CN107112480B - Non-aqueous secondary battery spacer and its manufacturing method and non-aqueous secondary battery - Google Patents

Non-aqueous secondary battery spacer and its manufacturing method and non-aqueous secondary battery Download PDF

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Publication number
CN107112480B
CN107112480B CN201580071472.9A CN201580071472A CN107112480B CN 107112480 B CN107112480 B CN 107112480B CN 201580071472 A CN201580071472 A CN 201580071472A CN 107112480 B CN107112480 B CN 107112480B
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functional layer
spacer
organic filler
secondary battery
polymer
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CN107112480A (en
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秋池纯之介
大浦庆
浅井一辉
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Zeon Corp
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Nippon Zeon Co Ltd
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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
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides a kind of cementability and ionic conductance in the electrolytic solution excellent spacer.The functional layer that non-aqueous secondary battery of the invention has spacer substrate with spacer and formed at least one surface of spacer substrate, functional layer has the phase of organic filler to construct existing for irregular shape, above-mentioned organic filler has core-shell structure, the shell portion that above-mentioned core-shell structure has core portion and covers the outer surface part in core portion, core portion is 5 times or more by electrolyte swellbility and 30 times of polymer below are formed, shell portion is more than 1 times by electrolyte swellbility and 4 times of polymer below are formed, the area of part existing for the phase of organic filler is 20% or more and 80% or less relative to the ratio of the area of the functional layer forming face of spacer substrate.

Description

Non-aqueous secondary battery spacer and its manufacturing method and non-aqueous secondary battery
Technical field
The present invention relates to non-aqueous secondary battery spacer, non-aqueous secondary battery spacer manufacturing method and Non-aqueous secondary battery.
Background technique
The non-aqueous secondary batteries such as lithium ion secondary battery (hereinafter, be only abbreviated as " secondary cell " sometimes.) have it is small-sized, Lightweight and energy density are high, and then the characteristic that can be repeatedly charged and discharged, extensive with using on the way.Moreover, non-water system two Primary cell usually has positive, cathode and anode and cathode is isolated and prevents spacer etc. short-circuit between anode and cathode Battery components.
Wherein, in recent years, it has used in the secondary battery with the porous membrane layer for improving heat resistance and intensity, use In the battery components of adhesive layer that battery components are bonded to each other etc. (hereinafter, these are referred to as " functional layer " sometimes).Specifically For, it has used and functional layer is for example formed in spacer made of on spacer substrate as battery components.
Moreover, energetically having carried out changing for the spacer with functional layer for the further high performance of secondary cell Into (for example, referenced patent document 1).
Specifically, for example Patent Document 1 discloses following technologies, that is, for by polyolefin micro porous polyolefin membrane shape At spacer substrate on form the spacer of adhesive layer formed by thermoplastic polymer coating, by using thermoplastic poly Object coating is closed, and it includes that thermoplasticity with defined glass transition temperature polymerize that the thermoplastic polymer coating, which has, The part of object and part not comprising thermoplastic polymer existing for the shape of island to construct, to make cementability and ionic conductance The technology of raising.According to spacer described in the patent document 1, by using the thermoplastic with defined glass transition temperature Property polymer, so as to make with the cementability of electrode improve, and by make comprising thermoplastic polymer part and do not wrap Part containing thermoplastic polymer is with the presence of island shape, so as to improve ionic conductance.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2014/017651.
Summary of the invention
Problems to be solved by the invention
But in above-mentioned existing spacer, the cementability of adhesive layer (functional layer) in the electrolytic solution is simultaneously insufficient. Therefore, for above-mentioned existing spacer, the bonding of the functional layer in electrolyte is made while ensuring ionic conductance Property further increases, makes the battery behavior of the non-aqueous secondary battery with spacer, and (high-temperature cycle and low temperature output are special Property) it leaves some room for improvement in the aspect that further increases.
Therefore, the interval excellent the purpose of the present invention is to provide a kind of cementability and ionic conductance in the electrolytic solution Part.
In addition, the purpose of the present invention, which is lain also in, provides a kind of high-temperature cycle and the excellent non-water system of low temperature output characteristics Secondary cell.
The solution to the problem
The present inventor has made intensive studies to achieve the goals above.In turn, the inventors discovered that, for being spaced Spacer made of functional layer is formed on part substrate, by the way that the construction of functional layer is set as construction below, that is, by organic filler The phase of formation with irregular shape exist and the phase of organic filler shared by area ratio be specific range in and The organic filler has with specific core-shell structure, the specific core-shell structure is respectively provided with specific electrolyte swellbility The construction in core portion and shell portion, so as to further increase cementability in the electrolytic solution while ensuring ionic conductance. In addition, the present inventors have additionally discovered that, it will include that the functional layer of above-mentioned organic filler is coated on spacer substrate with composition, makes The functional layer of coating is dried with composition when forming functional layer on spacer substrate, will be formed with the spacer base of functional layer The water droplet contact angle on the surface of material and the surface tension of functional layer composition are set as in specific range, thus can be easy landform At with the above-mentioned functional layer specifically constructed.In turn, the present inventor completes the present invention based on above-mentioned new opinion.
That is, the present invention to be for the purpose of advantageously solving the above subject, non-aqueous secondary battery spacer of the invention It is characterized in that, with spacer substrate and the functional layer formed at least one surface of above-mentioned spacer substrate, above-mentioned function Ergosphere has the phase of organic filler to construct existing for irregular shape, and above-mentioned organic filler has core-shell structure, above-mentioned core The shell portion that shell structure has core portion and covers the outer surface part in above-mentioned core portion, above-mentioned core portion are 5 by electrolyte swellbility Times or more and 30 times of polymer below formed, above-mentioned shell portion is more than 1 times and 4 times polymer shape below by electrolyte swellbility At, part existing for the phase of above-mentioned organic filler area relative to above-mentioned spacer substrate functional layer forming face area Ratio is 20% or more and 80% or less.If setting includes having with above-mentioned defined core-shell structure and character like this The ratio of the area of part existing for the functional layer of the phase of machine particle and phase in functional layer forming face by organic filler is set as 20% or more, then it can be improved the cementability of the functional layer in electrolyte, spacer excellent in adhesion be provided.In addition, if There is the phase of the organic filler of the defined core-shell structure and character that have above-mentioned with irregular shape and in functional layer shape 80% is set as hereinafter, then can be in improving electrolyte at the ratio of the area of part existing for the phase in face by organic filler There is provided ionic conductance excellent spacer while the cementability of functional layer.
It is noted that in the present invention, the polymer in the composition core portion of organic filler and the polymer for constituting shell portion " electrolyte swellbility " be able to use measuring method described in the embodiment of this specification to measure.In addition, in the present invention, " area ratio of part existing for the phase of organic filler " can observe spacer by using scanning electron microscope (SEM) Functional layer, calculated in field of view using image analysis software the ratio of the area of part existing for the phase of organic filler from And it acquires.
In addition, in non-aqueous secondary battery spacer of the invention, the glass transition of the polymer in above-mentioned core portion Temperature is preferably -50 DEG C or more and 150 DEG C hereinafter, the glass transition temperature of the polymer in above-mentioned shell portion is preferably 50 DEG C or more And 200 DEG C or less.This is because if by the glass of the polymer in the composition core portion of organic filler and the polymer for constituting shell portion Change transition temperature to be respectively set as in above-mentioned range, then it can be in the intensity and functional layer for improving the organic filler in electrolyte Cementability while improve spacer operability.
It is noted that in the present invention, the polymer in the composition core portion of organic filler and the polymer for constituting shell portion " glass transition temperature " be able to use measuring method described in the embodiment of this specification to measure.
In addition, the present invention to be for the purpose of advantageously solving the above subject, non-aqueous secondary battery spacer of the invention Manufacturing method be characterized in that, be the manufacturing method of above-mentioned non-aqueous secondary battery spacer, comprising the following steps: Prepare the process of spacer substrate, the water droplet contact angle at least one surface of above-mentioned spacer substrate is 80 ° or more and 130 ° Below；Prepare the process of non-aqueous secondary battery functional layer composition, above-mentioned non-aqueous secondary battery functional layer composition Containing above-mentioned organic filler and decentralized medium and surface tension is 33mN/m or more and 39mN/m or less；By above-mentioned non-water system two Primary cell functional layer is coated on the above-mentioned surface of above-mentioned spacer substrate with composition, makes the non-aqueous secondary battery function of coating Ergosphere be dried with composition and on spacer substrate formed functional layer process.If connect like this with defined water droplet Coating has the non-aqueous secondary battery functional layer composition of defined surface tension on the surface of the spacer substrate of feeler, Then the non-aqueous secondary battery functional layer composition containing organic filler is moderately repelled on the surface of spacer substrate, Therefore the phase with organic filler is able to easily form with the functional layer of construction existing for irregular shape.Therefore, can Cementability in the electrolytic solution and the excellent above-mentioned spacer of ionic conductance is easily manufactured.
In addition, in the present invention, " water droplet contact angle " can be by being added dropwise the ion exchange of 1 μ L on spacer substrate Water, the contact angle after measurement dropwise addition 60 seconds is to acquire.In addition, in the present invention, the combination of non-aqueous secondary battery functional layer " surface tension " of object is able to use flat band method to measure.
Moreover, the present invention, for the purpose of advantageously solving the above subject, the feature of non-aqueous secondary battery of the invention exists In any with above-mentioned non-aqueous secondary battery spacer.If like this using cementability in the electrolytic solution High-temperature cycle and low temperature output then can be obtained in the excellent above-mentioned non-aqueous secondary battery spacer with ionic conductance The non-aqueous secondary battery of excellent.
Invention effect
In accordance with the invention it is possible to provide a kind of cementability and ionic conductance in the electrolytic solution excellent spacer.
In addition, in accordance with the invention it is possible to providing a kind of high-temperature cycle and the excellent non-water system two of low temperature output characteristics Primary cell.
Detailed description of the invention
Fig. 1 is the SEM image of the functional layer of non-aqueous secondary battery spacer of the invention.
Fig. 2 is the organic grain for schematically showing the functional layer of non-aqueous secondary battery spacer of the invention and being included The sectional view of the structure of one example of son.
Specific embodiment
Hereinafter, detailed description of embodiments of the present invention.
Here, non-aqueous secondary battery of the invention can be used as the secondary electricity of the non-water systems such as lithium ion secondary battery with spacer The spacer in pond and use, be able to use the manufacturing method of non-aqueous secondary battery spacer for example of the invention and manufacture. Moreover, non-aqueous secondary battery of the invention is the secondary electricity of non-water system with non-aqueous secondary battery spacer of the invention Pond.
(non-aqueous secondary battery spacer)
Non-aqueous secondary battery of the invention spacer has spacer substrate and at least one of spacer substrate The functional layer formed on surface (functional layer forming face).Moreover, the functional layer of non-aqueous secondary battery spacer of the invention Comprising the organic filler with specific core-shell structure, above-mentioned specific core-shell structure refer to have it is molten with specific electrolyte The core portion and shell portion of expansibility.In addition, the organic filler forms to independent or multiple aggregations the phase of organic filler in functional layer.Into And the phase of organic filler is deposited as the SEM image of an example of functional layer for example shown in fig. 1 with irregular shape , and with the presence of specific area ratio in functional layer forming face.In addition, having in SEM image as shown in Fig. 1 Machine particle is observed as about 0.3~0.7 μm of diameter or so of spherical point.
Moreover, being provided with the function comprising specific organic filler in non-aqueous secondary battery spacer of the invention Ergosphere, therefore can be improved the cementability of functional layer in the electrolytic solution.Therefore, non-aqueous secondary battery of the invention interval Part can play excellent cementability in the electrolytic solution.In addition, in non-aqueous secondary battery spacer of the invention, because Make the phase of organic filler exist with irregular shape and phase in functional layer forming face by organic filler existing for part The ratio of area is set as in specific range, so the same of the cementability of functional layer in the electrolytic solution can fully improved When ensure good ionic conductance.
<spacer substrate>
Here, not limited especially as the spacer substrate for forming functional layer at least one surface (functional layer forming face) Calmly, spacer substrate known to being able to use such as the microporous membrane recorded in Japanese Unexamined Patent Publication 2012-204303 bulletin.? Among these, from the film thickness that can make spacer entirety, thinning thus, it is possible to improve the ratio of the electrode active material in secondary cell Rate to improve unit volume capacity it is such from the perspective of, preferably by polyolefin (polyethylene, polypropylene, polybutene, Polyvinyl chloride) resin formed microporous membrane (organic spacer part substrate).Moreover, the thickness of spacer substrate can be set as appointing The thickness of choosing, usually 0.5 μm or more, preferably 5 μm or more, usually 40 μm hereinafter, preferably 30 μm hereinafter, more preferably 20 μm or less.
