接着剤担持多孔質フイルムとそれを用いる電池の製造方法
JP5611505B2 (ja) * 2006-03-29 2014-10-22 日立マクセル株式会社 電池用セパレータおよびリチウム二次電池
JP5403857B2 (ja) * 2006-05-18 2014-01-29 日立マクセル株式会社 電池用セパレータ、その製造方法およびリチウム二次電池
JP5588964B2 (ja) * 2008-04-08 2014-09-10 エスケー イノベーション カンパニー リミテッド 高耐熱性多孔性被覆層を有するポリオレフィン系複合微多孔膜
CN101707242A (zh) * 2009-10-14 2010-05-12 东莞新能源科技有限公司 有机/无机复合多孔隔离膜
KR101287467B1 (ko) * 2010-03-24 2013-07-19 데이진 가부시키가이샤 폴리올레핀 미다공막 및 그 제조 방법, 비수계 2차 전지용 세퍼레이터, 및 비수계 2차 전지
JP5699576B2 (ja) * 2010-12-08 2015-04-15 ソニー株式会社 積層型微多孔膜、電池用セパレータおよび非水電解質電池
WO2013051079A1 (fr) * 2011-10-03 2013-04-11 日立マクセル株式会社 Membrane poreuse résistant à la chaleur, séparateur pour cellule non aqueuse et cellule non aqueuse
KR101996361B1 (ko) * 2012-03-28 2019-07-04 제온 코포레이션 2 차 전지용 다공막 및 그 제조 방법, 2 차 전지용 전극, 2 차 전지용 세퍼레이터 그리고 2 차 전지
WO2014098519A1 (fr) * 2012-12-21 2014-06-26 주식회사 아모그린텍 Membrane de séparation poreuse, batterie secondaire utilisant celle-ci, et procédé de fabrication de ladite batterie secondaire

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011001848A1 (fr) * 2009-06-30 2011-01-06 日本ゼオン株式会社 Électrode pour batterie secondaire, et batterie secondaire
WO2013080946A1 (fr) * 2011-11-29 2013-06-06 日立マクセル株式会社 Séparateur destiné à une pile à électrolyte non aqueux et pile à électrolyte non aqueux utilisant celui-ci
WO2014017651A1 (fr) * 2012-07-26 2014-01-30 旭化成イーマテリアルズ株式会社 Séparateur destiné à un dispositif de stockage d'énergie, corps stratifié et membrane poreuse
WO2015005145A1 (fr) * 2013-07-10 2015-01-15 日本ゼオン株式会社 Batterie secondaire au lithium-ion, et adhésif ainsi que séparateur pour celle-ci

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10985354B2 (en) 2015-11-19 2021-04-20 Asahi Kasei Kabushiki Kaisha Separator for electricity storage devices, electrode body using same, and electricity storage device
WO2017086466A1 (fr) * 2015-11-19 2017-05-26 旭化成株式会社 Séparateur pour des dispositifs de stockage d'électricité, corps d'électrode utilisant ce dernier et dispositif de stockage d'électricité
WO2018163761A1 (fr) * 2017-03-10 2018-09-13 日本ゼオン株式会社 Composition pour couches fonctionnelles de batterie secondaire non aqueuse, couche fonctionnelle pour batteries secondaires non aqueuses, et batterie secondaire non aqueuse
WO2019151118A1 (fr) * 2018-01-31 2019-08-08 日本ゼオン株式会社 Composition pour séparateur d'accumulateur au lithium-ion, composition en deux parties pour séparateur d'accumulateur au lithium-ion, procédé de fabrication d'un séparateur d'accumulateur au lithium-ion, et procédé de fabrication d'un accumulateur au lithium-ion
EP3748729A4 (fr) * 2018-01-31 2021-10-27 Zeon Corporation Composition pour séparateur d'accumulateur au lithium-ion, composition en deux parties pour séparateur d'accumulateur au lithium-ion, procédé de fabrication d'un séparateur d'accumulateur au lithium-ion, et procédé de fabrication d'un accumulateur au lithium-ion
US12021262B2 (en) 2018-08-10 2024-06-25 Zeon Corporation Slurry composition including organic particles, sulfosuccinic acid ester, hydrocarbon, and water, adhesive layer formed from the same, separator with adhesive layer, and non-aqueous secondary battery
WO2020031614A1 (fr) 2018-08-10 2020-02-13 日本ゼオン株式会社 Composition de bouillie pour couches adhésives de batterie secondaire non aqueuse, couche adhésive pour batteries secondaires non aqueuses, séparateur pour batteries secondaires non aqueuses et batterie secondaire non aqueuse
JP2022029305A (ja) * 2020-08-04 2022-02-17 三星エスディアイ株式会社 非水電解質二次電池用バインダー組成物、非水電解質二次電池用負極、非水電解質二次電池及びこれらの製造方法
JP7555213B2 (ja) 2020-08-04 2024-09-24 三星エスディアイ株式会社 非水電解質二次電池用バインダー組成物、非水電解質二次電池用負極、非水電解質二次電池及びこれらの製造方法
WO2022163591A1 (fr) * 2021-01-29 2022-08-04 日本ゼオン株式会社 Composition pour couche fonctionnelle d'élément électrochimique, stratifié pour élément électrochimique et élément électrochimique
JPWO2022163591A1 (fr) * 2021-01-29 2022-08-04
JP7800452B2 (ja) 2021-01-29 2026-01-16 日本ゼオン株式会社 電気化学素子機能層用組成物、電気化学素子用積層体及び電気化学素子
JP2022125963A (ja) * 2021-02-17 2022-08-29 東レ株式会社 電気化学素子用セパレータおよび電気化学素子用セパレータの製造方法

