WO2016103559A1 - Composition pour des couches fonctionnelles de batterie rechargeable non aqueuse, séparateur pour des batteries rechargeables non aqueuses et batterie rechargeable non aqueuse - Google Patents

Composition pour des couches fonctionnelles de batterie rechargeable non aqueuse, séparateur pour des batteries rechargeables non aqueuses et batterie rechargeable non aqueuse Download PDF

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WO2016103559A1
WO2016103559A1 PCT/JP2015/005677 JP2015005677W WO2016103559A1 WO 2016103559 A1 WO2016103559 A1 WO 2016103559A1 JP 2015005677 W JP2015005677 W JP 2015005677W WO 2016103559 A1 WO2016103559 A1 WO 2016103559A1
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functional layer
polymer
secondary battery
separator
organic particles
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PCT/JP2015/005677
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English (en)
Japanese (ja)
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智一 佐々木
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日本ゼオン株式会社
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Priority to JP2016565871A priority Critical patent/JP6565935B2/ja
Publication of WO2016103559A1 publication Critical patent/WO2016103559A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the 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
    • H01M50/443—Particulate 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

Definitions

  • the present invention relates to a composition for a non-aqueous secondary battery functional layer, 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 abbreviated as “secondary batteries”) have the characteristics of being small and lightweight, having high energy density, and capable of repeated charge and discharge. It is used for a wide range of purposes.
  • the 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.
  • Patent Document 1 a functional layer composition containing inorganic fine particles and a particulate polymer A having a melting point of 80 ° C. or lower and 100 ° C. or lower is applied onto a separator substrate made of a thermoplastic resin and dried. It describes that a separator having a functional layer for the purpose of improving heat resistance is produced. And this separator is used for a secondary battery together with a positive electrode provided with a positive electrode mixture layer comprising a positive electrode active material and a particulate polymer B having a melting point within a specific range.
  • the porosity of the functional layer before immersion in the electrolyte is set to 30% or more and 70% or less, so that the ion conductivity between the positive electrode and the negative electrode is improved and the secondary battery is improved.
  • the internal temperature rises excessively it is possible to secure a shutdown function that blocks ion conduction and prevents thermal runaway of the secondary battery.
  • the functional layer formed using the functional layer composition has poor adhesion after being immersed in the electrolyte, and the electrode and the separator are sufficiently disposed in the secondary battery via the functional layer. It was difficult to make it adhere to. Moreover, in the said patent document 1, it was also difficult to exhibit battery characteristics, such as the high temperature cycle characteristic and low temperature output characteristic which were excellent in the secondary battery. That is, the above-described conventional technology has room for improvement in terms of enhancing the battery characteristics of the secondary battery while improving the adhesion of the functional layer after being immersed in the electrolyte solution.
  • the present invention provides a composition for a functional layer of a non-aqueous secondary battery that can form a functional layer that can exhibit excellent adhesive properties after immersion in an electrolyte and can provide excellent battery characteristics to a secondary battery.
  • the purpose is to do.
  • the present invention also provides a separator for a non-aqueous secondary battery that can exhibit excellent battery characteristics for a non-aqueous secondary battery while firmly adhering to an electrode through a functional layer after immersion in an electrolytic solution. Objective.
  • an object of this invention is to provide the non-aqueous secondary battery which is excellent in a battery characteristic.
  • the present inventor has intensively studied for the purpose of solving the above problems. Then, the present inventor firstly, the functional layer including organic particles having a specific core-shell structure including a core portion having a specific electrolyte solution swelling degree and a shell portion and a binder for the functional layer is immersed in the electrolyte solution. The idea was to improve the battery characteristics of the secondary battery with excellent adhesion later.
  • the present inventors have further studied and have come to pay attention to the viscous behavior of the functional layer composition. Specifically, for the purpose of reducing the functional layer ion diffusibility and cost, the functional layer has been conventionally thinned, but the present inventor should apply the functional layer composition thinly on the substrate. If the viscosity of the functional layer composition is simply reduced, the particulate component (such as the functional layer binder) in the functional layer composition settles after application to the base material. It was found that the ion diffusibility of the separator and the like is impaired by clogging.
  • the present inventor has determined that the viscosity component ⁇ 0 under a low shear condition (shear rate of 100 sec ⁇ 1 ) is within a specific range, so that the particulate component in the composition for a functional layer after coating.
  • Viscosity ⁇ 1 under high shear conditions (shear rate 10000 sec ⁇ 1 ) in view of the fact that high shear is normally applied to the composition for the functional layer at the time of application to the substrate, while preventing clogging of the voids by suppressing sedimentation of the voids by but setting the ratio of eta 0 for such eta 1 falls within the range it is easy coating ( ⁇ 0 / ⁇ 1), the battery characteristics of the adhesive and the secondary battery after the electrolyte immersing the functional layer further It was newly found that it becomes possible to increase.
  • the present inventor forms a functional layer on the separator base material from the viewpoint of ensuring ion diffusibility in the electrolyte as the whole separator in the separator having the functional layer on the separator base material.
  • the idea was that it was important to estimate the degree of voids inherent in the porous separator base material after immersion in the electrolyte. And by keeping the degree of change of the porosity within a specific range, the ion diffusion property of the separator as a whole is enhanced while ensuring the adhesiveness after immersion of the functional layer in the electrolyte solution, and the battery characteristics of the secondary battery It was newly found that it is possible to further increase
  • the composition for non-aqueous secondary battery functional layers of this invention is a non-aqueous type
  • the organic particles having the specific core-shell structure including the core portion and the shell portion having the specific electrolyte swelling degree and the binder for the functional layer, and the values of ⁇ 0 and ⁇ 0 / ⁇ 1 can be formed by using a functional layer composition having a specific range within a specific range, which is excellent in adhesiveness after immersion in an electrolytic solution and can exhibit battery characteristics excellent in a secondary battery. .
  • the “electrolyte swelling degree” of the polymer of the core part and the shell part of the organic particles can be measured by using the measuring method described in the examples of the present specification.
  • the "viscosity eta 1 at a shear rate of 10000 sec -1" and “viscosity eta 0 at a shear rate of 100 sec -1" functional layer composition is a viscosity at a measurement temperature of 25 ° C. at each shear rate, the It can measure using the measuring method as described in the Example of a specification.
  • the glass transition temperature of the polymer in the core part is ⁇ 50 ° C. or more and 150 ° C. or less, and the glass transition temperature of the polymer in the shell part is 50 ° C. or more and 200 ° C. or less is preferable. This is because if the glass transition temperatures of the polymer in the core part and the shell part are within the above-mentioned ranges, the adhesion of the functional layer after immersion in the electrolyte and the battery characteristics of the secondary battery can be further improved.
  • the “glass transition temperature” of the polymer of the core part and the shell part of the organic particles can be measured using the measuring method described in the examples of the present specification.
  • the polymer of the core part preferably includes at least one of a reactive surfactant monomer unit and a macromonomer structural unit.
  • the polymer of the shell part preferably includes at least one of a reactive surfactant monomer unit and a macromonomer structural unit.
  • the polymer constituting the organic particles includes at least one of a reactive surfactant monomer unit and a macromonomer structural unit, an appropriate viscosity is imparted to the functional layer composition, and the functional layer This is because it is possible to further improve the adhesion and the battery characteristics of the secondary battery after immersion of the electrolyte.
  • “comprising a monomer unit” means “a polymer-derived structural unit is contained in a polymer obtained using the monomer”.
  • “including a macromonomer structural unit” means “a polymer obtained using the macromonomer contains a structural unit derived from a macromonomer”.
  • the separator for non-aqueous secondary batteries of this invention is a separator base material, On the surface of at least one of the said separator base material, A separator for a non-aqueous secondary battery comprising a functional layer including organic particles and a functional layer binder, wherein the organic particles partially cover the core portion and the outer surface of the core portion.
  • the core portion is made of a polymer having a swelling degree with respect to the electrolytic solution of 5 to 30 times, and the shell portion has a swelling degree with respect to the electrolytic solution of more than 1 times 4
  • a porosity M 0 after immersion of the separator substrate in the electrolyte solution and a porosity M 1 after immersion of the electrolyte solution in the non-aqueous secondary battery separator ( 1 ) Porosity change ratio calculated in 1) Characterized in that C is 5 to 50%.