In addition, optional layer other than functional layer, can playing desired function can also be included by spacer substrate In part of it.
In addition, the manufacturing method for the non-aqueous secondary battery of the invention spacer that face is described in detail after use is made In the case where making spacer, as spacer substrate, it is preferable to use following microporous membrane, that is, the formation function of the microporous membrane The water droplet contact angle on the surface (functional layer forming face) of ergosphere side is preferably 80 ° or more, more preferably 85 ° or more, further excellent 90 ° or more are selected as, furthermore it is preferred that being 130 ° hereinafter, more preferably 120 ° or less, further preferably 110 ° or less.This be because For landform can be easy if the use of there is water droplet contact angle being the spacer substrate on 80 ° or more and 130 ° surfaces below At the phase of the organic filler with irregular shape and specific area ratio.
Here, the water droplet contact angle on the surface of spacer substrate is able to use tree used in the formation of such as microporous membrane Method known to the change of the composition of rouge, surface treatment of microporous membrane etc. is adjusted.Wherein, heat-resisting from can ensure that in use Water drop contact is easily adjusted while resin (such as polyethylene, the polypropylene etc.) of performances such as property, intensity and ionic conductance From the perspective of the size at angle, the water droplet contact angle of spacer substrate is preferably adjusted by the surface treatment of microporous membrane.Into It is micro- porous and from the viewpoint of ensuring the porous of microporous membrane while easily adjusting the size of water droplet contact angle It is preferable to use the dry process such as corona treatment, Corona discharge Treatment, UV processing for film to be surface-treated, and more preferably use Corona discharge Treatment is surface-treated.
In addition, the case where using Corona discharge Treatment, processing intensity can be preferably set to 20Wmin/m2More than, it is more excellent Choosing is set as 30Wmin/m2More than, further preferably it is set as 40Wmin/m2More than, furthermore it is possible to be preferably set to 80Wmin/ m2Hereinafter, being more preferably set as 70Wmin/m2Hereinafter, being further preferably set as 60Wmin/m2Below.This is because handling In the case that intensity is excessive, water droplet contact angle is possible to excessively reduce.In addition, this is because the situation too small in processing intensity Under, water droplet contact angle is possible to that desired size can not be reduced to.
<functional layer>
In non-aqueous secondary battery spacer of the invention, the functional layer for being formed in spacer substrate, which can be, to be used for Make the heat resistance of spacer and the porous membrane layer of intensity raising, be also possible to the adhesive layer for keeping spacer Nian Jie with electrode, It can also be the layer for playing the function of both porous membrane layer and adhesive layer.
Here, the functional layer of non-aqueous secondary battery spacer of the invention has following construction, that is, organic filler Phase exist with irregular shape, above-mentioned organic filler have core-shell structure, above-mentioned core-shell structure have core portion and shell portion, on It is that 5 times or more and 30 times of polymer below are formed that core portion, which is stated, by electrolyte swellbility, and above-mentioned shell portion is surpassed by electrolyte swellbility 1 times and 4 times polymer below is crossed to be formed and cover the outer surface part in core portion.In addition, in functional layer, organic grain The ratio of the area of part existing for the phase of son is 20% or more and 80% or less relative to the area of functional layer forming face.And And the functional layer plays excellent cementability in the electrolytic solution and has good ionic conductance.
In addition, functional layer can be made only in a surface of spacer substrate, two surfaces can also be formed in.This Outside, non-aqueous secondary battery spacer of the invention can also have the functional layer of above-mentioned construction on a surface, another One surface has the functional layer of non-above-mentioned construction (for example, the face of functional layer, the phase of organic filler without containing organic filler Product ratio is unsatisfactory for the functional layer etc. of above range).
In addition, functional layer can also optionally contain functional layer binding material, non-conductive grain other than organic filler Sub (substance in addition to being equivalent to organic filler and functional layer binding material), other ingredients.
In addition, the content of the organic filler in functional layer is preferably 50 mass % or more, more preferably 60 mass % or more, Further preferably 70 mass % or more, particularly preferably 80 mass % or more.
[organic filler]
Organic filler included in functional layer is responsible for the function for making functional layer play excellent cementability in the electrolytic solution Energy.
Moreover, organic filler is characterized in that, there is core-shell structure, above-mentioned core-shell structure has core portion and will be outside core portion The shell portion covered to surface portion, above-mentioned core portion is 5 times or more by electrolyte swellbility and 30 times of polymer below are formed, on State that shell portion is more than 1 times by electrolyte swellbility and 4 times of polymer below are formed.
Here, the organic filler with above structure and character plays excellent cementability in the electrolytic solution, and to electricity Solve dissolving out less, excellent cementability capable of being kept for a long time for the ingredient in liquid.Moreover, the functional layer comprising organic filler can make The battery behavior of secondary cell improves well.In addition, the organic filler is not playing big bonding force to electrolyte dipping is preceding, Therefore the spacer with the functional layer comprising organic filler is not likely to produce the adhesion (adhesion between the spacer of functional layer Deng), it is also excellent in terms of operability.
In addition, the reasons why above-mentioned such excellent effect can be obtained by using above-mentioned organic filler is still not clear, But it is speculated as described below.
That is, constituting the polymer phase in the shell portion of above-mentioned organic filler has swelling to a certain degree for electrolyte.At this moment, example The activation of the functional group as possessed by the polymer in the shell portion of swelling, and with the surface of the spacer substrate that is formed with functional layer or with Functional group existing for the surface of the electrode of spacer bonding with functional layer etc. generates chemistry or the interaction of electricity etc., due to The reason, shell portion can be bonded securely with spacer substrate, electrode etc..On the other hand, shell portion before swelling in electrolyte not Play big bonding force.Therefore it could be speculated that in the functional layer comprising the organic filler, the same of the generation of adhesion can inhibited When keep spacer strongly be bonded in the electrolytic solution with electrode.
In addition, the electrolyte swellbility of the polymer of the polymer and core portion in shell portion be set as defined in value hereinafter, because This will not exceedingly be swollen relative to electrolyte.Therefore it could be speculated that can be filled for example after secondary cell works long hours Ground is divided to play above-mentioned excellent cementability.
Moreover, in the case where using the functional layer comprising above-mentioned organic filler, since functional layer can as described above Strongly bonding force is played in the electrolytic solution, therefore in the secondary cell with the functional layer, is bonded across functional layer Spacer and electrode between be not likely to produce gap.Therefore, the interval with the functional layer comprising the organic filler is being used In the secondary cell of part, the distance of positive electrode and negative electrode is not easy to increase in secondary cell, and the internal resistance of secondary cell can be made to reduce, And the reacting field of the electrochemical reaction in electrode is not easy to become uneven.In turn, in the secondary cell, even if repeated charge Also it is not easy to generate gap between spacer and electrode, battery capacity is not easy to reduce.Thus it could be speculated that being capable of providing high temperature circulation The excellent secondary cell such as characteristic.
In turn, the polymer phase for constituting the core portion of above-mentioned organic filler is significantly swollen electrolyte.Moreover, poly- The intermolecular gap increase of polymer in the state that object significantly be swollen relative to electrolyte is closed, intermolecular is become at this It is easy to pass through ion.In addition, the polymer in the core portion of organic filler is not covered fully by shell portion.Therefore, in the electrolytic solution Ion becomes easy through core portion, and thus organic filler can show high Ionic diffusion.Therefore, if using above-mentioned organic Particle can also then inhibit the rising of resistance caused by functional layer, inhibit the reduction of the battery behaviors such as low temperature output characteristics.
In addition, as described above, organic filler plays excellent cementability and being swollen in the electrolytic solution, to electrolyte Big bonding force is not played before dipping.But organic filler does not play bonding not completely as long as not being swollen in the electrolytic solution Property, even in the state of not being swollen in the electrolytic solution, for example, by being heated to certain temperature or more (such as 50 DEG C or more) Cementability can be shown.
[[structure of organic filler]]
Here, organic filler has core-shell structure, what above-mentioned core-shell structure was covered with core portion and by the outer surface in core portion Shell portion.In addition, shell portion partly covers the outer surface in core portion.Although that is, organic filler shell portion covering core portion outer surface but It is and the outer surface in non-covered entire core portion.Even if seeming that the outer surface in core portion is fully covered by shell portion in appearance sometimes Lid, but as long as forming the hole inside and outside connection shell portion, then the shell portion is the shell portion for covering the outer surface part in core portion.Cause This, such as have the shell of the pore with the outer surface for being communicated to core portion from the outer surface (that is, circumferential surface of organic filler) in shell portion The organic filler in portion is contained in above-mentioned organic filler.
Specifically, the cross-section structure of an example of organic filler is such as shown in Figure 2, organic filler 100 With core-shell structure, above-mentioned core-shell structure has core portion 110 and shell portion 120.Wherein, core portion 110 is in the organic filler 100 Positioned at the part than 120 inside of shell portion.In addition, shell portion 120 is the part for covering the outer surface 110S in core portion 110, usually The part on the outermost side in organic filler 100.Moreover, the entirety of the outer surface 110S in core portion 110 is not covered in shell portion 120 Lid, but the outer surface 110S in core portion 110 is partly covered.
Covering rate-
Here, the outer surface in core portion is preferably 10% by the average proportions (covering rate) that shell portion covers in organic filler More than, more preferably 30% or more, further preferably 50% or more, preferably 95% hereinafter, more preferably 90% hereinafter, into One step is preferably 80% or less.By making covering rate become the lower limit value of above range or more, so as to inhibit the production of adhesion It is raw and improve cementability in the electrolytic solution, improve the high-temperature cycle of secondary cell.In addition, by make covering rate at For above range upper limit value hereinafter, so as to make functional layer show high Ionic diffusion, keep the low temperature of secondary cell defeated Characteristic improves out.
It is noted that in the present invention, " average proportions (covering rate) that the outer surface in core portion is covered by shell portion " energy Enough measured using measuring method described in the embodiment of this specification.
Volume average particle size D50-
In addition, the volume average particle size D50 of organic filler is preferably 0.01 μm or more, and more preferably 0.1 μm or more, into one Step preferably 0.2 μm or more, preferably 10 μm hereinafter, more preferably 5 μm hereinafter, further preferably 1 μm or less.By making to have The volume average particle size D50 of machine particle become above range lower limit value more than, so as to inhibit functional layer internal resistance it is upper It rises, improves the low temperature output characteristics of secondary cell.In addition, by making the volume average particle size D50 of organic filler become above-mentioned The upper limit value of range improves the high-temperature cycle of secondary cell hereinafter, so as to improve cementability in the electrolytic solution.
It is noted that in the present invention, " the volume average particle size D50 " of organic filler is able to use this specification The measurement of measuring method described in embodiment.
Nucleocapsid ratio-
In turn, have preferably with respect to the volume average particle size D50 shell portion of organic filler flat in the range of regulation Equal thickness.Specifically, the average thickness (nucleocapsid ratio) in the shell portion of the volume average particle size D50 relative to organic filler is preferred Be 1.5% or more, more preferably 3% or more, further preferably 5% or more, preferably 30% hereinafter, more preferably 25% with Under, further preferably 20% or less.By making nucleocapsid ratio become the lower limit value of above range or more, so as to further The cementability for improving functional layer in the electrolytic solution, improves the high-temperature cycle of secondary cell.In addition, by making nucleocapsid ratio Rate becomes the upper limit value of above range hereinafter, so as to further increase the low temperature output characteristics of secondary cell.
It is noted that in the present invention, " nucleocapsid ratio " is able to use measurement described in the embodiment of this specification Method measurement.
As long as in addition, indistinctively damage desired effect, organic filler can have above-mentioned core portion and shell portion with Outer optional constituent element.Gathered specifically, such as organic filler can also have in the inside in core portion with different from core portion Close the part that object is formed.It is used in the case where manufacturing organic filler with seeded polymerization if enumerating concrete example Seed particles can also remain in the inside in core portion.But, from the viewpoint of playing desired effect significantly, preferably have Machine particle only has core portion and shell portion.