Also Published As

Publication number Publication date
KR102477891B1 (ko) 2022-12-14
CN107112480A (zh) 2017-08-29
JP6750506B2 (ja) 2020-09-02
JPWO2016110894A1 (ja) 2017-10-19
CN107112480B (zh) 2019-09-13
KR20170102876A (ko) 2017-09-12

Similar Documents

Publication Publication Date Title
JP6750506B2 (ja) 非水系二次電池用セパレータおよびその製造方法、並びに、非水系二次電池
JP6520938B2 (ja) 非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池
JP6601486B2 (ja) 非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池
JP6504168B2 (ja) 非水系二次電池機能層用組成物、非水系二次電池用機能層付き基材、非水系二次電池用積層体の製造方法および非水系二次電池
KR102494518B1 (ko) 비수계 이차 전지용 적층체 및 비수계 이차 전지 부재의 제조 방법
JP6614141B2 (ja) 非水系二次電池用積層体およびその製造方法、並びに、非水系二次電池
JP6413419B2 (ja) 非水系二次電池多孔膜用複合粒子、非水系二次電池用多孔膜、非水系二次電池用電池部材、および非水系二次電池
JP6398431B2 (ja) 非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池
JP6455140B2 (ja) 非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池
JP6737182B2 (ja) 非水系二次電池機能層用組成物、非水系二次電池用機能層および非水系二次電池
JP6589269B2 (ja) 非水系二次電池接着層用組成物、非水系二次電池用接着層および非水系二次電池
WO2020090395A1 (fr) Composition de couche fonctionnelle de batterie secondaire non aqueuse, couche fonctionnelle de batterie secondaire non aqueuse, séparateur pour batterie secondaire non aqueuse et batterie secondaire non aqueuse
JP6565935B2 (ja) 非水系二次電池機能層用組成物、非水系二次電池用セパレータおよび非水系二次電池
WO2016051674A1 (fr) Composition adhésive pour élément électrochimique, couche adhésive pour élément électrochimique et élément électrochimique
WO2018096975A1 (fr) Composition pour couches fonctionnelles de batterie rechargeable à électrolyte non aqueux, couche fonctionnelle pour batteries rechargeables à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux
JP6834127B2 (ja) 非水系二次電池用機能層の形成方法、および非水系二次電池の製造方法
JP6536017B2 (ja) 非水系二次電池接着層用組成物、非水系二次電池用接着層、非水系二次電池部材、非水系二次電池、および非水系二次電池用接着層の製造方法
JP6891392B2 (ja) 非水系二次電池用積層体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15876775

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016568172

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20177017829

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15876775

Country of ref document: EP

Kind code of ref document: A1