  • a functional layer containing organic particles having a specific core-shell structure including a core portion and a shell portion having a specific degree of electrolyte swelling and a binder for a functional layer is provided on the separator substrate, and the above formula (1) a separator value of M C is within a specific range obtained from the after electrolyte immersion, firmly adhered to the electrode through the functional layer, also to exhibit excellent battery characteristics to the secondary battery be able to.
  • the porosity M 0 after immersion in the electrolyte solution” of the separator substrate and “the porosity M 1 after immersion in the electrolyte solution” of the separator for the non-aqueous secondary battery are the same as those in the present specification It can be measured using the measurement method described in the examples.
  • the glass transition temperature of the polymer in the core portion is ⁇ 50 ° C. or more and 150 ° C. or less, and the glass transition temperature of the polymer in the shell portion is 50 ° C.
  • the temperature is preferably 200 ° C. or lower. If the glass transition temperatures of the polymer in the core and shell are within the above ranges, the battery characteristics of the secondary battery can be further improved while further improving the adhesion between the separator and the electrode after immersion in the electrolyte. Because you can.
  • the polymer of the core part includes at least one of a reactive surfactant monomer unit and a macromonomer structural unit.
  • the polymer of the shell portion includes at least one of a reactive surfactant monomer unit and a macromonomer structural unit.
  • the nonaqueous secondary battery of this invention is equipped with one of the separators for nonaqueous secondary batteries mentioned above, It is characterized by the above-mentioned. .
  • a secondary battery including any of the above-described separators for non-aqueous secondary batteries is excellent in battery characteristics such as high-temperature cycle characteristics and low-temperature output characteristics.
  • a composition for a non-aqueous secondary battery functional layer capable of forming a functional layer that can exhibit excellent adhesive properties after immersion in an electrolytic solution and provide excellent battery characteristics to a secondary battery. can do.
  • a separator for a non-aqueous secondary battery capable of exhibiting excellent battery characteristics for a non-aqueous secondary battery while firmly adhering to an electrode through a functional layer after immersion in an electrolytic solution. be able to.
  • the non-aqueous secondary battery excellent in a battery characteristic can be provided.
  • the composition for a nonaqueous secondary battery functional layer of the present invention is used as a material for preparing a functional layer constituting a battery member such as a separator or an electrode.
  • the functional layer formed using the nonaqueous secondary battery functional layer composition of the present invention may be a porous film layer for improving the heat resistance and strength of battery members such as separators and electrodes.
  • an adhesive layer for adhering battery members may be used, or a layer that exhibits both functions of the porous membrane layer and the adhesive layer may be used.
  • the separator for non-aqueous secondary batteries of the present invention comprises a separator base material and a functional layer on the separator base material, and the functional layer is, for example, the composition for a non-aqueous secondary battery functional layer of the present invention. It is formed using things.
  • the non-aqueous secondary battery of this invention is equipped with the separator for non-aqueous secondary batteries of this invention at least.
  • composition for functional layer of non-aqueous secondary battery contains at least organic particles having a specific structure and a binder for a functional layer other than the organic particles, optionally containing other components, water and the like as a dispersion medium Slurry composition. Further, the nonaqueous secondary battery functional layer composition, a ratio of the eta 0 on the viscosity eta 1 at viscosity eta 0, and shear rate 10000 sec -1 at a shear rate of 100 sec -1 is within a specific range, respectively It is characterized by that.
  • the functional layer formed using the composition for a non-aqueous secondary battery functional layer of the present invention has contributed to the properties of the organic particles and the viscous behavior of the functional layer composition described above, after immersion in the electrolyte solution. Exhibits excellent adhesive properties, and can provide excellent battery characteristics to the secondary battery. Specifically, since the functional layer formed using the composition for a non-aqueous secondary battery functional layer of the present invention contains predetermined organic particles that exhibit excellent adhesiveness in the electrolytic solution, Even after immersion in the electrolytic solution, excellent adhesiveness can be exhibited, and excellent battery characteristics can be exhibited in the non-aqueous secondary battery.
  • the composition for a non-aqueous secondary battery functional layer of the present invention has a viscosity ⁇ 0 at a shear rate of 100 sec ⁇ 1 within a specific range, and the ⁇ against the viscosity ⁇ 1 at a shear rate of 10000 sec ⁇ 1. Since the ratio of 0 is within a specific range, it is possible to suppress sedimentation of the particulate component after application while ensuring applicability to the base material of the composition for the functional layer. Can be improved.
  • Organic particles contained in the composition for a non-aqueous secondary battery functional layer bear a function of exerting excellent adhesiveness in a functional layer formed using the composition for a non-aqueous secondary battery functional layer.
  • 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, and the electrolyte swelling degree of the core portion is not less than 5 times and not more than 30 times.
  • the shell part is made of a polymer having an electrolyte solution swelling degree of more than 1 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 obtained using the composition for functional layers can improve the battery characteristic of a secondary battery favorably.
  • the functional layer obtained using the functional layer composition does not exhibit a large adhesive force before being immersed in the electrolytic solution, the functional layer itself and the member including the functional layer are blocked (functional layer). Or sticking between members via the functional layer), and handling properties are 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 of the swollen shell part is activated, and the separator base or electrode base on which the functional layer is formed, or the electrode or separator adhered to the battery member having the functional layer, etc.
  • the shell part can be firmly bonded to the battery member due to factors such as causing a chemical or electrical interaction with a functional group on the surface of the battery member.
  • the shell portion does not exhibit a large adhesive force before it swells in the electrolytic solution.
  • the functional layer containing the said organic particle it is guessed that it is possible to adhere
  • 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 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 particles 100 have a core-shell structure including a core part 110 and a shell part 120.
  • 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” of the organic particles can be measured using the measurement method described in the examples of the present specification.
  • the volume average particle diameter D50 of the organic particles is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, further preferably 0.4 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less. is there.
  • the volume average particle diameter D50 of the organic particles is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, further preferably 0.4 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less. is there.
  • volume average particle diameter D50 of the organic particles not more than the upper limit of the above range, it is possible to improve the adhesion between battery members in the electrolytic solution and improve the high-temperature cycle characteristics of the secondary battery. Further, it is possible to bring about an improvement in adhesiveness that the functional layer before immersion in the electrolyte exhibits by heating.
  • 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, further preferably 5% or more, preferably Is 40% or less, more preferably 30% or less, still more preferably 25% or less, and particularly preferably 15% or less.
  • the “core-shell ratio” of the organic particles can be measured using the measuring method described in the examples of the present specification.
  • 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 in the core part needs to be 5 times or more, preferably 6 times or more, more preferably 7 times or more, and 9.6. More preferably, it is more than double, and it is necessary that it is 30 times or less, preferably 25 times or less, and more preferably 20 times or less.
  • the organic particles are swollen to some extent in the electrolytic solution, so that the adhesion of the functional layer is ensured and the high-temperature cycle characteristics of the secondary battery can be improved.
  • 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 type and amount of the monomer for producing the polymer of the core part are determined. Appropriate selection can be mentioned. Generally, when 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. On the other hand, when 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 5 ° C. or higher, more preferably 10 ° C. It is particularly preferable that the temperature is 150 ° C. or lower, more preferably 140 ° C. or lower, and more preferably 130 ° C. or lower.
  • 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) acrylic acid ester monomer unit or a (meth) acrylonitrile monomer unit, and more preferably contains a (meth) acrylic acid ester monomer unit. It is particularly preferred that it contains a monomer unit derived from methyl methacrylate. This makes it easy to control the degree of swelling of the polymer and further enhances the ion diffusibility of the functional layer using organic particles.
  • the proportion of the (meth) acrylic acid ester monomer unit in the polymer of the core part is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 95% by mass. Hereinafter, it is more preferably 90% by mass or less, and further preferably 80% by mass or less.
  • the ratio of the (meth) acrylic acid ester monomer unit below the upper limit of the above range, the adhesion of the functional layer in the electrolytic solution is improved, and the high-temperature cycle characteristics of the secondary battery are further improved. be able to.
  • the polymer of a core part contains at least one of a reactive surfactant monomer unit and a macromonomer structural unit.