[[core portion]]
The electrolyte swellbility-of the polymer in core portion
The core portion of organic filler is by relative to electrolyte there is the polymer of defined swellbility to be formed.Specifically, core The electrolyte swellbility of the polymer in portion needs to be 5 times or more, preferably 7 times or more, more preferably 8 times or more, furthermore, it is necessary to For 30 times hereinafter, preferably 28 times hereinafter, more preferably 25 times or less.By make core portion polymer electrolyte swellbility at More than the lower limit value of above range, so as to make functional layer show high Ionic diffusion, keep the low temperature of secondary cell defeated Characteristic improves out.In addition, the electrolyte swellbility of the polymer by making core portion become above range upper limit value hereinafter, to The cementability that can be improved functional layer in the electrolytic solution improves the high-temperature cycle of secondary cell.
It is noted that in the present invention, " the electrolyte swellbility " of the polymer in core portion is able to use this specification Embodiment described in measuring method measurement.
In addition, the method for the electrolyte swellbility as the polymer for adjusting core portion, can enumerate and for example consider electrolyte SP value properly selects the type and amount for being used to prepare the monomer of polymer in the core portion.It is usually close in the SP value of polymer In the case where the SP value of electrolyte, which has the tendency that being easy to be swollen in the electrolyte.On the other hand, when polymer SP value far from electrolyte SP value when, which has the tendency that being difficult to be swollen in the electrolyte.
Wherein, SP value refers to the meaning of solubility parameter.
Moreover, SP value is able to use Hansen Solubility Parameters A User ' s Handbook, 2ndEd Method for introducing in (CRC Press) and calculate.
In addition, the SP value of organic compound can also be calculated according to the molecular structure of its organic compound.Specifically, can Use simulation softward (such as " HSPiP " (http=//www.hansen- that SP value can be calculated according to SMILE formula Solubility.com it)) calculates.In the simulation softward, it is based on Hansen SOLUBILITY PARAMETERS A Theory described in User ' s Handbook Second Edition, Charles M.Hansen, acquires SP value.
The glass transition temperature-of the polymer in core portion
In addition, the glass transition temperature for constituting the polymer in the core portion of organic filler is preferably -50 DEG C or more, more preferably It is 0 DEG C or more, further preferably 20 DEG C or more, furthermore it is preferred that for 150 DEG C hereinafter, more preferably 120 DEG C hereinafter, further Preferably 100 DEG C or less.By making the glass transition temperature of the polymer in core portion become the lower limit value of above range or more, from And the intensity of functional layer, resistance to blocking can be made to further increase.In addition, the glass transition temperature of the polymer by making core portion Degree becomes the upper limit value of above range hereinafter, height so as to make functional layer cementability in the electrolytic solution and secondary cell Warm cycle characteristics improves.
In addition, the method for the glass transition temperature as the polymer for adjusting core portion, can enumerate and for example consider for making The type and amount of the monomer are properly selected for the glass transition temperature of the homopolymer of the monomer of the polymer in core portion.Example Such as, in the case where the preparation for the polymer that (methyl) acrylate monomer is used in core portion, (methyl) acrylate monomer The part from alcohol carbon atom number it is more, the glass transition temperature for obtaining polymer more has the tendency that reduction.
It is noted that in the present invention, (methyl) acrylic acid refers to the meaning of acrylic acid and/or methacrylic acid.
The composition-of the polymer in core portion
As the monomer for the polymer for being used to prepare core portion, it is upper for can properly selecting the electrolyte swellbility of its polymer State range monomer come using.It as such monomer, can enumerate for example: the vinyl chlorides monomer such as vinyl chloride, vinylidene chloride；Vinegar The vinylacetates such as vinyl acetate system monomer；Styrene, α-methylstyrene, styrene sulfonic acid, butyl phenyl ether ethylene, vinyl The aromatic vinyl monomers such as naphthalene；The vinyl amine system monomer such as vinyl amine；N- vinyl formamide, N- vinyl acetamide etc. Vinylamide system monomer；Methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methacrylic acid second Ester, acrylic acid-2-ethyl caproite etc. (methyl) acrylate monomer；Acrylamide, Methacrylamide etc. (methyl) acryloyl Amine monomers；Acrylonitrile, methacrylonitrile etc. (methyl) acrylonitrile monemer；Methacrylic acid -2- (perfluoro hexyl) ethyl ester, propylene Fluorine-containing (methyl) acrylate monomer such as acid -2- (perfluoro butyl) ethyl ester；Maleimide；The Malaysias such as phenyl maleimide acyl Imine derivative；Diene monomers such as 1,3- butadiene, isoprene etc..It, can also be in addition, these can be used alone Two or more is applied in combination with arbitrary ratio.
It is noted that in the present invention, (methyl) acrylate refers to acrylate and/or methacrylate The meaning, (methyl) acrylonitrile refer to the meaning of acrylonitrile and/or methacrylonitrile.
In these monomers, monomer used in the preparation as the polymer in core portion is, it is preferable to use (methyl) propylene Acid ester monomer more preferably uses methyl methacrylate and/or butyl acrylate.That is, the polymer in core portion preferably comprises (first Base) acrylate monomeric units further preferably include the monomer list from methyl methacrylate and/or butyl acrylate Member.By using above-mentioned monomer, thus make the control of the electrolyte swellbility of the polymer in core portion, core portion polymer glass The control of glass transition temperature becomes easy, and can further increase the ion diffusion for the functional layer for having used organic filler Property.
In addition, the polymer in core portion may include the monomeric unit containing acidic group.Here, as the monomer containing acidic group, it can Enumerate the monomer with acidic group, for example, the monomer with carboxylic acid group, with sulfonic monomer, the monomer with phosphate and Monomer with hydroxyl.
Moreover, can be enumerated such as monocarboxylic acid, dicarboxylic acids as the monomer with carboxylic acid group.As monocarboxylic acid, can enumerate Such as acrylic acid, methacrylic acid, crotonic acid etc..As dicarboxylic acids, can enumerate such as maleic acid, fumaric acid, itaconic acid.
In addition, such as vinyl sulfonic acid, methyl ethylene sulfonic acid, (methyl) can be enumerated as with sulfonic monomer Allyl sulphonic acid, (methyl) acrylic acid -2- sulfonic acid, 2- acrylamide-2-methylpro panesulfonic acid, 3- aryloxy group -2- hydroxyl Propane sulfonic acid etc..
In turn, as the monomer with phosphate, such as phosphoric acid -2- (methyl) acryloyloxyethyl ester, phosphoric acid can be enumerated Methyl -2- (methyl) acryloyloxyethyl ester, ethyl-(methyl) acryloyloxyethyl ester etc..
In addition, such as 2-Hydroxy ethyl acrylate, acrylic acid -2- hydroxyl third can be enumerated as the monomer with hydroxyl Ester, methacrylic acid -2- hydroxy methacrylate, methacrylic acid -2- hydroxy propyl ester etc..
It is noted that in the present invention, " (methyl) allyl " refers to the meaning of allyl and/or methacrylic Think, (methyl) acryloyl refers to the meaning of acryloyl and/or methacryl.
In these, as the monomer containing acidic group, preferably with the monomer of carboxylic acid group, wherein it is preferred that monocarboxylic acid, more excellent Select (methyl) acrylic acid.
In addition, the monomer containing acidic group can be used alone, two or more use can also be combined with arbitrary ratio.
In addition, the ratio of the monomeric unit containing acidic group in the polymer in core portion is preferably 0.1 mass % or more, it is more excellent Be selected as 1 mass % or more, preferably 20 mass % hereinafter, more preferably 10 mass % hereinafter, further preferably 7 mass % with Under.By will the ratio containing the monomeric unit of acidic group within the above range, so as to the raising when preparing organic filler The dispersibility of the polymer in core portion makes the outer surface of the polymer in core portion be readily formed the outer surface for partly covering core portion Shell portion.
In addition, the polymer in core portion also includes cross-linking monomer units preferably other than above-mentioned monomeric unit.Bridging property Monomer refers to the monomer that can form cross-linked structure in polymerization or after polymerization by heating or the irradiation of energy line.By the inclusion of Cross-linking monomer units, so as to be in the electrolyte swellbility of polymer in above-mentioned range.
As cross-linkable monomer, can enumerate has the multifunctional of 2 or more polymerisation reactivity groups for example in the monomer Monomer.It as such polyfunctional monomer, can enumerate for example: the divinyl compounds such as divinylbenzene；Dimethacrylate Vinyl acetate, diethyleneglycol dimethacrylate, ethylene glycol dimethacrylate, diethyleneglycol diacrylate, two propylene Acid -1,3 butylene glycol ester etc. two (methyl) acrylate compounds；Trimethacrylate acid trihydroxy methyl propyl ester, three acrylic acid, three hydroxyl Methyl propyl ester etc. three (methyl) acrylate compounds；Allyl glycidyl ether, glycidyl methacrylate etc. contain There is the ethylenically unsaturated monomer etc. of epoxy group.In these, from the electrolyte swellbility for the polymer for easily controlling core portion Viewpoint is set out, preferably dimethacrylated conjunction object and the ethylenically unsaturated monomer containing epoxy group, more preferable dimethyl propylene Enoic acid ester compounds.In addition, these can be used alone, two or more can also be applied in combination with arbitrary ratio.
Wherein, usually when the ratio of cross-linking monomer units in the polymer increases, then the polymer relative to electricity The swellbility of solution liquid has the tendency that becoming smaller.Therefore, the ratio of cross-linking monomer units preferably consider the monomer used type and Amount is to determine.The specific ratio of cross-linking monomer units in the polymer in core portion is preferably 0.1 mass % or more, more preferably For 0.2 mass % or more, further preferably 0.5 mass % or more, preferably 10 mass % hereinafter, more preferably 8 mass % Hereinafter, further preferably 6 mass % or less.By make cross-linking monomer units ratio become above range lower limit value with On, so as to improve the cementability of functional layer.In addition, by making the ratio of cross-linking monomer units become the upper of above range Limit value is hereinafter, so as to improve the cycle characteristics of non-aqueous secondary battery.
[[shell portion]]
The electrolyte swellbility-of the polymer in shell portion
The shell portion of organic filler is by the polymerization with the defined electrolyte swellbility smaller than the electrolyte swellbility in core portion Object is formed.Specifically, the electrolyte swellbility of the polymer in shell portion is needed more than 1 times, preferably 1.1 times or more, more preferably It is 1.2 times or more, furthermore, it is necessary to for 4 times hereinafter, preferably 3.5 times hereinafter, more preferably 3 times or less.By making the poly- of shell portion The electrolyte swellbility for closing object makes more than the lower limit value of above range so as to make functional layer show high Ionic diffusion The low temperature output characteristics of secondary cell improve.In addition, the electrolyte swellbility of the polymer by making shell portion becomes above range Upper limit value hereinafter, so as to improve the cementability of functional layer in the electrolytic solution, make the high-temperature cycle of secondary cell It improves.
It is noted that in the present invention, " the electrolyte swellbility " of the polymer in shell portion is able to use this specification Embodiment described in measuring method measurement.
In addition, the method for the electrolyte swellbility as the polymer for adjusting shell portion, can enumerate and for example consider electrolyte SP value properly selects the type and amount of the monomer of the polymer for manufacturing the shell portion.
The glass transition temperature-of the polymer in shell portion
In addition, the glass transition temperature for constituting the polymer in the shell portion of organic filler is preferably 50 DEG C or more, more preferably It is 60 DEG C or more, further preferably 70 DEG C or more, furthermore it is preferred that for 200 DEG C hereinafter, more preferably 180 DEG C hereinafter, further Preferably 150 DEG C or less.By the way that the glass transition temperature of the polymer in shell portion is set as 50 DEG C or more, so as to inhibit viscous Generation even, in addition to this, additionally it is possible to improve the low temperature output characteristics of secondary cell.In addition, by by the polymer in shell portion Glass transition temperature be set as 200 DEG C hereinafter, so as to further increase the cementability of functional layer.
In addition, the method for the glass transition temperature as the polymer for adjusting shell portion, can enumerate and for example consider for making The type and amount of the monomer are properly selected for the glass transition temperature of the homopolymer of the monomer of the polymer in shell portion.
The composition-of the polymer in shell portion
As the monomer for the polymer for being used to prepare shell portion, it is upper for can properly selecting the electrolyte swellbility of its polymer State range monomer come using.As such monomer, can enumerate for example with the list as the polymer that can be used for manufacturing core portion The same monomer of monomer that body illustrates.In addition, such monomer can be used alone, can also with arbitrary ratio by 2 kinds with On be applied in combination.
In these monomers, the monomer as the polymer that can be used for preparing shell portion is, it is preferable to use aromatic ethenyl list Body.That is, the polymer in shell portion preferably comprises aromatic vinyl monomer unit.In addition, in aromatic vinyl monomer, it is more excellent Select the styrene derivatives such as styrene and styrene sulfonic acid.If being easy to control polymer using aromatic vinyl monomer Electrolyte swellbility.Furthermore it is possible to further increase the cementability of functional layer.
Moreover, the ratio of the aromatic vinyl monomer unit in the polymer in shell portion is preferably 20 mass % or more, more Preferably 40 mass % or more, further preferably 50 mass % or more are still more preferably 60 mass % or more, especially excellent 80 mass % or more, preferably 100 mass % are selected as hereinafter, more preferably 99.5 mass % are hereinafter, further preferably 99 matter Measure % or less.By making the ratio of aromatic vinyl monomer unit within the above range, to be easy to the polymerization in shell portion The electrolyte swellbility and glass transition temperature of object are controlled in desired range.Furthermore it is possible to further increase electrolyte In functional layer cementability.
In addition, the polymer in shell portion also may include the monomer list containing acidic group other than aromatic vinyl monomer unit Member.Here, the monomer with acidic group can be enumerated as the monomer containing acidic group, for example, the monomer with carboxylic acid group, there is sulphur The monomer of acidic group, the monomer with phosphate and the monomer with hydroxyl.Specifically, as the monomer containing acidic group, it can It enumerates and may include the same monomer of the monomer containing acidic group in core portion.
In these, as the monomer containing acidic group, preferably there is the monomer of carboxylic acid group, wherein more preferable monocarboxylic acid, into One step preferably (methyl) acrylic acid.
In addition, the monomer containing acidic group can be used alone, two or more can also be applied in combination with arbitrary ratio.
The ratio of the monomeric unit containing acidic group in the polymer in shell portion is preferably 0.1 mass % or more, and more preferably 1 Quality % or more, further preferably 3 mass % or more, preferably 20 mass % hereinafter, more preferably 10 mass % hereinafter, into One step is preferably 7 mass % or less.By making the ratio of the monomeric unit containing acidic group within the above range, so as to make The dispersibility of organic filler in functional layer improves.
In addition, the polymer in shell portion may include cross-linking monomer units.As cross-linkable monomer, can enumerate for example with conduct It can be used for the same monomer of monomer that the cross-linkable monomer of the polymer in core portion illustrates.In addition, cross-linkable monomer can individually make With a kind, two or more can also be applied in combination with arbitrary ratio.
Moreover, the ratio of the cross-linking monomer units in the polymer in shell portion is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, further preferably 0.5 mass % or more, preferably 5 mass % hereinafter, more preferably 4 mass % with Under, further preferably 3 mass % or less.
The form-in shell portion
In addition, the form in shell portion is not particularly limited, but preferably shell portion is made of the particle of polymer.In shell portion by gathering In the case where the particle composition for closing object, the particle for constituting shell portion can be in the multiple overlappings of radial direction of organic filler.However, it is preferred to constitute The particle in shell portion is not overlapped in the radial direction of organic filler each other, the particles of these polymer is constituted shell portion with single layer.
[preparation method of organic filler]
Moreover, the organic filler with above-mentioned core-shell structure can be prepared for example, by following methods, that is, use core The monomer of the polymer of the monomer and shell portion of the polymer in portion, changes over time the ratio of these monomers and is periodically gathered It closes.Connect specifically, organic filler can be successively coated as the polymer in first stage by the polymer in the rear stage Continuous multistage emulsion polymerization and multistage suspension polymerization and prepare.
Therefore, there is the organic filler of above-mentioned core-shell structure obtained from the emulsion polymerization described below as the multistage One example of situation.
In polymerization, conventionally, as emulsifier, it is able to use such as neopelex, dodecane The anionic surfactants such as base sodium sulphate；The nonionics such as ethylene nonyl phenyl ether, sorbitan monolaurate The cationic surfactants such as surfactant or octadecylamine acetate.In addition, can make as polymerization initiator With for example: the peroxide such as peroxide -2-ethyl hexanoic acid tert-butyl, potassium peroxydisulfate, cumene peroxide；Bis- (the 2- first of 2,2 '-azos Base-N- (2- hydroxyethyl)-propionamide), the azo-compounds such as bis- (2- amidine propane) hydrochlorides of 2,2 '-azos.
Then, as polymerization procedure, firstly, being mixed to form the monomer and emulsifier in core portion, it is poly- disposably to carry out lotion It closes, thus obtains the polymer for constituting the particle shape in core portion.In turn, in the presence of the polymer of the particle shape in this composition core portion To be formed the polymerization of the monomer in shell portion, thus, it is possible to the organic fillers for the core-shell structure for obtaining having above-mentioned.
At this moment, from the viewpoint of being partly covered the outer surface in core portion by shell portion, the polymerization in shell portion will preferably be formed The monomer of object repeatedly or is continuously fed in polymerization system in batches.By will be formed the monomer of the polymer in shell portion in batches or Person is continuously fed to polymerization system, so as to which the polymer for constituting shell portion is formed as particle shape, leads to the particle and core portion is tied It closes, so as to form the shell portion for partly covering core portion.
In addition, can divide according to by monomer in the case where the monomer that will form the polymer in shell portion repeatedly supplies in batches Batch ratio control the average thickness in shell portion.In addition, the case where the monomer for forming the polymer in shell portion is continuously fed Under, the average thickness in shell portion can be controlled by adjusting the supply amount of monomer per unit time.
In addition, formed shell portion after organic filler volume average particle size D50 can for example, by adjust emulsifier amount, Amount of monomer etc. is to become desired range.In turn, the average proportions (covering rate) that the outer surface in core portion is covered by shell portion It can be for example, by the amount of the monomer of the polymer of the amount and formation shell portion of adjusting emulsifier to become desired range.
[functional layer binding material]
Here, as described above, organic filler in be not swollen in the electrolytic solution and when under unheated state usually not Show big cementability.Therefore, from inhibit functional layer formed after followed by (heating before or to electrolyte dipping before) organic filler Just from the viewpoint of falling off functional layer, even preferred function layer includes in not being swollen in the electrolytic solution and unheated Also the functional layer binding material of cementability is played under state.By using functional layer binding material, even so as to It falls off being in not to be swollen in the electrolytic solution and be also able to suppress the ingredients such as organic filler under unheated state from functional layer.
Moreover, known binding material can be enumerated as the functional layer binding material that can be shared with above-mentioned organic filler Such as thermoplastic elastomer (TPE).Moreover, preferably conjugated diene polymer and acrylic ester polymerize as thermoplastic elastomer (TPE) Object, more preferable acrylic ester polymer.
Here, conjugated diene polymer refers to the polymer comprising conjugated diene monomeric unit, as conjugated diene The specific example of polymer, can enumerate styrene-butadiene copolymer (SBR) etc. includes aromatic vinyl monomer unit and rouge The polymer of fat race conjugated diene monomeric unit, acrylic rubber (NBR) are (poly- comprising acrylonitrile unit and butadiene unit Close object) etc..In addition, acrylic ester polymer refers to the polymer comprising (methyl) acrylate monomeric units.Here, conduct (methyl) acrylate monomer that (methyl) acrylate monomeric units can be formed, is able to use and is used to prepare organic filler core The same monomer of the monomer of the polymer in portion.
In addition, these functional layers can be used alone with binding material, two or more can also be applied in combination.But It is using the functional layer binding material for being combined with polymer of more than two kinds, to be used as such functional layer viscous The polymer for tying material is set as having the organic filler of core-shell structure formed by defined polymer is different to gather from above-mentioned Close object.
In turn, the acrylic ester polymer as functional layer binding material further preferably includes (methyl) propylene Nitrile monomer unit.Thereby, it is possible to improve the intensity of functional layer.
Here, in the acrylic ester polymer as functional layer binding material, (methyl) acrylonitrile monomer unit Amount relative to the ratio of (methyl) acrylonitrile monomer unit and the total amount of (methyl) acrylate monomeric units be preferably 1 matter % or more is measured, more preferably 2 mass % or more, preferably 30 mass % are hereinafter, more preferably 25 mass % or less.On making Stating ratio becomes the lower limit value of above range or more, poly- as the acrylic ester of functional layer binding material so as to improve The intensity for closing object, further increases the intensity for having used the functional layer of the acrylic ester polymer.In addition, by making above-mentioned ratio Example becomes the upper limit value of above range hereinafter, to which the acrylic ester polymer as functional layer binding material is relative to electricity Solution liquid is moderately swollen, therefore is able to suppress the reduction of the ionic conductance of functional layer and the low temperature output characteristics of secondary cell It reduces.
In addition, the glass transition temperature of functional layer binding material usually than the core portion of organic filler polymer glass The glass transition temperature of the polymer in glass transition temperature and shell portion is low, preferably -100 DEG C or more, more preferably -90 DEG C with On, further preferably -80 DEG C or more, furthermore it is preferred that being 0 DEG C hereinafter, being more preferably -5 DEG C hereinafter, further preferably -10 DEG C or less.By making the glass transition temperature of functional layer binding material become the lower limit value of above range or more, so as to Enough improve the cementability and intensity of functional layer binding material.In addition, the glass transition by making functional layer binding material Temperature becomes the upper limit value of above range hereinafter, so as to improve the flexibility of functional layer.
In addition, heating when the low functional layer of glass transition temperature is typically due to be formed functional layer with binding material etc. and Liquidation, thus such as becoming to be not easy in SEM in hold shape degree widely disperse in functional layer.
Moreover, the above-mentioned organic filler relative to 100 mass parts, the content of the functional layer binding material in functional layer More than preferably 1 mass parts, more than more preferably 3 mass parts, more than further preferably 5 mass parts, furthermore it is preferred that being 30 matter Part is measured hereinafter, more preferably 25 below the mass, further preferably 20 below the mass.By making functional layer binding material Content become above range lower limit value more than, so as to improve the caking property of functional layer, before fully preventing heating Or organic filler falls off from functional layer before impregnating to electrolyte.In addition, by making the content of functional layer binding material become upper The upper limit value of range is stated hereinafter, the reduction of the ionic conductance so as to inhibit functional layer and the low temperature output of secondary cell are special The reduction of property.
As the manufacturing method of functional layer binding material, it is poly- that such as solution polymerization process, suspension polymerization, lotion can be enumerated It is legal etc..Wherein, because can polymerize in water, can be straight by the aqueous dispersions of the functional layer binding material comprising particle shape The formation for performing well in functional layer is connect, it is advantageous to emulsion polymerizations and suspension polymerization.In addition, being used as functional layer in manufacture When with the polymer of binding material, preferably its reaction system includes dispersing agent.Functional layer is with binding material usually substantially by structure It is formed at its polymer, but can also be with optional compositions such as the additives used in polymerization.
[non-conductive particles]
In turn, in the case where functional layer is also functioned as porous membrane layer, functional layer also may include non-conductive Particle.It is not particularly limited as the non-conductive particles cooperated in functional layer, can enumerate and can be used for the secondary electricity of non-water system The known non-conductive particles in pond.
Specifically, being able to use inorganic particles and above-mentioned organic filler and functional layer as non-conductive particles With both organic fine particles other than binding material, but usually using inorganic particles.Wherein, as the material of non-conductive particles, It is preferred that steadily existing under the use environment of non-aqueous secondary battery, the material that electrochemistry is stable.When from such viewpoint Set out the preferred example for enumerating the material of non-conductive particles when, can enumerate: aluminium oxide (alumina), hydrated aluminum oxide (boehmite), silica, magnesia (magnesia), calcium oxide, titanium oxide (titania), BaTiO3, ZrO, aluminium oxide-two The oxide particles such as monox composite oxides；The nitride particles such as aluminium nitride, boron nitride；Silicon, diamond etc. are covalently bonded Crystalline particle；The slightly solubilities ionic crystal particle such as barium sulfate, calcirm-fluoride, barium fluoride；Small bits of clay such as talcum powder, montmorillonite etc.. In addition, these particles, which can according to need, implements element substitution, surface treatment, solid solution etc..
In addition, above-mentioned non-conductive particles can be used alone, two or more can also be applied in combination.
[other ingredients]
Moreover, functional layer also may include optional other ingredients in addition to the above ingredients.As long as above-mentioned other ingredients Cell reaction is not influenced to be not particularly limited, is able to use well known ingredient.In addition, these other ingredients can be independent Using a kind, two or more can also be applied in combination.