  • the organic particles having the polymer in the core part into which the reactive surfactant monomer unit and / or the macromonomer structural unit are introduced can impart an appropriate viscosity to the functional layer composition. The cause of this is not clear, but by incorporating reactive surfactant monomer units and / or macromonomer structural units, the polymer having these structures has graft chains, and the functional layer composition It is presumed that the resistance to water is increased due to the contribution of the graft chain extending from the organic particles.
  • the polymer of the core part preferably contains a reactive surfactant monomer unit.
  • Reactive surfactant monomer units are easy to introduce into organic particles and are difficult to desorb from organic particles, increase the wettability of organic particles to electrolytes, and further improve battery characteristics such as low-temperature output characteristics. Because it is possible. In addition, since the introduction into the organic particles is easy as described above, the high temperature cycle is less likely to decrease due to the decomposition of the unreacted monomer as compared with the macromonomer. It should be noted that the reactive surfactant monomer unit can be introduced into the polymer of the shell part as will be described later, but it suppresses an excessive increase in the coverage of the organic particles and reduces the low temperature of the secondary battery. From the viewpoint of securing output characteristics, it is preferable to introduce the polymer into the core polymer.
  • the reactive surfactant monomer that can form the reactive surfactant monomer unit has a polymerizable group that can be copolymerized with other monomers, and the surfactant group. It represents a monomer having (that is, a hydrophilic group and a hydrophobic group).
  • the reactive surfactant monomer unit obtained by the polymerization of the reactive surfactant monomer constitutes a part of the polymer contained in the organic particles and can function as a surfactant.
  • the reactive surfactant monomer has a polymerizable unsaturated group, and this polymerizable unsaturated group can also act as a hydrophobic group after polymerization.
  • the polymerizable unsaturated group include vinyl group, allyl group, vinylidene group, propenyl group, isopropenyl group, and isobutylidene group.
  • the type of the polymerizable unsaturated group may be one type or two or more types.
  • the reactive surfactant monomer usually has a hydrophilic group as a portion that exhibits hydrophilicity.
  • Reactive surfactant monomers are classified into anionic, cationic and nonionic surfactants depending on the type of hydrophilic group.
  • the number average molecular weight of the reactive surfactant monomer is preferably 500 or more, more preferably 1000 or more, still more preferably 2000 or more, preferably 4000 or less, more preferably 3500 or less, and still more preferably 3000. It is as follows.
  • the number average molecular weight of the reactive surfactant monomer is equal to or higher than the lower limit of the above range, so that the organic particles including the polymer containing the reactive surfactant monomer unit are good for the functional layer composition. Can be given viscosity.
  • the number average molecular weight of the reactive surfactant monomer is not more than the upper limit of the above range, polymerization using the reactive surfactant monomer is facilitated.
  • the “number average molecular weight” of the reactive surfactant monomer is determined by using polystyrene as a standard substance and a solution obtained by dissolving 0.85 g / ml sodium nitrate in a 10% by volume aqueous solution of dimethylformamide as a developing solvent. It can be measured by gel permeation chromatography (GPC) used.
  • a reactive surfactant having a polyoxyalkylene group is preferably used from the viewpoint of easy introduction into organic particles and improvement of low-temperature output characteristics of the secondary battery.
  • a compound represented by the following formula (I) is more preferable.
  • R represents a divalent linking group. Examples of R include —Si—O— group, methylene group and phenylene group.
  • R 1 represents a hydrophilic group. An example of R 1 includes —SO 3 NH 4 .
  • n represents an integer of 1 or more and 100 or less.
  • polyoxyalkylene alkenyl ether ammonium sulfate can be mentioned without being specifically limited.
  • a reactive surfactant monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the ratio of the reactive surfactant monomer unit in the polymer of the core part is preferably 0.05% by mass or more, More preferably, it is 0.1 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 4 mass% or less.
  • the ratio of the reactive surfactant monomer unit is set to the lower limit of the above range or more, the viscosity imparting ability of the organic particles to the functional layer composition is secured, and the dispersibility of the organic particles is improved.
  • the wettability of the organic particles to the electrolytic solution can be improved, and the low-temperature output characteristics of the secondary battery can be further improved.
  • the high temperature cycling characteristic of a secondary battery can further be improved by making the ratio of a reactive surfactant monomer unit below the upper limit of the said range.
  • a macromonomer that can form a macromonomer structural unit is a polymer that has a polymerizable group that can be copolymerized with other monomers, and functions as a monomer to form a new polymer by a polymerization reaction.
  • the polymeric group which can be copolymerized with another monomer exists in the terminal of the polymer chain which comprises a macromonomer.
  • the polymerizable group is introduced into the terminal of the polymer after obtaining a predetermined polymer, for example, and by this introduction, a macromonomer having a polymerizable group at the terminal of the polymer chain can be obtained.
  • the compound included in the reactive surfactant monomer described above is not included in the macromonomer.
  • the number average molecular weight of the macromonomer which is a polymer is preferably 500 or more, more preferably 600 or more, further preferably 650 or more, preferably 9000 or less, more preferably 8000 or less, and further preferably 7000 or less. It is.
  • the organic particles including the polymer containing the macromonomer structural unit can impart good viscosity to the functional layer composition.
  • the number average molecular weight of the macromonomer is not more than the upper limit of the above range, polymerization using the macromonomer becomes easy.
  • the “number average molecular weight” of the macromonomer is measured by GPC using polystyrene as a standard substance and 0.85 g / ml sodium nitrate dissolved in a 10% by volume aqueous solution of dimethylformamide as a developing solvent. be able to.
  • (meth) acrylic acid ester macromonomer containing a (meth) acrylic acid ester monomer unit (for example, 50 mass% or more), an aromatic vinyl monomer unit (for example, 50 mass) % Or more), and polycaprolactone-modified hydroxyalkyl acrylate obtained by reacting hydroxyalkyl acrylate with polycaprolactone.
  • (meth) acrylic acid ester macromonomer and polycaprolactone-modified hydroxyalkyl acrylate are preferable from the viewpoint of increasing the resistance between the organic particles and water and increasing the viscosity of the functional layer composition.
  • a macromonomer may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the ratio of the macromonomer structural unit in the polymer of the core part is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. Yes, preferably 5% by mass or less, more preferably 3% by mass or less.
  • the polymer of the core part may contain either a reactive surfactant monomer unit or a macromonomer structural unit, and both the reactive surfactant monomer unit and the macromonomer structural unit. May be included.
  • the total of the ratio of the reactive surfactant monomer unit and the ratio of the macromonomer structural unit in the polymer of the core part is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably Is 5% by mass or less, more preferably 4% by mass or less.
  • the total of the ratio of the reactive surfactant monomer unit and the ratio of the macromonomer structural unit equal to or higher than the lower limit of the above range, the ability to impart viscosity to the composition for the functional layer of the organic particles is secured, The dispersibility of the particles is improved.
  • the sum of the ratio of the reactive surfactant monomer unit and the ratio of the macromonomer structural unit not more than the upper limit of the above range, the high temperature cycle characteristics of the secondary battery can be further improved.
  • 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, further 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 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 degree of swelling of the polymer can be easily 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 (meth) acrylic acid esters such as diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and 1,3-butylene glycol diacrylate.
  • di (meth) acrylic acid esters such as diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and 1,3-butylene glycol diacrylate.
  • 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; and the like.
  • ethylene glycol dimethacrylate, allyl glycidyl ether, and glycidyl methacrylate are preferable, and ethylene glycol dimethacrylate is more preferable from the viewpoint of easily controlling the degree of electrolyte solution swelling of the polymer in the core portion.
  • 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 5 mass% or less, More preferably, it is 4 mass% or less, More preferably, it is 3 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. 1.3 times or more, more preferably 4 times or less, 3.5 times or less, and more preferably 3 times or less.
  • the electrolyte swelling degree of the polymer of the shell part exceed the lower limit of the above range, the adhesion of the organic particles in the electrolyte can be secured, and the high temperature cycle characteristics of the secondary battery can be improved.
  • the electrolyte solution swelling degree of the polymer of the shell part below the upper limit of the above range, the adhesion between the battery members through the functional layer in the electrolyte solution is improved, and the high temperature cycle characteristics of the secondary battery Can be improved.