As above-mentioned other ingredients, the wetting agent such as ethylene oxide-propylene oxide copolymer, viscosity-adjusting agent can be enumerated Agent, electrolysis additive etc. form the known additive used when functional layer.
[construction of functional layer]
Moreover, the functional layer forming face in spacer substrate is formed by functional layer, such as functional layer as shown in Figure 1 An example surface SEM image as, had by what multiple organic fillers of individual organic filler or aggregation were formed The part that the phase (that is, part existing for organic filler) and organic filler of machine particle are not present is (for example, only functional layer bonds material Existing part of ingredient other than the organic fillers such as material etc.) it is mixed.In addition, in the functional layer forming face of spacer substrate In, there may also be the parts that the ingredient that organic filler, functional layer binding material etc. constitute functional layer is not present.
[[phase of organic filler]]
Here, the entirety for not needing covering function layer forming face mutually of organic filler, but need relative to functional layer The area of forming face exists with 20% or more and 80% ratio below.This is because present on the functional layer forming face The area of the phase of organic filler relative to the area of functional layer forming face ratio (=(part existing for the phase of organic filler Area/functional layer forming face area) × 100%) less than 20% in the case where, play excellent bonding force in the electrolytic solution The amount of organic filler becomes very few, and the cementability of functional layer in the electrolytic solution reduces, and has used the secondary cell of spacer High-temperature cycle reduces.In addition, although organic filler plays ionic conductance high to a certain degree, if organic filler Existing part is compared with the part that organic filler is not present, and the ionic conductance of part existing for organic filler reduces. Therefore, from improving the ionic conductance in the electrolytic solution of functional layer, improve to have used the low temperature of the secondary cell of spacer From the perspective of output characteristics, formed in the area of the phase of organic filler present on the functional layer forming face relative to functional layer The ratio of the area in face needs to be set as 80% or less.
Moreover, from fully ensuring the cementability of functional layer in the electrolytic solution, making the high-temperature cycle of secondary cell From the perspective of raising, the area of part existing for the phase of organic filler is preferred relative to the ratio of the area of functional layer forming face It is 25% or more, more preferably 30% or more, further preferably 35% or more.In addition, from further increase functional layer Ionic conductance in electrolyte further increases the viewpoint of the low temperature output characteristics of secondary cell of spacer has been used to go out Hair, the area of part existing for the phase of organic filler relative to the ratio of the area of functional layer forming face be preferably 70% hereinafter, More preferably 60% hereinafter, further preferably 45% or less.
In addition, the phase of organic filler exists with irregular shape.Specifically, in functional layer, by individually organic Multiple phases that particle or the organic filler of aggregation are formed are not certain repeat patterns shapes (for example, striated, clathrate Deng), but with the presence of irregular shape.In turn, it in functional layer, is deposited by the phase of organic filler with irregular shape So as to improve cementability in the electrolytic solution.
Here, as organic filler phase with existing for irregular shape construction be not particularly limited, can enumerate for example, The island phase that formed by the condensate of individual organic filler or 10 organic fillers below and by 11 or more organic grains The alternate construction etc. being mixed across the part that organic filler is not present of continent shape that son is formed.
In addition, the shape of the phase of the area and organic filler of part existing for the phase of organic filler can for example, by pair between The type and functional layer of spacing body substrate and the material (non-aqueous secondary battery functional layer composition) for being used to form functional layer Forming method change and adjust.
(manufacturing method of non-aqueous secondary battery spacer)
Moreover, the non-aqueous secondary battery spacer of the invention of the functional layer with above-mentioned construction can for example make It is easily made of the manufacturing method of non-aqueous secondary battery of the invention spacer.
Here, the manufacturing method of non-aqueous secondary battery spacer of the invention be characterized in that, comprising the following steps: Prepare the process (substrate preparatory process) of spacer substrate, the water droplet contact angle of the functional layer forming face of above-mentioned spacer substrate is 80 ° or more and 130 ° or less；Prepare the process (composition preparatory process) of non-aqueous secondary battery functional layer composition, it is above-mentioned Non-aqueous secondary battery functional layer contains the decentralized media such as ingredient and the water for constituting functional layer with composition and surface tension is 33mN/m or more and 39mN/m or less；Non-aqueous secondary battery functional layer is coated on to the functional layer of spacer substrate with composition In forming face, it is dried with composition the non-aqueous secondary battery functional layer of coating and forms functional layer on spacer substrate Process (functional layer formation process).Moreover, in the manufacturing method of non-aqueous secondary battery spacer of the invention, will be non- Aqoue seconary battery functional layer is coated in the functional layer forming face of spacer substrate with composition, keeps the non-water system of coating secondary Battery functi on layer be dried with composition and on spacer substrate formed functional layer when, by using the water droplet of functional layer forming face Contact angle is 80 ° or more and 130 ° spacer substrates below and the use of surface tension is 33mN/m or more and 39mN/m or less Non-aqueous secondary battery functional layer composition, so as to be readily formed the functional layer of above-mentioned construction.
<substrate preparatory process>
In substrate preparatory process, the water droplet contact angle for preparing at least one surface (functional layer forming face) is 80 ° or more And 130 ° of spacer substrates below.
Here, in the case where the water droplet contact angle of functional layer forming face is less than 80 °, organic grain in the functional layer of formation The area ratio of part existing for the phase of son can become excessive.In addition, the water droplet contact angle in functional layer forming face is more than 130 ° In the case where, the area ratio of part existing for the phase of organic filler can become too small in the functional layer of formation.Moreover, from will The area ratio of part existing for the phase of organic filler is set as from the perspective of appropriate size, and the water droplet of functional layer forming face connects Feeler is preferably 85 ° or more, and more preferably 90 ° or more, furthermore it is preferred that for 120 ° hereinafter, more preferably 110 ° or less.
In addition, water droplet contact angle is that 80 ° or more and 130 ° spacer substrates below are not particularly limited, purchase can be passed through Enter the commercially available spacer substrate on the surface with water droplet contact angle within the above range and is prepared, it can also be by using The surface treatments such as the Corona discharge Treatment as described in the item of above-mentioned<spacer substrate>are come to can be used as spacer base The size of the water droplet contact angle on the surface of the microporous membrane of material is adjusted to be prepared.
<composition preparatory process>
In composition preparatory process, prepare non-aqueous secondary battery functional layer composition, the above-mentioned secondary electricity of non-water system Pond functional layer is paste compound with composition and surface tension is 33mN/m or more and 39mN/m hereinafter, above-mentioned slurry compositions Object at least contains above-mentioned organic filler, optionally contains functional layer binding material, non-conductive particles, other ingredients, will Water etc. is used as decentralized medium.
Here, having in the functional layer of formation in the case where the surface tension of functional layer composition is less than 33mN/m The ratio regular meeting of the area of part existing for the phase of machine particle becomes excessive.In addition, the surface tension in functional layer composition is super In the case where crossing 39mN/m, the ratio regular meeting of the area of part existing for the phase of organic filler became in the functional layer of formation It is small.Moreover, the ratio of the area of the part existing for the phase by organic filler is set as appropriate size, functional layer Be preferably 34mN/m or more with the surface tension of composition, more preferably 35mN/m or more, furthermore it is preferred that be 38mN/m hereinafter, More preferably 37mN/m or less.
In addition, the preparation method of functional layer composition is not particularly limited, usually by organic filler, as decentralized medium Water, functional layer used as needed binding material, non-conductive particles and other ingredients mixed and prepare function Ergosphere composition.Mixed method is not particularly limited, in order to disperse each ingredient effectively, usually using dispersion machine as mixed It attaches together to set and be mixed.
As dispersion machine, it is preferable to use mentioned component can be uniformly dispersed and mixed device.As dispersion machine Example can enumerate ball mill, sand mill, pigment dispersion machine, shredding machine, ultrasonic dispersing machine, homogenizer, planetary stirring machine Deng.In addition, it is preferable to use the high dispersives such as ball mill, roller mill, filmix from the viewpoint of it can apply high dispersive shearing force Device.
In addition, the size of the surface tension of functional layer composition is not particularly limited, wetting agent can be added to function Ergosphere is adjusted in composition, such as the additive amount by increasing wetting agent is so as to reducing functional layer composition Surface tension.
Here, being not particularly limited as wetting agent, it is able to use nonionic surfactant, ionic surface active agent etc. Known surfactant.Wherein, as wetting agent, it is preferable to use nonionic surfactant, more preferably total using polyether system Polymers further preferably uses ethylene oxide-propylene oxide copolymer.In turn, as long as the use level of wetting agent can make function The surface tension of layer composition is not particularly limited as above range, for example, organic grain relative to 100 mass parts Son, is preferably set to 0.1 mass parts or more, is more preferably set as 0.5 mass parts or more, is further preferably set as 1.0 mass parts or more, 1.5 mass parts or more particularly preferably are set as, 5.0 is preferably set to below the mass, is more preferably set as 3.0 below the mass, into one Step is preferably set to 2.5 below the mass, is particularly preferably set as 2.2 below the mass.In the very few situation of the use level of wetting agent Under, the surface tension of functional layer composition is possible to fully to reduce.On the other hand, excessive in the use level of wetting agent In the case where, the surface tension of functional layer composition is possible to become too small.In addition, the feelings excessive in the use level of wetting agent Under condition, the cementability of functional layer is likely to decrease, the high-temperature cycle of secondary cell is likely to decrease.
<functional layer formation process>
Functional layer formation process includes that functional layer is coated on to the work of the functional layer forming face of spacer substrate with composition Sequence (painting process), the process for being dried with composition the functional layer being coated on spacer substrate and forming functional layer are (dry Process).Moreover, in functional layer formation process will there is the functional layer of above-mentioned surface tension to be coated on tool with composition When having in the functional layer forming face of above-mentioned water droplet contact angle, functional layer composition is moderately repelled, to will not cover The all surfaces of functional layer forming face and in unevenly dispersing.As a result, functional layer is dried and shape with composition At functional layer become with above-mentioned specific shape and specific area ratio organic filler phase functional layer.
Here, functional layer is not limited especially with the method that composition is coated on spacer substrate in painting process The methods of system, such as spray coating method, scraper method can be enumerated, reverse roll coating process, direct roll coating process, gravure method, extrusion, spread coating. Wherein, the functional layer aspect thinner from formation, preferably gravure method, spray coating method.
In addition, in drying process, as the method for being dried with composition the functional layer on spacer substrate without spy Do not limit, be able to use well known method, can enumerate for example using warm wind, hot wind, the seasoning of low wet wind, boulton process, Utilize the seasoning of the irradiation of infrared ray, electron ray etc..Drying condition is not particularly limited, and drying temperature is preferably 30~80 DEG C, drying time is preferably 30 seconds~10 minutes.
Alternatively, it is also possible to use next pair of mold press or roll press etc. after the drying of functional layer composition Functional layer implements pressurized treatments.By pressurized treatments so as to improving the adaptation of functional layer and substrate.
Moreover, the thickness of the functional layer formed on spacer substrate is preferably 0.01 μm or more, more preferably 0.1 μm with On, further preferably 0.5 μm or more, preferably 20 μm hereinafter, more preferably 10 μm hereinafter, further preferably 5 μm or less. More than the lower limit value with a thickness of above range of functional layer, so as to fully ensure the intensity of functional layer.In addition, logical The upper limit value with a thickness of above range of functional layer is crossed hereinafter, Ionic diffusion so as to ensure functional layer, makes secondary electricity The low temperature output characteristics in pond further increase.
(non-aqueous secondary battery)
Non-aqueous secondary battery of the invention is characterized in that, has anode, cathode, spacer and electrolyte, as Spacing body uses the non-aqueous secondary battery spacer with above-mentioned functional layer.Moreover, in the secondary electricity of non-water system of the invention Chi Zhong, in the case where above-mentioned functional layer is functioned as adhesive layer, anode and spacer, and/or cathode and spacer It is bonded well across functional layer.In addition, because non-aqueous secondary battery of the invention has spacer of the invention, this The spacer of invention has the excellent functional layer of both cementability and ionic conductances in the electrolytic solution, so high temperature circulation is special The battery behaviors such as property and low temperature output characteristics are excellent.
In addition, as anode and cathode, being able to use in non-aqueous secondary battery can make in non-aqueous secondary battery Known anode and cathode.In addition, being able to use workable known in non-aqueous secondary battery as electrolyte Electrolyte.