  • 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 equal to or higher than the lower limit value of the above range, in addition to suppressing the occurrence of blocking between battery members, the high-temperature cycle characteristics of the secondary battery can be further improved.
  • the adhesiveness of the functional layer in electrolyte solution can further be improved by making a glass transition temperature below into the upper limit of the said range.
  • 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.
  • an aromatic vinyl monomer is preferable as the monomer used for the preparation of the shell polymer. That is, 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. Particularly preferably, it is 80% by mass or more, preferably 100% by mass or less, more preferably 99.5% by mass or less, and further preferably 99% by mass or less.
  • the polymer of a shell part contains at least one of a reactive surfactant monomer unit and a macromonomer structural unit.
  • the organic particles having the polymer in the shell portion into which the reactive surfactant monomer unit and / or the macromonomer structural unit are introduced can impart an appropriate viscosity to the functional layer composition.
  • the polymer of a shell part contains a macromonomer structural unit from a viewpoint of suppressing the excessive raise of the coverage of an organic particle, and ensuring the low temperature output characteristic of a secondary battery.
  • the reactive surfactant monomer capable of forming the reactive surfactant monomer unit the same monomer as the reactive surfactant monomer described above in the section of “core part” is used.
  • a reactive surfactant monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the reactive surfactant monomer is a reactive surfactant monomer having a polyoxyalkylene group from the viewpoint of easy introduction into organic particles and improvement of low-temperature output characteristics of a secondary battery. Is preferable, and the compound represented by the above formula (I) is more preferable.
  • the ratio of the reactive surfactant monomer unit in the polymer of the shell part is preferably 0.25% by mass or more, more preferably It is 0.5 mass% or more, preferably 25 mass% or less, more preferably 20 mass% or less.
  • examples of the macromonomer that can form the macromonomer structural unit include the same monomers as the macromonomer described above in the section “core part”.
  • a macromonomer may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • (meth) acrylic acid ester macromonomer and polycaprolactone-modified hydroxyalkyl acrylate are preferable from the viewpoint of increasing the resistance between the organic particles and water and increasing the viscosity of the functional layer composition.
  • the ratio of the macromonomer structural unit in the polymer of the shell part is preferably 0.5% by mass or more, more preferably 2.5% by mass or more. Yes, preferably 25% by mass or less, more preferably 15% by mass or less.
  • the polymer of the shell part may contain either a reactive surfactant monomer unit or a macromonomer structural unit, or both of the reactive surfactant monomer unit and the macromonomer structural unit. May be included.
  • the total of the ratio of the reactive surfactant monomer unit and the ratio of the macromonomer structural unit in the polymer of the shell part is preferably 0.5% by mass or more, more preferably 2.5% by mass or more, preferably Is 25% by mass or less, more preferably 15% by mass or less.
  • the total of the ratio of the reactive surfactant monomer unit and the ratio of the macromonomer structural unit equal to or higher than the lower limit of the above range, the ability to impart viscosity to the composition for the functional layer of the organic particles is secured, The dispersibility of the particles is improved.
  • the sum of the ratio of the reactive surfactant monomer unit and the ratio of the macromonomer structural unit not more than the upper limit of the above range, the high temperature cycle characteristics of the secondary battery can be further improved.
  • the polymer of the shell part may contain an acid group-containing monomer unit in addition to the aromatic vinyl monomer unit, the reactive surfactant monomer unit, and the macromonomer structural 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 monomers that can constitute the acid group-containing monomer unit that can be included 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.
  • composition for a non-aqueous secondary battery functional layer of the present invention needs to contain a binder for a functional layer (excluding the organic particles described above).
  • the organic particles are not swollen in the electrolytic solution and usually do not exhibit adhesiveness when not heated. Therefore, from the viewpoint of suppressing organic particles from falling off the functional layer immediately after the formation of the functional layer (before heating or before immersion in the electrolytic solution), the functional layer composition is not swollen in the electrolytic solution. And it is preferable that the binder for functional layers which exhibits adhesiveness in the state which is not heated is included. By using the binder for the functional layer, it is possible to prevent components such as organic particles from falling off the functional layer even when the electrolyte is not swollen and not heated.
  • the functional layer binder that can be used in combination with the organic particles includes a known binder that is water-insoluble and dispersible in a dispersion medium such as water, for example, a thermoplastic elastomer.
  • 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. Can be used.
  • These functional layer binders may be used alone or in combination of two or more. However, when a functional layer binding material combining two or more types is used, the polymer as the functional layer binding material is different from the organic particles having the core-shell structure made of the predetermined polymer described above. is there.
  • 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 equal to or less than the upper limit of the above range, the ion diffusibility 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 functional layer binder is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 90 ° C. or higher, still more preferably ⁇ 80 ° C. or higher, and particularly preferably ⁇ 50 ° C. or higher. Also, it is preferably 25 ° C. or lower, more preferably 5 ° C. or lower, and further preferably ⁇ 10 ° C. or lower.
  • the volume average particle diameter D50 of the functional layer binder is preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less.
  • the volume average particle diameter D50 of the binder for functional layers can be equal to or greater than the lower limit of the above range.
  • the dispersibility of the binder for functional layers can be enhanced.
  • the adhesiveness of the binder for functional layers can be improved by making volume average particle diameter D50 below the upper limit of the said range.
  • the “volume average particle diameter D50” of the functional layer binder can be measured using the method described in the examples of the present specification.
  • content of the binder for functional layers in the composition for functional layers is 1 mass part or more with respect to 100 mass parts of organic particles mentioned above, and it is more preferably 5 mass parts or more. Preferably, it is 10 parts by mass or more, more preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less.
  • 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 can be polymerized in water, and an aqueous dispersion containing a particulate functional layer binder can be suitably used as a material for the functional layer composition as it is. preferable.
  • 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.
  • composition for non-aqueous secondary battery functional layers 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 such as an electrolytic solution additive, and water-soluble polymers and non-conductive particles described later.
  • Water-soluble polymer Viscosity can be imparted to the functional layer composition by blending the water-soluble polymer into the functional layer composition that is an aqueous slurry composition.
  • the water-soluble polymer has adhesiveness and electrolytic solution resistance, it can play a role in assisting adhesion between the components in the functional layer and between the battery members in the secondary battery.
  • a substance in the present invention is “water-soluble” means that an insoluble content is less than 1.0% by mass when 0.5 g of the substance is dissolved in 100 g of water at 25 ° C. Say.
  • a substance whose solubility changes depending on the pH of water is considered to be “water-soluble” if it falls under the above-mentioned “water-soluble” at least at any pH.
  • water-soluble polymer include natural polymers, semi-synthetic polymers, and synthetic polymers.
  • natural polymers include plant- or animal-derived polysaccharides and proteins, fermentation-treated products of these microorganisms, and heat-treated products thereof. These natural polymers can be classified into plant-based natural polymers, animal-based natural polymers, and microorganism-produced natural polymers.
  • plant-based natural polymers include gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, cannan, quince seed (malmello), arche colloid (gasso extract), starch (rice, corn, potato, wheat) Etc.) and glycyrrhizin.
  • animal natural polymers include collagen, casein, albumin, and gelatin.
  • microorganism-produced natural polymer include xanthan gum, dextran, succinoglucan, and bullulan.
  • the semisynthetic polymer examples include cellulose semisynthetic polymers.
  • the cellulose semisynthetic polymer can be classified into nonionic cellulose semisynthetic polymer, anionic cellulose semisynthetic polymer and cationic cellulose semisynthetic polymer.
  • Nonionic cellulose-based semisynthetic polymers include, for example, alkyl celluloses such as methyl cellulose, methyl ethyl cellulose, ethyl cellulose, and microcrystalline cellulose; hydroxyethyl cellulose, hydroxybutyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxy Examples thereof include hydroxyalkylcelluloses such as propylmethylcellulose stearoxy ether, carboxymethylhydroxyethylcellulose, alkylhydroxyethylcellulose, and nonoxynylhydroxyethylcellulose.
  • anionic cellulose semisynthetic polymer examples include substituted products obtained by substituting the above nonionic cellulose semisynthetic polymer with various derivative groups and salts thereof (sodium salt, ammonium salt, etc.). Specific examples include sodium cellulose sulfate, methyl cellulose, methyl ethyl cellulose, ethyl cellulose, carboxymethyl cellulose (CMC) and salts thereof.
  • Examples of the cationic cellulose semisynthetic polymer include low nitrogen hydroxyethylcellulose dimethyl diallylammonium chloride (polyquaternium-4), chloride O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose (polyquaternium-10). ), And O- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydroxyethylcellulose (polyquaternium-24) chloride.
  • Synthetic polymers include polyacrylates such as sodium polyacrylate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, acrylic acid or copolymers of acrylate and vinyl alcohol, maleic anhydride, maleic acid or fumaric acid.
  • polyacrylates such as sodium polyacrylate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, acrylic acid or copolymers of acrylate and vinyl alcohol, maleic anhydride, maleic acid or fumaric acid.
  • water-soluble polymers carboxymethyl cellulose and its salts, and acrylamide polymers into which carboxylic acid groups have been introduced are preferred.
  • the water-soluble polymer has properties of imparting viscosity to the functional layer composition and improving the adhesion of the functional layer as described above.
  • the addition of the water-soluble polymer may impair the flexibility and ion diffusibility of the functional layer, which may reduce the adhesion of the functional layer and / or battery characteristics such as low-temperature output characteristics. . Therefore, in the present invention, from the viewpoint of securing the battery characteristics of the secondary battery, the content of the water-soluble polymer in the functional layer composition is preferably 5 parts by mass or less per 100 parts by mass of the organic particles. More preferably, it is 3 mass parts or less, More preferably, it is 0.1 mass part or less.
  • the lower limit of the content of the water-soluble polymer in the composition for the functional layer when adding a water-soluble polymer for the purpose of viscosity adjustment is preferably 0.05 parts by mass or more per 100 parts by mass of the organic particles. More preferably, it is 0.1 mass part or more.
  • the functional layer composition may contain non-conductive particles.
  • the non-conductive particles to be blended in the functional layer composition 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.
  • 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 method for preparing the composition for the functional layer is not particularly limited. Usually, the organic particles, the binder for the functional layer, water as a dispersion medium, and other components used as necessary are mixed. Thus, a composition for a functional layer is prepared.
  • 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 is preferably an apparatus capable of uniformly dispersing and mixing the above components. Examples include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, and a planetary mixer.
  • a high dispersion apparatus such as a bead mill, a roll mill, or a fill mix is also included.
  • the viscosity ⁇ 0 at a shear rate of 100 sec ⁇ 1 of the obtained composition for a non-aqueous secondary battery functional layer needs to be 10 mPa ⁇ s or more and 100 mPa ⁇ s or less, preferably 15 mPa ⁇ s or more. More preferably, it is 20 mPa ⁇ s or more, more preferably 31 mPa ⁇ s or more, and preferably 80 mPa ⁇ s or less, more preferably 50 mPa ⁇ s or less.
  • ⁇ 0 is equal to or more than the lower limit of the above range, sedimentation of particulate components in the functional layer composition applied onto the substrate can be suppressed, and clogging of the substrate can be prevented. Therefore, the space
  • the nonaqueous secondary battery functional layer composition viscosity eta 0 ratio of a shear rate 100 sec -1 for viscosities eta 1 at a shear rate of 10000sec -1 ( ⁇ 0 / ⁇ 1 ) is 1 to 5
  • ⁇ 0 / ⁇ 1 is not less than the lower limit of the above range, high viscosity under high shear conditions is suppressed, and applicability of the functional layer composition on the substrate is ensured.
  • ⁇ 0 / ⁇ 1 is not more than the upper limit of the above range, an excessive increase in voids in the obtained functional layer can be suppressed, and adhesion of the functional layer in the electrolytic solution is ensured. Therefore, battery characteristics such as low-temperature output characteristics can be improved.
  • ⁇ 0 , ⁇ 1 and ⁇ 0 / ⁇ 1 are the contents of the organic particles and the water-soluble polymer in the functional layer composition, the reactive surfactant monomer unit and the macromonomer structure in the organic particles. It can adjust suitably by adjusting content of a unit.
  • a functional layer can be formed on a suitable base material using the composition for a non-aqueous secondary battery functional layer described above.
  • the functional layer for a non-aqueous secondary battery can be formed by drying the composition for a non-aqueous secondary battery functional layer on an appropriate substrate. That is, the functional layer for a non-aqueous secondary battery of the present invention comprises a dried product of the above-described composition for a non-aqueous secondary battery functional layer, and usually contains the organic particles and the functional layer binder. Optionally, the above other components are contained.
  • the polymer and / or functional layer binder in the organic particles includes a crosslinkable monomer unit
  • the polymer and / or functional layer binder in the organic particles is a slurry.
  • the composition may be crosslinked at the time of drying or at the time of heat treatment optionally performed after drying (that is, the functional layer for a non-aqueous secondary battery is composed of the organic particles and / or the functional layer binder described above). It may contain a cross-linked product).
  • the suitable abundance ratio of each component contained in the functional layer for non-aqueous secondary battery is the same as the suitable abundance ratio of each component in the composition for non-aqueous secondary battery functional layer.
  • the functional layer for a non-aqueous secondary battery according to the present invention can provide high blocking resistance to a battery member, and can exhibit excellent adhesion after being immersed in an electrolytic solution.
  • the battery characteristics (high temperature cycle characteristics and low temperature output characteristics) excellent in the secondary battery can be exhibited.
  • the base material for forming the functional layer is not particularly limited.
  • the separator base material can be used as the base material.
  • an electrode substrate formed by forming an electrode mixture layer on a current collector can be used as the substrate.
  • a functional layer may be formed on a separator base material etc.
  • the functional layer may be formed on the substrate and used as an electrode, or the functional layer formed on the release substrate may be once peeled off from the substrate and attached to another substrate to be used as a battery member. .
  • a separator substrate or an electrode substrate as the substrate.
  • the functional layer provided on the separator substrate or electrode substrate functions as a protective layer that increases the heat resistance and strength of the separator or electrode, and particularly as an adhesive layer that firmly bonds the separator and the electrode in the electrolytic solution. It can be suitably used as a single layer that simultaneously exhibits the above functions.
  • the separator base material for forming the functional layer is not particularly limited, and for example, those described in JP 2012-204303 A 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 film made of a resin such as polyethylene, polypropylene, polybutene, or polyvinyl chloride is preferable.
  • the separator base material may contain an arbitrary layer that can exhibit an intended function other than the functional layer.
  • Electrode substrate Although it does not specifically limit as an electrode base material (a positive electrode base material and a negative electrode base material) which forms a functional layer, The electrode base material with which the electrode compound-material layer was formed on the electrical power collector is mentioned.
  • 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) As the material layer binder) and the like, and the method for forming the electrode mixture layer on the current collector known ones can be used, for example, those described in JP2013-145663A be able to.
  • the electrode base material may include an arbitrary layer having an intended function other than the functional layer in a part thereof.
  • Examples of the method for forming a functional layer on a substrate such as the separator substrate and electrode substrate described above include the following methods. : 1) A method in which the composition for a functional layer is applied to the surface of a separator substrate or an electrode substrate (in the case of an electrode substrate, the surface on the electrode mixture layer side, the same shall apply hereinafter) and then dried; 2) A method of drying a separator substrate or electrode substrate after immersing the separator layer or electrode substrate in the functional layer composition; 3) A method for producing a functional layer by applying and drying a composition for a functional layer on a release substrate, and transferring the obtained functional layer to the surface of a separator substrate or an electrode substrate.
  • the method 1) is particularly preferable because the thickness of the functional layer can be easily controlled.
  • the method 1) includes a step of applying a functional layer composition on a separator substrate or electrode substrate (application step), and a function layer applied on the separator substrate or electrode substrate.
  • a step of drying the composition to form a functional layer (drying step) is provided.
  • the method for coating the functional layer composition on the separator substrate or the electrode substrate is not particularly limited.
  • spray coating method, doctor blade method, reverse roll method, direct roll method, gravure method examples include an extrusion method and a brush coating method.
  • the gravure method is preferable from the viewpoint of forming a thinner functional layer.
  • the method for drying the composition for the functional layer on the substrate is not particularly limited, and a known method can be used. For example, drying with warm air, hot air, low-humidity air, vacuum drying, infrared rays, A drying method by irradiation with an electron beam or the like can be mentioned.