Specifically, being not particularly limited as electrode (anode and cathode), it is able to use and forms electrode on the current collector The electrode of composite layer.Here, the ingredient in collector, electrode composite material layer is (for example, (anode is living for electrode active material Property substance, negative electrode active material) and electrode composite material layer binding material (anode composite material layer binding material, cathode Composite layer binding material) etc.) and the method that forms on collector electrode composite material layer be able to use it is known Method.Specifically, being able to use the method recorded in such as Japanese Unexamined Patent Publication 2013-145763 bulletin.
In addition, can typically be used in organic solvent as electrolyte and dissolved the organic electrolyte of supporting electrolyte.Example Such as, in the case where non-aqueous secondary battery is lithium ion secondary battery, lithium salts can be used as supporting electrolyte.As lithium Salt can enumerate such as LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、 CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2) NLi etc..Wherein, high solution is shown because solvent is soluble in From degree, it is advantageous to LiPF6、LiClO4、CF3SO3Li, particularly preferred LiPF6.In addition, electrolyte can be used alone, Two or more can be applied in combination with arbitrary ratio.Usually there is supporting electrolyte lithium ion conductivity more high using degree of dissociation More raised tendency, therefore lithium ion conductivity can be adjusted by the type of supporting electrolyte.
In turn, as the organic solvent used in the electrolytic solution, as long as supporting electrolyte can be dissolved then without special It limits, preferably using for example: dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propene carbonate (PC), the carbonates such as butylene (BC), methyl ethyl carbonate (EMC)；The esters such as gamma-butyrolacton, methyl formate；1,2- bis- The ethers such as Ethyl Methyl Ether, tetrahydrofuran；Sulfur-containing compounds class such as sulfolane, dimethyl sulfoxide etc..Furthermore this also can be used The mixed solution of a little solvents.Wherein, because of high, the stable voltage belt field width of dielectric constant, it is advantageous to use carbonates, into It is preferable to use the mixtures of ethylene carbonate and methyl ethyl carbonate for one step.
In addition, the concentration of the electrolyte in electrolyte can be adjusted suitably, such as be preferably set to 0.5~15 mass %, 2~13 mass % more preferably are set as, are further preferably set as 5~10 mass %.In addition, in the electrolytic solution, can also add Additive known such as fluorinated ethylene carbonate, Methylethyl sulfone etc..
<manufacturing method of non-aqueous secondary battery>
Non-aqueous secondary battery is manufactured for example, by following manner, that is, is overlapped anode and cathode across spacer, root According to needing to be wound corresponding to cell shapes, fold, it is put into battery case, injects the electrolyte into battery case progress Sealing, to manufacture.The generation of the pressure rising, charge and discharge etc. excessively of the inside of non-aqueous secondary battery in order to prevent, can also root According to needing to be arranged the anti-overcurrent element such as fuse, PTC element, porous metal mesh, guide plate etc..The shape of non-aqueous secondary battery Or it is any such as Coin shape, coin shape, piece type, cylinder type, rectangular, platypelloid type.
Embodiment
Hereinafter, being specifically explained based on embodiment to the present invention, but the present invention is not limited to these embodiments.Separately Outside, in the following description, " % " and " part " of expression amount is then quality criteria unless otherwise specified.
In addition, the structural unit for forming certain monomer polymerization exists various of monomer to be copolymerized in the polymer of manufacture Ratio in above-mentioned polymer as long as no other explanation, usually with certain monomer used in the polymerizeing of the polymer all Shared ratio (charge ratio) is consistent in monomer.
In embodiment and comparative example, the electrolyte swellbility and vitrifying of the polymer in core portion and the polymer in shell portion turn Temperature, the glass transition temperature of functional layer binding material, the volume average particle size D50 of organic filler, organic filler Nucleocapsid ratio and covering rate, the surface tension of non-aqueous secondary battery functional layer composition, spacer substrate water drop contact Angle, organic filler phase existing for part area ratio, electrolyte dipping after electrode and spacer cementability and The high-temperature cycle and low temperature output characteristics of secondary cell are measured and evaluate according to following methods.
<the electrolyte swellbility of the polymer of the polymer and shell portion in core portion>
Using monomer and various additives etc. used in the formation in the core portion and shell portion of organic filler, with the core portion The aqueous dispersions of the polymer comprising core portion are prepared under polymerizing condition identical with the polymerizing condition in shell portion respectively and comprising shell portion Polymer aqueous dispersions.The aqueous dispersions are put into the culture dish of polytetrafluoroethylene (PTFE), in 110 DEG C, 10 hours items Part is dry, obtains the film of thickness 0.5mm.Then, obtained film is cut into 1cm square, obtains test film.Measure the test film Quality W0.In addition, above-mentioned test film is impregnated 72 hours at 60 DEG C in the electrolytic solution.Then, test film is taken out from electrolyte, The electrolyte on the surface of wipe test piece, the quality W1 of the test film after measuring immersion test.Then, using these quality W0 and W1 finds out electrolyte swellbility S (again) by S=W1/W0.
In addition, as electrolyte, using in ethylene carbonate (EC), diethyl carbonate (DEC) and vinylene carbonate (VC) mixed solvent (volumetric mixture ratio: EC/DEC/VC=68.5/30/1.5；SP value: 12.7 (cal/cm3)1/2) in make to make For the LiPF of supporting electrolyte6The product dissolved relative to solvent with the concentration of 1mol/L.
<glass transition temperature of the polymer in core portion, the polymer in shell portion and functional layer binding material>
Using monomer and various additives etc. used in the formation in the core portion and shell portion of organic filler, with the core portion It is prepared respectively under polymerizing condition identical with the polymerizing condition in shell portion comprising the polymer (polymer in core portion as measurement sample With the polymer in shell portion) aqueous dispersions.Then, using the aqueous dispersions of preparation as measurement sample.In addition, preparing includes function The layer aqueous dispersions of binding material, as measurement sample.
Secondly, being claimed using differential thermal analysis measurement device (SII Nano Technology system " EXSTARDSC6220 ") The measurement sample of 10mg dried is measured into aluminum dish, uses empty aluminum dish as referring to, -100 DEG C of measuring temperature range~ Between 500 DEG C, with 10 DEG C/min of heating rate, under ambient temperature and moisture, DSC curve is measured.In the temperature-rise period, according to Differential signal (DDSC) as 0.05mW/ minutes/mg or more DSC curve endothermic peak will occur before baseline and absorbing heat Initially occur the intersection point of the tangent line of the DSC curve of inflection point behind peak, acquires glass transition temperature.
<the volume average particle size D50 of organic filler>
In the grain using laser diffraction formula particle size distribution analyzer (Shimadzu Seisakusho Ltd.'s corporation " SALD-3100 ") measurement In diameter distribution, the volume average particle size D50 of organic filler is that the cumulative volume calculated since small particle side becomes 50% grain Diameter.
<the nucleocapsid ratio of organic filler>
The nucleocapsid ratio of organic filler is measured according to following step.
Divide the organic filler of preparation sufficiently in visible-light curing resin (Japan Electronics Co., Ltd system " D-800 ") After dissipating, is embedded, obtain the block-shaped chip containing organic filler.Next, using the ultramicrotome with diamond knife edge Obtained block-shaped chip is cut out as the flake of thickness 100nm, production measurement sample.Then, using ruthenium tetroxide come to survey It is fixed to implement dyeing processing with sample.
Next, the measurement sample for implementing dyeing processing is set to transmission electron microscope, (Japan Electronics is public Department's system " JEM-3100F ") in, photo is shot with cross-section structure of the acceleration voltage 80kV to organic filler.Times of electron microscope Rate is set in such a way that the section of 1 organic filler enters the visual field.Then, the cross-section structure of the organic filler of shooting, root are observed The construction in shell portion according to observations, according to the average thickness in the shell portion of following step measurement organic filler.Then, by that will measure Shell portion average thickness divided by organic filler volume average particle size D50, to acquire nucleocapsid ratio.
<<the case where shell portion is made of the particle of polymer>>
According to the cross-section structure of organic filler, measurement constitutes the longest diameter of the particle of the polymer in shell portion.For any 20 organic fillers measurement of selection constitutes the longest diameter of the particle of the polymer in shell portion, and the average value of the longest diameter is made For the average thickness in shell portion.
<<shell portion has the case where shape other than particle>>
According to the cross-section structure of organic filler, the maximum gauge in shell portion is measured.For optional 20 organic fillers The maximum gauge for measuring shell portion, using the average value of the maximum gauge as the average thickness in shell portion.
<covering rate of organic filler>
The covering rate of organic filler is measured according to following step.
It is carried out similarly with the measuring method of the nucleocapsid ratio of above-mentioned organic filler, the cross-section structure of organic filler is shot Photo, in the cross-section structure of the organic filler of shooting, what the outer surface of the perimeter D1 and core portion that measure core portion were abutted with shell portion Partial length D2, calculate ratio (coating ratio) Rc (%) that the outer surface in the core portion of the organic filler covered by shell portion= (D2/D1)×100.When calculating coating ratio Rc, image analysis software " AnalySIS Pro " (Olympus is used (Olympus) Co., Ltd manufactures).
Above-mentioned coating ratio Rc is measured for optional 20 organic fillers, using its average value as organic filler Core portion the average proportions (covering rate) that are covered by shell portion of outer surface.
<surface tension of non-aqueous secondary battery functional layer composition>
The non-aqueous secondary battery functional layer of preparation is injected on glass culture dish with composition.Then, using platinum sheet Surface tension is measured using flat band method.Measurement is carried out using the full-automatic surface tensiometer " CBVP-Z " of consonance interface science manufacture 2 times, the average value of surface tension is acquired according to measured value, using the average value as non-aqueous secondary battery functional layer composition Surface tension.
<water droplet contact angle of spacer substrate>
The fixation spacers substrate on plate.Then, the ion exchange water (surface of 1 μ L is added dropwise on spacer substrate Power 72mN/m), the contact angle after measurement dropwise addition 60 seconds.In addition, contact angle meter " DM- of the measurement using consonance interface science manufacture 901 " carry out 2 times, and the average value of water droplet contact angle is acquired according to measured value, is connect the average value as the water droplet of spacer substrate Feeler.
<ratio of the area of part existing for the phase of organic filler>
Using scanning electron microscope (SEM) " Hitachi S-4700 " with the functional layer of 5000 times of multiplying power observation spacer Surface, obtain 10 SEM images.Image analysis software (Olympus Corp system " Analysis is used to obtained image PRO ") according to calculating formula below calculate organic filler phase existing for part area ratio.Then, by the flat of calculating value Ratio of the area of part existing for phase of the mean value as organic filler relative to the area of functional layer forming face.But for The functional layer of the spacer of comparative example 5 calculates mutually depositing for organic filler with the formation interval of functional layer according to the width of functional layer Part area relative to functional layer forming face area ratio.
Ratio (%)=(face of part existing for the phase of organic filler of the area of part existing for the phase of organic filler Product/field area) × 100
<cementability of spacer and electrode after electrolyte dipping>
The laminated body with anode and spacer of preparation and the laminated body with cathode and spacer are cut respectively 10mm wide out obtains test film.The test film is impregnated 3 days in temperature 60 C in the electrolytic solution.Here, making as electrolyte Used in the mixed solvent (volumetric mixture ratio: EC/ of ethylene carbonate (EC), diethyl carbonate (DEC) and vinylene carbonate (VC) DEC/VC=68.5/30/1.5；SP value: 12.7 (cal/cm3)1/2) in make LiPF as supporting electrolyte6Relative to solvent with The product of the concentration dissolution of 1mol/L.
Then, test film is taken out, the electrolyte in surface attachment is wiped.Then, by the test film, with electrode, (anode is negative Pole) the mode downwards on current collection side transparent rubberized fabric is pasted on to the surface of electrode.At this moment, it is used as transparent rubberized fabric The transparent rubberized fabric of defined in JIS Z1522.In addition, transparent rubberized fabric is fixed on horizontal testing stand in advance.Then, it measures Stress when one end of spacer substrate is removed along vertical direction with tensile speed stretching in 50mm/ minutes.With with just The laminated body of pole and spacer and the laminated body with cathode and spacer carry out 3 times respectively, add up to and carry out 6 measurements, The average value of stress is acquired as peel strength, the electrode and spacer after electrolyte dipping is evaluated according to benchmark below Cementability.Peel strength is bigger, indicates that cementability is higher.
A: peel strength is 6.0N/m or more；
B: peel strength is 4.0N/m more than and less than 6.0N/m；
C: peel strength is 1.0N/m more than and less than 4.0N/m；
D: peel strength is less than 1.0N/m.
<high-temperature cycle>
By the lithium ion secondary battery of the winding type cell units of the discharge capacity 800mAh of manufacture in the environment of 25 DEG C Stand 24 hours.Then, it in the environment of 25 DEG C, carries out being charged to 4.35V with 0.1C, discharge into the charge and discharge of 2.75V with 0.1C It is electrically operated, measure initial capacity C0.Then further, in the environment of 60 DEG C, charge and discharge are repeated with condition similar to the above, Capacity C 1 after measuring 1000 circulations.Then, capacity retention ratio Δ C (%)=(C1/C0) × 100 of circulation front and back is calculated, According to following benchmark evaluation high-temperature cycles.The value of capacity retention ratio Δ C is bigger, indicates that high-temperature cycle is more excellent It is different, battery life is longer.
A: capacity retention ratio Δ C is 88% or more；
B: capacity retention ratio Δ C is 84% more than and less than 88%；
C: capacity retention ratio Δ C is 80% more than and less than 84%；
D: capacity retention ratio Δ C is less than 80%.
<low temperature output characteristics>
By the lithium ion secondary battery of the winding type cell units of the discharge capacity 800mAh of manufacture in the environment of 25 DEG C Stand 24 hours.Then, the operation for carrying out charging in 5 hours with the charge rate of 0.1C in the environment of 25 DEG C, determines this When voltage V0.Then, the operation that discharge rate in the environment of -10 DEG C with 1C is discharged, determines since electric discharge Voltage V1 after 15 seconds.Then, voltage change Δ V=V0-V1 is calculated, evaluates low temperature output characteristics according to following benchmark. The value of voltage change Δ V is smaller, indicates that low temperature output characteristics are more excellent.
A: voltage change Δ V is less than 300mV；
B: voltage change Δ V is 300mV more than and less than 350mV；
C: voltage change Δ V is 350mV or more；
(embodiment 1)
<preparation of the organic filler with core-shell structure>
In the pressure vessel of the 5MPa equipped with blender, 75 parts of the methyl as (methyl) acrylate monomer is added Methyl acrylate, 4 parts of the methacrylic acid as the monomer for containing acidic group, 1 part of the dimethyl propylene as cross-linkable monomer Olefin(e) acid glycol ester is formed as core portion and is used；1 part of the neopelex as emulsifier is added；150 parts of ion Exchanged water and 0.5 part of the potassium peroxydisulfate as polymerization initiator, are fully stirred.Then, 60 DEG C are heated to start to polymerize. So that polymerization is continued until that polymerisation conversion becomes 96%, obtains the aqueous dispersions of the polymer of the particle shape comprising constituting core portion.
In the aqueous dispersions, continuously add 19 parts as the styrene of aromatic vinyl monomer and 1 part of work Mixture for the methacrylic acid for the monomer for containing acidic group forms use as shell portion, is heated to 70 DEG C, continues to polymerize.It is polymerizeing At the time of object conversion ratio becomes 96%, cools down and terminate reaction, be prepared for the aqueous dispersions comprising organic filler, the organic filler It is the organic filler for the core-shell structure that there is the outer surface in core portion to be partly covered by shell portion.
In addition, the volume average particle size D50 of obtained organic filler is 0.45 μm.
Then, the nucleocapsid ratio and covering rate of obtained organic filler are evaluated.Show the result in table 1.
<preparation of functional layer binding material>
In the reactor equipped with blender, be supplied respectively to 70 parts ion exchange water, 0.15 part as emulsifier Lauryl sodium sulfate (manufacture of Hua Wang Chemical company, ProductName " Emal 2F ") and 0.5 part of ammonium persulfate, use nitrogen Gas phase portion is replaced, is warming up to 60 DEG C.
On the other hand, 50 parts of ion exchange water, 0.5 part of the dodecane as dispersing agent are mixed in other container Base benzene sulfonic acid sodium salt and 94 parts of the butyl acrylate, 2 parts of acrylonitrile, 2 parts of methyl as (methyl) acrylate monomer Acrylic acid, 1 part of N hydroxymethyl acrylamide, 1 part of acrylamide, to obtain monomer mixture.By the monomer mixture It was added continuously in above-mentioned reactor, is polymerize after 4 hours.In addition, reacted at 60 DEG C.After addition terminates, And then reacted in 70 DEG C of stirring terminations in 3 hours, the functional layer comprising particle shape is prepared with binding material (acrylate polymer) Aqueous dispersions.
In addition, the glass transition temperature of obtained functional layer binding material is -40 DEG C.
<preparation of non-aqueous secondary battery functional layer composition>
Relative to the above-mentioned water comprising the organic filler with core-shell structure for being calculated as 100 parts with solid component a great deal of Dispersion liquid, mixing with solid component a great deal of be calculated as 15 parts the above-mentioned aqueous dispersions comprising functional layer binding material, with Solid component a great deal of is calculated as 1.9 parts of ethylene oxide-propylene oxide copolymer (70 matter of solid component concentration as wetting agent Measure %, polymerization ratio: 5/5 (mass ratio)), and then hybrid ionic exchanged water is so that solid component concentration becomes 15 mass %, preparation The non-aqueous secondary battery functional layer of pulpous state is with composition (composition preparatory process).Then, measurement obtains the secondary electricity of non-water system The surface tension of pond functional layer composition.Show the result in table 1.
<preparation of spacer substrate>
Prepare the microporous membrane (16 μm of thickness, Ge Erlai value 210s/100cc) of polyethylene.Use springtime motor manufacturing " air plasma APW-602f " with 50Wmin/m2Processing intensity the microporous membrane of preparation is carried out at corona discharge Reason is as spacer substrate (substrate preparatory process).Then, the water droplet contact angle of measuring interval part substrate.Show the result in table 1。
<preparation of spacer>
It is used by gravure method (line number 300) in the non-aqueous secondary battery functional layer that the two sides of spacer substrate is coated with pulpous state Composition makes it dry 1 minute (functional layer formation process) at 50 DEG C.Formed on spacer substrate as a result, every layer with a thickness of 0.8 μm of functional layer obtains forming the spacer of functional layer on the two sides of spacer substrate.The spacer successively has function Layer, spacer substrate and functional layer.Then, using the functional layer of SEM observation spacer, portion existing for the phase of organic filler is acquired The ratio of the area divided.Obtained SEM image is shown in Fig. 1, shows the result in table 1.In addition, the phase of organic filler is in functional layer In with irregular shape presence.In addition, only organic filler is observed as particle, functional layer binding material is in SEM It is not observed as particle.
<manufacture of the particle shape binder of cathode>
Equipped with blender 5MPa pressure vessel in, be added 33.5 parts of 1,3-butadiene, 3.5 parts of itaconic acid, 62 parts of styrene, 1 part of 2-Hydroxy ethyl acrylate, 0.4 part as emulsifier neopelex, 150 parts Ion exchange water and 0.5 part of the potassium peroxydisulfate as polymerization initiator, fully stir after, be heated to 50 DEG C and start to gather It closes.It is cooling at the time of polymerisation conversion becomes 96%, reaction is terminated, the mixture comprising particle shape binder (SBR) is obtained. In the mixture comprising above-mentioned particle shape binder, 5% sodium hydrate aqueous solution is added, adjusts and arrives pH8.Then, by adding Heat is evaporated under reduced pressure and removes unreacted monomer from above-mentioned mixture, is cooled to 30 DEG C hereinafter, obtaining comprising desired grain The aqueous dispersions of sub- shape binder (anode material layer binding material).
<manufacture of negative electrode slurry composition>
The artificial graphite (volume average particle size: 15.6 μm) as negative electrode active material of 100 parts of mixing and with solid Ingredient a great deal of is calculated as 1 part of the sanlose (Nippon Paper corporation " MAC350HC ") as tackifier 2% aqueous solution, and then ion exchange water is added, solid component concentration is prepared into 68%, it is mixed 60 minutes at 25 DEG C.As this After solid component concentration is prepared into 62% by addition ion exchange water in the mixed liquor that sample obtains, and then 15 points are mixed at 25 DEG C Clock.Addition is calculated as 1.5 parts of the above-mentioned water dispersion comprising particle shape binder with solid component a great deal of in the mixed liquor Liquid, and then ion exchange water is added and adjusts so that final solid component concentration becomes 52%, and then mixes 10 minutes.It is being subtracted Pressure carries out deaeration processing, obtains the negative electrode slurry composition of good fluidity.
<manufacture of cathode>
Chipping wheel coater is used to be coated on 20 μm of thickness of the copper as collector above-mentioned negative electrode slurry composition So that the film thickness after dry becomes 150 μm or so on foil, make it dry.The drying by by copper foil with 0.5m/ minutes speed Degree is carried 2 minutes in 60 DEG C of baking oven and is carried out.Then, heat 2 minutes at 120 DEG C, the cathode before being suppressed is former Version.Cathode master before the compacting is rolled using roll press, obtain anode material layer with a thickness of 80 μm of pressure Cathode after system.
<manufacture of positive paste compound>
The LiCoO of 12 μm of volume average particle size as a positive electrode active material of 100 parts of mixing2, 2 parts of conduct conduction material The acetylene carbon black (Denki Kagaku Kogyo kabushiki manufacture, ProductName " HS-100 ") of material and 2 parts are calculated as with solid component a great deal of The Kynoar as anode binder (anode composite material layer binding material) (KUREHA company manufactures, product Name " #7208 "), N-Methyl pyrrolidone is added wherein so that all solids constituent concentration becomes 70%.It is stirred using planetary It mixes machine to mix these, obtains anode paste compound.
<positive manufacture>
Use paste compound that chipping wheel coater is used to be coated on 20 μm of thickness of the aluminium as collector at above-mentioned anode So that the film thickness after dry becomes 150 μm or so on foil, make it dry.The drying by by aluminium foil with 0.5m/ minutes speed Degree is carried 2 minutes in 60 DEG C of baking oven and is carried out.Then, heat 2 minutes at 120 DEG C, the anode before being suppressed is former Version.Positive master before the compacting is rolled using roll press, obtains anode.
<manufacture of cathode or anode and the laminated body of spacer>
Pressed anode is cut into the circle of diameter 13mm, obtains circular anode.In addition, pressed cathode is cut At the circle of diameter 14mm, circular cathode is obtained.In turn, above-mentioned spacer is cut into the circle of diameter 18mm, obtains circle Spacer.
Then, in the one side of circular spacer, only by cathode or anode according to electrode composite material layer side facing towards The mode of spacer is contacted with spacer.Then, implement heating compression process 10 seconds in 80 DEG C of temperature, pressure 0.5MPa, it will just Pole or cathode are pressed together on spacer, obtain the laminated body with anode and spacer and the layer with cathode and spacer Stack.Then, the laminated body of use production come evaluate electrolyte dipping after spacer and electrode cementability.It shows the result in Table 1.
<manufacture of lithium ion secondary battery>
Pressed anode is cut out as 49cm × 5cm.It configures and cuts on the anode composite material layer for the anode being cut out It is out the spacer of 55cm × 5.5cm.In turn, pressed cathode is cut out as 50cm × 5.2cm, by the cathode cut out with The surface of anode material layer side is configured towards the mode of spacer in the opposite side with anode of above-mentioned spacer.In turn, Configuration cuts out the spacer for 55cm × 5.5cm on cathode.It is wound using up- coiler, has obtained coiling body.By the volume It is suppressed around body in 60 DEG C, 0.5MPa, bluff body is made.The bluff body is used as to the aluminium packaging material outsourcing of the outer packing of battery Put into row packaging, injected in a manner of air noresidue electrolyte (solvent: ethylene carbonate (EC)/diethyl carbonate (DEC)/ Vinylene carbonate (VC)=68.5/30/1.5 (volume ratio), electrolyte: the LiPF of concentration 1M6).Then, for sealed aluminum packet The opening of package material outer packing carries out 150 DEG C of heat-sealing, and aluminium packaging material outer packing is sealed.Manufacture 800mAh's as a result, Winding type lithium ion secondary cell.
Then, to obtained lithium ion secondary battery evaluation high-temperature cycle and low temperature output characteristics.It shows the result in Table 1.