  • 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 substrate is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, still more preferably 0.5 ⁇ m or more, preferably 3 ⁇ m or less, more preferably 1. It is 5 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the thickness of the functional layer is not less than the lower limit value of the range, the strength of the functional layer can be sufficiently secured, and by being not more than the upper limit value of the range, the ion diffusibility of the functional layer is ensured.
  • the low temperature output characteristics of the secondary battery can be further improved.
  • the separator for a non-aqueous secondary battery according to the present invention includes a separator base material and a functional layer containing specific organic particles and a binder for a functional layer on at least one surface of the separator base material, and preferably has a function.
  • the layer is a functional layer for a non-aqueous secondary battery formed by using the composition for a non-aqueous secondary battery functional layer of the present invention described above.
  • the nonaqueous secondary battery separator of the present invention, the void ratio calculated by the porosity M 0 of the separator base material, the following equation from porosity M 1 Tokyo separator for a nonaqueous secondary battery (1) change ratio M C is 5 to 50%.
  • M C (M 0 ⁇ M 1 ) / M 0 ⁇ 100 (1)
  • Nonaqueous secondary battery separator of the present invention the contribution of the organic particles described above and, due contribution that M C is within a specific range, strongly the electrode through the functional layer in an electrolytic solution
  • the battery characteristic which was excellent in the non-aqueous secondary battery can be exhibited, closely_contact
  • the separator substrate As the separator substrate, the same materials as those described in the section “Functional layer for non-aqueous secondary battery” can be used.
  • the porosity M 0 after electrolyte immersion of the separator substrate used in the non-aqueous secondary battery separator of the present invention are preferably 30% or more, more preferably 35% or more, more preferably 40% or more .
  • M 0 is 30% or more, the low-temperature output characteristics of the secondary battery including the non-aqueous secondary battery separator can be improved.
  • M 0 after electrolyte immersion can be adjusted in a known manner, such as changing the production conditions of the separator substrate.
  • the functional layer provided on the separator substrate contains at least organic particles having a specific structure and a binder for the functional layer, and optionally contains other components.
  • the organic particles contained in the functional layer, the binder for the functional layer, and other components can be the same as those listed in the section “Composition for functional layer of non-aqueous secondary battery”.
  • the preferred abundance ratio of each component is the same as the preferred abundance ratio of each component in the composition for a non-aqueous secondary battery functional layer.
  • the functional layer can be formed on the separator substrate using the method described in the section “Functional layer for non-aqueous secondary battery”, and the suitable thickness range of the functional layer on the separator substrate is This is the same as the range disclosed in “Functional layer for non-aqueous secondary battery”.
  • the porosity M 1 of the nonaqueous secondary battery separator of the present invention after immersion in the electrolyte is preferably 25% or more, more preferably 35% or more, and further preferably 38% or more.
  • M 1 is 25% or more, the low-temperature output characteristics of the secondary battery including the non-aqueous secondary battery separator can be further improved.
  • the upper limit of M 1 is not particularly limited, from the viewpoint of ensuring the strength of the separator for a nonaqueous secondary battery, usually not more than 50%.
  • the porosity M 1 after immersion in the electrolytic solution can be adjusted by changing the ⁇ 0 / ⁇ 1 of the functional layer composition, the drying conditions of the functional layer composition, or the like.
  • M C is at least as large as the lower limit of the range, adhesion to the separator base material of the functional layer after the electrolyte immersion is ensured.
  • the M C is not more than the upper limit of the range, and such as clogging of the separator substrate by forming a functional layer are suppressed, ion diffusion resistance of the separator for a nonaqueous secondary battery is secured, the secondary The low temperature output characteristics of the battery are improved.
  • the non-aqueous secondary battery of the present invention includes the above-described separator for non-aqueous secondary battery of the present invention. More specifically, the non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolytic solution, and the separator includes a separator substrate and a functional layer. It is. Since the non-aqueous secondary battery of the present invention includes the non-aqueous secondary battery separator of the present invention, the battery characteristics such as high-temperature cycle characteristics and low-temperature output characteristics are excellent.
  • the separator has a functional layer, but the positive electrode and the negative electrode may each have a functional layer.
  • a positive electrode and a negative electrode having a functional layer an electrode in which a functional layer is provided on an electrode substrate formed by forming an electrode mixture layer on a current collector can be used.
  • an electrode base material and a separator base material the thing similar to what was mentioned by the term of the "functional layer for non-aqueous secondary batteries" can be used.
  • the electrode which consists of an electrode base material mentioned above can be used, without being specifically limited.
  • an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
  • a lithium salt is used in a lithium ion secondary battery.
  • 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 because they are easily dissolved in a solvent and exhibit a high degree of dissociation.
  • electrolyte may be used individually by 1 type and may be used in combination of 2 or more types.
  • 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) dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC).
  • Carbonates such as propylene carbonate (PC), butylene carbonate (BC), and methyl ethyl carbonate (MEC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfolane, Sulfur-containing compounds such as dimethyl sulfoxide; are preferably used.
  • carbonates are preferable because they have a high dielectric constant and a wide stable potential region.
  • the lower the viscosity of the solvent used the higher the lithium ion conductivity tends to be, so the lithium ion conductivity can be adjusted depending on the type of solvent.
  • the concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate.
  • the non-aqueous secondary battery is formed by stacking the positive electrode and the negative electrode through the non-aqueous secondary battery separator of the present invention, and winding and folding the battery, if necessary, into the battery container. It can be manufactured by injecting an electrolytic solution into the sealing.
  • an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like may be placed in the battery container as necessary to prevent an increase in pressure inside the battery or overcharge / discharge.
  • the shape of the 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.
  • a polymer to be a measurement sample under the same polymerization conditions as the polymerization conditions of the core part and the shell part (polymer and shell of the core part) Part of the polymer) was prepared.
  • the obtained aqueous dispersion is put in a petri dish made of polytetrafluoroethylene, dried at a temperature of 60 ° C. for 72 hours, then taken out of the petri dish and hot-pressed for 5 minutes under the conditions of 100 ° C. and 20 kg / cm 2. A film with a thickness of 0.5 mm was produced.
  • the weight of this test piece was measured and designated as W0.
  • LiPF 6 dissolved at a concentration of 1 mol / L was used as the supporting electrolyte.
  • Tg Glass transition temperature
  • volume average particle diameter D50 The volume average particle diameter D50 of each particle is 50% of the cumulative volume calculated from the small diameter side in the particle diameter distribution measured by a laser diffraction particle size distribution measuring device (“SALD-3100” manufactured by Shimadzu Corporation). The particle diameter was taken.
  • SALD-3100 laser diffraction 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 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.
  • the covering ratio Rc can be calculated manually from the cross-sectional structure, but can also be calculated using commercially available image analysis software.
  • image analysis software for example, “AnalySIS Pro” (manufactured by Olympus Corporation) can be used.
  • ⁇ Viscosity of composition for functional layer> Rheometer (Anton Paar, "MCR502") was used to measure the viscosity eta 1 at a shear rate of 10000 sec -1 in viscosity eta 0 and a temperature 25 ° C. at a shear rate of 100 sec -1 at a temperature 25 ° C., respectively.
  • LiPF 6 dissolved at a concentration of 1 mol / L was used as the supporting electrolyte.
  • the porosity M 0 of the separator substrate and the porosity M 1 of the separator were calculated by a mercury intrusion method. The porosity measurement by the mercury intrusion method was performed under the following conditions.
  • Measuring device Autopore IV 9510 manufactured by Micromeritics Measurement range: ⁇ 0.003 ⁇ m to 400 ⁇ m
  • the porosity change ratio M C (M 0 ⁇ M 1 ) / M 0 ⁇ 100 was calculated.
  • GPC measurement was performed using polystyrene as a standard substance, and using a solution obtained by dissolving 0.85 g / ml sodium nitrate in a 10% by volume aqueous solution of dimethylformamide as a developing solvent.
  • the GPC measuring apparatus is HLC-8220GPC (manufactured by Tosoh Corporation)
  • the detector is HLC-8320GPCRI detector (manufactured by Tosoh Corporation)
  • the measuring column is TSKgeISsuperHZM-M (manufactured by Tosoh Corporation)
  • the measurement temperature is 40 ° C.