[embodiment 2~4]
In the preparation of organic filler, it will be used to manufacture the methyl methacrylate, methacrylic acid and dimethyl in core portion As shown in the quantitative change of acrylic acid glycol ester more table 1, in addition to this, carries out similarly to Example 1, make organic grain Son, functional layer binding material, non-aqueous secondary battery functional layer composition, spacer substrate, spacer, cathode, anode, Laminated body and lithium ion secondary battery.Then, various measurements, evaluation are carried out similarly to Example 1.Show the result in table 1.
In addition, using the phase that the result of SEM observation is organic filler with the presence of irregular shape in functional layer.This Outside, only organic filler is observed as particle, and functional layer uses binding material not to be observed as particle in SEM.
(embodiment 5)
In the preparation of organic filler, for the monomer composition for manufacturing core portion, by the amount of methyl methacrylate 43 parts are changed to, by more 1 part of the quantitative change of methacrylic acid, and then third as (methyl) acrylate monomer of 35 parts of addition Olefin(e) acid butyl ester carries out similarly to Example 1 in addition to this, makes organic filler, functional layer binding material, non-water system two Primary cell functional layer composition, spacer substrate, spacer, cathode, anode, laminated body and lithium ion secondary battery.Then, Various measurements, evaluation are carried out similarly to Example 1.Show the result in table 1.
In addition, using the phase that the result of SEM observation is organic filler with the presence of irregular shape in functional layer.This Outside, only organic filler is observed as particle, and functional layer uses binding material not to be observed as particle in SEM.
(embodiment 6)
In the preparation of organic filler, for the monomer composition for manufacturing shell portion, by the quantitative change of styrene more 18 Part, new additional 1.7 parts of the acrylonitrile and 0.3 part of the dimethyl propylene as cross-linkable monomer as (methyl) acrylonitrile monemer Olefin(e) acid glycol ester does not add methacrylic acid, in addition to this, carries out similarly to Example 1, makes organic filler, function Layer binding material, non-aqueous secondary battery functional layer composition, spacer substrate, spacer, cathode, anode, laminated body And lithium ion secondary battery.Then, various measurements, evaluation are carried out similarly to Example 1.Show the result in table 1.
In addition, using the phase that the result of SEM observation is organic filler with the presence of irregular shape in functional layer.This Outside, only organic filler is observed as particle, and functional layer uses binding material not to be observed as particle in SEM.
(embodiment 7)
In the preparation of organic filler, for the monomer composition for manufacturing shell portion, by the quantitative change of styrene more 15 Part, new additional 4.5 parts of the acrylonitrile and 0.5 part of the dimethyl propylene as cross-linkable monomer as (methyl) acrylonitrile monemer Olefin(e) acid glycol ester does not add methacrylic acid, in addition to this, carries out similarly to Example 1, makes organic filler, function Layer binding material, non-aqueous secondary battery functional layer composition, spacer substrate, spacer, cathode, anode, laminated body And lithium ion secondary battery.Then, various measurements, evaluation are carried out similarly to Example 1.Show the result in table 1.
In addition, using the phase that the result of SEM observation is organic filler with the presence of irregular shape in functional layer.This Outside, only organic filler is observed as particle, and functional layer uses binding material not to be observed as particle in SEM.
[embodiment 8~9]
In the preparation of non-aqueous secondary battery functional layer composition, by ethylene oxide-epoxy third as wetting agent The use level of alkyl copolymer is changed to as shown in table 1, in addition to this, is carried out similarly to Example 1, is made organic grain Son, functional layer binding material, non-aqueous secondary battery functional layer composition, spacer substrate, spacer, cathode, anode, Laminated body and lithium ion secondary battery.Then, various measurements, evaluation are carried out similarly to Example 1.Show the result in table 1.
In addition, using the phase that the result of SEM observation is organic filler with the presence of irregular shape in functional layer.This Outside, only organic filler is observed as particle, and functional layer uses binding material not to be observed as particle in SEM.
[embodiment 10~11]
When preparing spacer substrate, the processing intensity that Corona discharge Treatment is carried out to the microporous membrane of polyethylene is become More shown in table 1 as, in addition to this, carry out similarly to Example 1, production organic filler, functional layer binding material, Non-aqueous secondary battery functional layer composition, spacer substrate, spacer, cathode, anode, laminated body and lithium ion secondary electricity Pond.Then, various measurements, evaluation are carried out similarly to Example 1.Show the result in table 1.
In addition, using the phase that the result of SEM observation is organic filler with the presence of irregular shape in functional layer.This Outside, only organic filler is observed as particle, and functional layer uses binding material not to be observed as particle in SEM.
(comparative example 1)
In the preparation of non-aqueous secondary battery functional layer composition, ethylene oxide-ring as wetting agent is mismatched Ethylene Oxide copolymer carries out similarly to Example 1 in addition to this, production organic filler, functional layer binding material, non-aqueous It is secondary cell functional layer composition, spacer substrate, spacer, cathode, anode, laminated body and lithium ion secondary battery. Then, various measurements, evaluation are carried out similarly to Example 1.Show the result in table 1.
In addition, using the phase that the result of SEM observation is organic filler with the presence of irregular shape in functional layer.This Outside, only organic filler is observed as particle, and functional layer uses binding material not to be observed as particle in SEM.
(comparative example 2)
In the preparation of non-aqueous secondary battery functional layer composition, by ethylene oxide-epoxy third as wetting agent The use level of alkyl copolymer is changed to as shown in table 1, in addition to this, is carried out similarly to Example 1, is made organic grain Son, functional layer binding material, non-aqueous secondary battery functional layer composition, spacer substrate, spacer, cathode, anode, Laminated body and lithium ion secondary battery.Then, various measurements, evaluation are carried out similarly to Example 1.Show the result in table 1.
In addition, the use of the result of SEM observation being that organic filler is uniformly present in substantially whole table on spacer substrate Face.In addition, only organic filler is observed as particle, functional layer uses binding material not to be observed as particle in SEM.
(comparative example 3)
In the preparation of organic filler, for the monomer composition for manufacturing core portion, by the amount of methyl methacrylate 99 parts are changed to, by more 1 part of the quantitative change of methacrylic acid, does not add ethylene glycol dimethacrylate, and do not form shell portion, In addition to this, it carries out similarly to Example 1, makes organic filler without core-shell structure, functional layer binding material, non- Aqoue seconary battery functional layer composition, spacer substrate, spacer, cathode, anode, laminated body and lithium ion secondary electricity Pond.Then, various measurements, evaluation are carried out similarly to Example 1.Show the result in table 1.
In addition, using the phase that the result of SEM observation is the organic filler without core-shell structure not advise in functional layer Shape then exists.In addition, only the organic filler without core-shell structure is observed as particle, functional layer binding material It is not observed as particle in SEM.
(comparative example 4)
In the preparation of organic filler, for the monomer composition for manufacturing shell portion, by the quantitative change of styrene more 1 Part, do not add methacrylic acid, new additional 19 parts of the methyl methacrylate as (methyl) acrylate monomer, except this with Outside, it carries out similarly to Example 1, makes organic filler, functional layer binding material, non-aqueous secondary battery functional layer group Close object, spacer substrate, spacer, cathode, anode, laminated body and lithium ion secondary battery.Then, similarly to Example 1 Carry out various measurements, evaluation.Show the result in table 1.
In addition, using the phase that the result of SEM observation is organic filler with the presence of irregular shape in functional layer.This Outside, only organic filler is observed as particle, and functional layer uses binding material not to be observed as particle in SEM.
(comparative example 5)
In the preparation of non-aqueous secondary battery functional layer composition, by ethylene oxide-epoxy third as wetting agent The use level of alkyl copolymer is changed to as shown in table 1, and then in the preparation of spacer, and coiling is used instead of gravure method Non-aqueous secondary battery functional layer is used combination article pattern coating waste water in spacer substrate by stick method, in addition to this, with embodiment 1 It is carried out similarly, makes organic filler, functional layer binding material, non-aqueous secondary battery functional layer composition, spacer Substrate, spacer, cathode, anode, laminated body and lithium ion secondary battery.Then, various surveys are carried out similarly to Example 1 Fixed, evaluation.Show the result in table 1.
In addition, the use of the result of SEM observation being that wide 100 μm of functional layer is advised on spacer substrate with 150 μm of interval It then is formed, organic filler equably exists in functional layer.In addition, only organic filler is observed as particle, functional layer Binding material is used not to be observed as particle in SEM.
In addition, in table 1 as shown below,
" MMA " indicates methyl methacrylate；
" BA " indicates butyl acrylate；
" MAA " indicates methacrylic acid；
" EDMA " indicates ethylene glycol dimethacrylate；
" ST " indicates styrene；
" AN " indicates acrylonitrile；
" NMA " indicates N hydroxymethyl acrylamide；
" AAm " indicates acrylamide.
[table 1]
According to table 1, in the embodiment 1~11 for having used the spacer with following functional layer, electrolyte leaching Spacer and electrode after stain it is excellent in adhesion, and then the batteries such as high-temperature cycle and low temperature output characteristics spy can be obtained The good secondary cell of property, which is to have the phase of the organic filler of defined core-shell structure and character with irregular shape The ratio of the area of part existing for shape presence and the phase of organic filler is 20% or more and 80% functional layer below.
In addition, according to table 1, used the ratio of the area of part existing for the phase of organic filler less than 20% In the comparative example 1 of spacer, the cementability and high-temperature cycle of spacer and electrode after electrolyte dipping are reduced.
It in turn, according to table 1, is more than 80% in the ratio for having used the area of part existing for the phase of organic filler In the comparative example 2 of spacer, low temperature output characteristics are reduced.In addition, according to table 1, in the comparison more than the usage amount of wetting agent In example 2, the cementability and high-temperature cycle of spacer and electrode after electrolyte dipping are reduced.
In addition, according to table 1, using without containing between the organic filler with defined core-shell structure and character In the comparative example 3 and comparative example 4 of spacing body, the cementability and high-temperature cycle of spacer and electrode after electrolyte dipping drop It is low.
In turn, according to table 1, in the phase for having used organic filler not with the ratio of spacer existing for irregular shape Compared in example 5, the cementability and high-temperature cycle of spacer and electrode after electrolyte dipping are reduced.
Industrial availability
In accordance with the invention it is possible to provide a kind of cementability and ionic conductance in the electrolytic solution excellent spacer.
In addition, in accordance with the invention it is possible to providing a kind of high-temperature cycle and the excellent non-water system two of low temperature output characteristics Primary cell.
Description of symbols
100: organic filler；
110: core portion；
110S: the outer surface in core portion；
120 shell portions.

Claims (4)

1. a kind of non-aqueous secondary battery spacer, which is characterized in that there is spacer substrate and in the spacer substrate At least one surface on the functional layer that is formed,
The functional layer is the porous membrane layer of the heat resistance and intensity raising for making spacer, for keeping spacer and electrode viscous The layer of the adhesive layer that connects or the function of playing the porous membrane layer and the adhesive layer both,
The functional layer has the phase of organic filler to construct existing for irregular shape, and the organic filler has nucleocapsid knot Structure, the shell portion that the core-shell structure has core portion and covers the outer surface part in the core portion,
The core portion is 5 times or more by electrolyte swellbility and 30 times of polymer below are formed,
The shell portion is more than 1 times by electrolyte swellbility and 4 times of polymer below are formed,
Area of the area of part existing for the phase of the organic filler relative to the functional layer forming face of the spacer substrate Ratio be 20% or more and 80% or less.
2. non-aqueous secondary battery spacer according to claim 1, wherein
The glass transition temperature of the polymer in the core portion be -50 DEG C or more and 150 DEG C hereinafter,
The glass transition temperature of the polymer in the shell portion is 50 DEG C or more and 200 DEG C or less.
3. a kind of manufacturing method of non-aqueous secondary battery spacer is the secondary electricity of non-water system of any of claims 1 or 2 The manufacturing method of pond spacer, it includes:
Prepare the process of spacer substrate, the water droplet contact angle at least one surface of the spacer substrate be 80 ° or more and 130 ° hereinafter,
Prepare the process of non-aqueous secondary battery functional layer composition, the non-aqueous secondary battery functional layer is contained with composition Have the organic filler and a decentralized medium, and surface tension be 33mN/m or more and 39mN/m hereinafter, and
The non-aqueous secondary battery functional layer is coated on the surface of the spacer substrate with composition, makes to be coated with Non-aqueous secondary battery functional layer be dried with composition and on spacer substrate formed functional layer process.
4. a kind of non-aqueous secondary battery, with non-aqueous secondary battery spacer of any of claims 1 or 2.
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