  • a separator provided with a separator base material and a functional layer was prepared, cut into a size of width 10 cm ⁇ length 10 cm, and used as a test piece. After this test piece was immersed in an electrolytic solution at 60 ° C. for 24 hours, the electrolytic solution adhering to the surface was wiped off.
  • LiPF 6 dissolved at a concentration of 1 mol / L was used as the supporting electrolyte.
  • a cellophane tape was attached to the surface of the functional layer of the test piece.
  • a cellophane tape defined in JIS Z1522 was used.
  • the cellophane tape was fixed on a horizontal test bench. Thereafter, the stress was measured when one end of the separator was pulled vertically upward at a pulling speed of 50 mm / min and peeled off.
  • Peel strength is 20 N / m or more
  • B Peel strength is 15 N / m or more and less than 20 N / m
  • C Peel strength is less than 15 N / m ⁇ High-temperature cycle characteristics of secondary battery> The manufactured wound lithium ion secondary battery with a discharge capacity of 1000 mAh was allowed to stand in an environment of 25 ° C. for 24 hours.
  • Capacity maintenance factor ⁇ C is 85% or more
  • the manufactured wound lithium ion secondary battery with a discharge capacity of 1000 mAh was allowed to stand in an environment of 25 ° C. for 24 hours. Thereafter, 4.4 V, 0.1 C, and 5 hours of charging were performed in an environment of 25 ° C., and the voltage V0 at that time was measured. Thereafter, a discharge operation was performed at a discharge rate of 1 C in an environment of ⁇ 10 ° C., and the voltage V1 15 seconds after the start of discharge was measured.
  • Example 1 ⁇ Preparation of organic particles> In a 5 MPa pressure vessel with a stirrer, 74 parts of methyl methacrylate as a (meth) acrylic acid ester monomer, 4 parts of methacrylic acid as an acid group-containing monomer, a crosslinkable monomer 1 part of ethylene glycol dimethacrylate as a body, polyoxyalkylene alkenyl ether ammonium sulfate as a reactive surfactant monomer (product name “Latemul (registered trademark) PD-104”, number average molecular weight 2500, manufactured by Kao Corporation) 1 And 150 parts of ion-exchanged water and 0.5 part of potassium persulfate as a polymerization initiator were added and sufficiently stirred, and then heated to 60 ° C.
  • a reactive surfactant monomer product name “Latemul (registered trademark) PD-104”, number average molecular weight 2500, manufactured by Kao Corporation
  • ⁇ Preparation of functional layer binder 70 parts of ion-exchanged water, 0.15 part of sodium lauryl sulfate (product name “Emal 2F” manufactured by Kao Chemical Co., Ltd.) as an emulsifier and 0.5 part of ammonium persulfate are supplied to a reactor equipped with a stirrer. The gas phase portion was replaced with nitrogen gas, and the temperature was raised to 60 ° C.
  • the resulting acrylic polymer had a volume average particle diameter D50 of 0.15 ⁇ m and a glass transition temperature of ⁇ 35 ° C.
  • ⁇ Preparation of functional layer composition 100 parts by weight of an aqueous dispersion containing organic particles, 15 parts by weight of an aqueous dispersion containing an acrylic polymer as a binder for a functional layer, and a surface tension adjusting agent (manufactured by San Nopco, “ SN366 ”) 1 part was mixed, and ion exchange water was further added so that the solid content concentration was 30% to obtain a composition for a functional layer. Viscosity ⁇ 0 and viscosity ⁇ 1 of the obtained functional layer composition were measured, and ⁇ 0 / ⁇ 1 was calculated.
  • ⁇ Preparation of separator with functional layer> As a separator base material, a separator base material made of a polyethylene porous material (“Celguard 2500” manufactured by Celgard) was prepared. The porosity M 0 of the separator substrate was measured. The results are shown in Table 1. And the composition for functional layers was apply
  • a 5% aqueous sodium hydroxide solution was added to the mixture containing the particulate binder and the pH was adjusted to 8, and then the unreacted monomer was removed by heating under reduced pressure. Then, it cooled to 30 degrees C or less, and obtained the water dispersion liquid containing a desired particulate-form binder.
  • 100 parts of artificial graphite (volume average particle diameter D50: 15.6 ⁇ m) as a negative electrode active material, and a 2% aqueous solution of carboxymethylcellulose sodium salt (“MAC350HC” manufactured by Nippon Paper Industries Co., Ltd.) as a water-soluble polymer were solidified.
  • the negative electrode slurry composition obtained as described above 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. , 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.
  • the positive electrode slurry composition obtained as described above was applied onto a 20 ⁇ m-thick aluminum foil as a current collector with a comma coater so that the film thickness after drying was about 150 ⁇ m and dried. I let you. This drying was performed by transporting 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. The positive electrode raw material before pressing was rolled with a roll press to obtain a positive electrode after pressing with a positive electrode mixture layer thickness of 80 ⁇ m.
  • the positive electrode after pressing obtained above is cut out to 49 cm ⁇ 5 cm and placed so that the surface of the positive electrode mixture layer side is on the upper side, and a separator provided with functional layers on both sides cut out to 55 cm ⁇ 5.5 cm thereon. Arranged. Further, the pressed negative electrode obtained above was cut into 50 cm ⁇ 5.2 cm, and this was placed on the separator so that the surface on the negative electrode mixture layer side faces the separator. This was wound with a winding machine to obtain a wound body. The wound body is pressed at 60 ° C.
  • Examples 2, 3, 10 and 11 In the same manner as in Example 1 except that the ratio of the monomer added for forming the core part of the organic particles was changed as shown in Table 1 when the aqueous dispersion containing the organic particles was prepared, The binder for functional layers, the composition for functional layers, the separator provided with a functional layer, a negative electrode, a positive electrode, and the lithium ion secondary battery were manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 When preparing the aqueous dispersion containing the organic particles, the ratio of the monomer added for forming the core part and the shell part of the organic particles was changed as shown in Table 1, and dodecylbenzenesulfone was used as an emulsifier when forming the core part. Except for using 1 part of acid sodium, as in Example 1, organic particles, functional layer binder, functional layer composition, separator provided with functional layer, negative electrode, positive electrode, and lithium ion secondary battery Manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 Instead of 1 part of polyoxyalkylene alkenyl ether ammonium sulfate as the reactive surfactant monomer added for forming the shell part of the organic particles during the preparation of the aqueous dispersion containing the organic particles, methyl methacrylate as the macromonomer, respectively.
  • 1 part of a macromonomer manufactured by Toagosei Co., Ltd., “AA-6”, number average molecular weight 6000
  • 1 part of polycaprolactone-modified hydroxyalkyl acrylate manufactured by Daicel, “Placcel (registered trademark) FA5”, molecular weight 689) was used.
  • Example 7 When preparing the aqueous dispersion containing the organic particles, the ratio of the monomer added for forming the core portion of the organic particles was changed as shown in Table 1, and sodium dodecylbenzenesulfonate was used as an emulsifier when forming the core portion.
  • An aqueous solution containing an acrylamide polymer (produced by Arakawa Chemical Co., Ltd., “Polystron (registered trademark) 117”) having a carboxylic acid group introduced as a water-soluble polymer at the time of preparing a functional layer composition was used.
  • Example 9 When preparing the functional layer composition, an aqueous solution containing carboxymethyl cellulose sodium salt (manufactured by Nippon Paper Industries Co., Ltd., “MAC800LC”) instead of the acrylamide polymer into which the carboxylic acid group was introduced was used as the water-soluble polymer. Except for adding 0.2 part, in the same manner as in Example 7, organic particles, binder for functional layer, composition for functional layer, separator provided with functional layer, negative electrode, positive electrode, and lithium ion secondary battery Manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 12 In the same manner as in Example 1 except that the ratio of the monomer added for forming the shell part of the organic particles was changed as shown in Table 1 when preparing the aqueous dispersion containing the organic particles, The binder for functional layers, the composition for functional layers, the separator provided with a functional layer, a negative electrode, a positive electrode, and the lithium ion secondary battery were manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 In the same manner as in Example 1 except that the ratio of the monomer added for forming the shell part of the organic particles was changed as shown in Table 1 when preparing the aqueous dispersion containing the organic particles, The binder for functional layers, the composition for functional layers, the separator provided with a functional layer, a negative electrode, a positive electrode, and the lithium ion secondary battery were manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 2 In the same manner as in Example 1 except that the ratio of the monomer added for forming the core part of the organic particles was changed as shown in Table 1 when the aqueous dispersion containing the organic particles was prepared, The binder for functional layers, the composition for functional layers, the separator provided with a functional layer, a negative electrode, a positive electrode, and the lithium ion secondary battery were manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 In the same manner as in Example 5, except that the ratio of the monomer added for forming the shell part of the organic particles was changed as shown in Table 1 when the aqueous dispersion containing the organic particles was prepared, The binder for functional layers, the composition for functional layers, the separator provided with a functional layer, a negative electrode, a positive electrode, and the lithium ion secondary battery were manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Example 4 Organic particles were prepared in the same manner as in Comparative Example 3 except that 7 parts of an aqueous solution containing an acrylamide polymer having a carboxylic acid group introduced as a water-soluble polymer was added as a water-soluble polymer at the time of preparation of the functional layer composition.
  • the binder for functional layers, the composition for functional layers, the separator provided with a functional layer, the negative electrode, the positive electrode, and the lithium ion secondary battery were manufactured.
  • Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • MMA indicates methyl methacrylate
  • MAA indicates methacrylic acid
  • EDMA refers to ethylene glycol dimethacrylate
  • PD-104 indicates Latemul PD-104 manufactured by Kao Corporation.
  • SDBS sodium dodecylbenzenesulfonate
  • ST indicates styrene
  • AN indicates acrylonitrile
  • AA-6 indicates AA-6 manufactured by Toagosei Co., Ltd.
  • FA5 indicates Placel FA5 manufactured by Daicel Corporation.
  • ACL indicates an acrylic polymer
  • Polystron indicates PORISTORON 117 manufactured by Arakawa Chemical Co., Ltd.
  • CMC indicates MAC800LC manufactured by Nippon Paper Industries Co., Ltd.
  • PE indicates polyethylene.
  • a predetermined core-shell structure comprising a core part and a shell part respectively formed of a polymer having an electrolyte solution swelling degree within a predetermined range is obtained. And a functional layer composition having a value of ⁇ 0 and ⁇ 0 / ⁇ 1 within a predetermined range, and an organic electrolyte swelling degree within a predetermined range.
  • the functional layer consisting of a core part and a shell part formed respectively by a polymer having a comprises organic particles and the functional layer binder having a predetermined core-shell structure, functional layer M 0 and M C is within a predetermined range
  • the functional layer exhibits good adhesion after immersion in the electrolyte, and the secondary battery has excellent high-temperature cycle characteristics and low-temperature output characteristics. It can be shown that That. Further, from Examples 1 to 3, 10, and 11 in Table 1 above, by changing the composition of the core part of the organic particles, the adhesion of the functional layer, the high temperature cycle characteristics and the low temperature output characteristics of the secondary battery can be improved. It can be seen that it can be improved.
  • a composition for a non-aqueous secondary battery functional layer capable of forming a functional layer that can exhibit excellent adhesive properties after immersion in an electrolytic solution and provide excellent battery characteristics to a secondary battery. can do.
  • a separator for a non-aqueous secondary battery capable of exhibiting excellent battery characteristics for a non-aqueous secondary battery while firmly adhering to an electrode through a functional layer after immersion in an electrolytic solution. be able to.
  • the non-aqueous secondary battery excellent in a battery characteristic can be provided.

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Abstract

La présente invention a pour objet de fournir une composition pour des couches fonctionnelles de batterie rechargeable non aqueuse, qui peut être un matériau pour une couche fonctionnelle qui présente une excellente adhérence après immersion dans une solution électrolytique et contribue à l'amélioration des caractéristiques de la batterie. Cette composition contient des particules organiques et un liant pour les couches fonctionnelles. Dans ce contexte, chaque particule organique comporte une partie noyau qui est formée d'un polymère présentant un degré de gonflement dans une solution électrolytique compris entre 5 fois et 30 fois (inclus) et une partie enveloppe qui est formée d'un polymère présentant un degré de gonflement dans une solution électrolytique supérieur à 1 fois, mais égal ou inférieur à 4 fois, et la partie enveloppe recouvre partiellement la surface externe de la partie noyau. Cette composition présente une viscosité η0 à une vitesse de cisaillement de 100 s-1 comprise entre 10 mPa·s et 100 mPa·s (inclus), et le rapport entre la viscosité η0 et la viscosité η1 à une vitesse de cisaillement de 10 000 s-1 est compris entre 1 et 5 (inclus).
PCT/JP2015/005677 2014-12-25 2015-11-13 Composition pour des couches fonctionnelles de batterie rechargeable non aqueuse, séparateur pour des batteries rechargeables non aqueuses et batterie rechargeable non aqueuse WO2016103559A1 (fr)

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Cited By (9)

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WO2018151122A1 (fr) * 2017-02-15 2018-08-23 株式会社大阪ソーダ Liant pour électrodes
JP2018181833A (ja) * 2017-04-14 2018-11-15 住友化学株式会社 非水電解液二次電池用塗料
EP3382777A4 (fr) * 2015-11-27 2019-07-10 Zeon Corporation Composition pour couches adhésives de batterie rechargeable non aqueuse, couche adhésive pour batteries rechargeables non aqueuses, et batterie rechargeable non aqueuse
WO2019221381A1 (fr) * 2018-05-18 2019-11-21 삼성에스디아이 주식회사 Membrane de séparation pour accumulateur au lithium et accumulateur au lithium le comprenant
JP2020507188A (ja) * 2017-12-11 2020-03-05 エルジー・ケム・リミテッド セパレータ及びそれを含む電気化学素子
WO2020045246A1 (fr) 2018-08-29 2020-03-05 日本ゼオン株式会社 Composition pour couche adhésive de batterie secondaire non aqueuse, élément de batterie pour batterie secondaire non aqueuse et procédé de fabrication dudit élément de batterie pour batterie secondaire non aqueuse, ainsi que procédé de fabrication de stratifié pour batterie secondaire non aqueuse, et procédé de fabrication de batterie secondaire non aqueuse
JPWO2019131710A1 (ja) * 2017-12-26 2020-12-24 昭和電工株式会社 非水系電池電極用バインダー、非水系電池電極用スラリー、非水系電池電極、及び非水系電池
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JP7220023B2 (ja) 2017-04-14 2023-02-09 住友化学株式会社 非水電解液二次電池用塗料
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JPWO2019131710A1 (ja) * 2017-12-26 2020-12-24 昭和電工株式会社 非水系電池電極用バインダー、非水系電池電極用スラリー、非水系電池電極、及び非水系電池
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US12002987B2 (en) 2018-05-18 2024-06-04 Samsung Sdi Co., Ltd. Separator for rechargeable lithium battery and rechargeable lithium battery comprising same
WO2020045246A1 (fr) 2018-08-29 2020-03-05 日本ゼオン株式会社 Composition pour couche adhésive de batterie secondaire non aqueuse, élément de batterie pour batterie secondaire non aqueuse et procédé de fabrication dudit élément de batterie pour batterie secondaire non aqueuse, ainsi que procédé de fabrication de stratifié pour batterie secondaire non aqueuse, et procédé de fabrication de batterie secondaire non aqueuse
KR20210049098A (ko) 2018-08-29 2021-05-04 니폰 제온 가부시키가이샤 비수계 이차 전지 접착층용 조성물, 비수계 이차 전지용 전지 부재 및 그 제조 방법, 그리고 비수계 이차 전지용 적층체의 제조 방법 및 비수계 이차 전지의 제조 방법
US11811087B2 (en) 2018-08-29 2023-11-07 Zeon Corporation Composition for non-aqueous secondary battery adhesive layer, battery member for non-aqueous secondary battery and method of producing same, method of producing laminate for non-aqueous secondary battery, and method of producing non-aqueous secondary battery
WO2021172425A1 (fr) * 2020-02-28 2021-09-02 住友理工株式会社 Électrode flexible en forme de feuille et procédé de production de celle-ci
JP6975365B1 (ja) * 2020-02-28 2021-12-01 住友理工株式会社 シート状柔軟電極およびその製造方法

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