CN105900270A

CN105900270A - Binder composition for secondary cell electrode, slurry composition for secondary cell electrode, secondary cell electrode, and secondary cell

Info

Publication number: CN105900270A
Application number: CN201580003267.9A
Authority: CN
Inventors: 松尾祐作
Original assignee: Nippon Zeon Co Ltd
Current assignee: Zeon Corp
Priority date: 2014-01-16
Filing date: 2015-01-15
Publication date: 2016-08-24
Anticipated expiration: 2035-01-15
Also published as: WO2015107896A1; JPWO2015107896A1; CN105900270B; KR102292440B1; JP6398995B2; KR20160110363A

Abstract

The purpose of the present invention is to provide a binder composition for a secondary cell electrode capable of forming a slurry composition having excellent thixotropic properties, as well as excellent adhesion to a collector when formed into an electrode mixture layer. This binder composition for a secondary cell contains a particulate polymer (A), a hydrophilic organic fiber (B), and water; and contains 0.01-20 parts by mass of the hydrophilic organic fiber (B) to 100 parts by mass of the particulate polymer (A).

Description

Binder composition for secondary battery electrode, slurry for secondary battery electrode compositions, Electrode for secondary battery and secondary cell

Technical field

The present invention relates to binder composition for secondary battery electrode, slurry for secondary battery electrode combination Thing, electrode for secondary battery and secondary cell.

Background technology

The secondary cells such as lithium rechargeable battery are small-sized, lightweight and energy density high and have can Repeat the such characteristic of discharge and recharge, therefore have been used for extensive use.Thus, in recent years, in order to realize The further high performance of secondary cell, the improvement having been for the battery components such as electrode is studied.

Here, the battery components such as electrode (positive pole and negative pole) of secondary cell is to utilize binding agent (binding agent) By the composition contained by these battery components each other or this composition and base material (such as, collector body etc.) it Between carry out boning and being formed.Specifically, the electrode of secondary cell is generally configured with collector body and is formed Electrode on the current collector closes sheet material layers (also referred to as " electrode active material layer ").Wherein, electrode closes sheet material layers such as Formed: such as, the electrode that binding agent, electrode active material etc. will be made to be scattered in disperse medium lowerly It is coated with on the current collector with paste compound so that it is be dried, and utilize binding agent by electrode active material etc. Bonding, is consequently formed electrode and closes sheet material layers.

To this end, in the electrode of secondary cell, closely sealed in order to improve that electrode closes between sheet material layers and collector body Property, attempt binder composition for electrode, the improvement of slurry composition for electrode.

Such as in patent documentation 1, it is proposed that a kind of binder composition for secondary battery electrode, it contains Have containing functional group's resin particle with as the multifunctional hydrazide compound of cross-linking agent, described containing functional group tree Fat microgranule is to make to enter containing the ethylenically unsaturated monomer containing oxo base (keto group) ethylenically unsaturated monomer The polymerization of row emulsion and the resin particle that obtains, and report, the electrolyte resistance of this adhesive composition, With the adaptation of collector body and flexible excellence.

It addition, such as in patent documentation 2, it is proposed that a kind of non-aqueous secondary batteries electrode binding agent group Compound, it contains and is obtained by the monomer copolymerization comprising the ethylenically unsaturated monomer with particular functional group Containing functional group's crosslinked resin microgranule, and report, the electrolyte resistance of this adhesive composition and The adaptation of collector body, flexible excellence.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2011-134618 publication

Patent documentation 2: International Publication the 2010/114119th

Summary of the invention

The problem that invention is to be solved

But, in the paste compound comprising above-mentioned existing adhesive composition, by taking particle shape shape The proportion of the binding agent (particle shaped polymer) that the resin of state is constituted is little, it addition, comprise water-fast grain The viscosity of the paste compound of sub-shaped polymer is low.Therefore, above-mentioned existing paste compound is being employed Electrode in, when being dried by the paste compound coated on collector body, there is following tendency: Particle shaped polymer can rise in this paste compound due to thermal convection current, after dry end, concentrates It is distributed in (migrating to) electrode and closes the surface of sheet material layers.And then, due to this migration, exist and cause electrode to close material The amount of particle shaped polymer present on the face connected with collector body in Ceng reduces, electrode closes sheet material layers and collection The impaired problem of adaptation between electricity body.

For this problem, in order to suppress the migration of particle shaped polymer, it is also contemplated that such as by using Thickening agent etc. and make paste compound high viscosity, thus the particle shaped polymer that caused by thermal convection current of suppression The method of migration.But, there is the problem being difficult to be coated with on the current collector in full-bodied paste compound.

Therefore, from the migration of suppression particle shaped polymer and guarantee that paste compound is on the current collector From the viewpoint of coating easiness, for slurry composition for electrode, it is desirable to it has is coating current collection For being prone to the low viscosity of coating (under high shear) time on body, and on the other hand, after coating (under low sheraing) For suppressing to migrate the full-bodied character (such viscosity behavior is referred to as " thixotropy ") occurred.

Then, it is an object of the invention to provide that can to form thixotropy excellent and close making electrode During sheet material layers, the binder for secondary battery electrode with the paste compound of the excellent adhesion of collector body combines Thing.

It addition, it is an object of the invention to provide thixotropy excellent and can be formed with collector body close The electrode that conjunction property is excellent closes the slurry for secondary battery electrode compositions of sheet material layers.

It is a further object of the invention to provide electrode closes the excellent adhesion between sheet material layers and collector body Electrode for secondary battery.

It is further an object that the adaptation being provided with between electrode conjunction sheet material layers and collector body is excellent The secondary cell of different electrode for secondary battery.

The method of solution problem

The present inventor conducts in-depth research in order to achieve the above object.And then, the present inventor's new discovery: If using the binding agent being combined with hydrophilic organic fiber relative to particle shaped polymer with special ratios Compositions, then can form thixotropy excellent and formed coating on collector body and be dried The aqueous electrode slurry combination of the excellent adaptation that electrode is able to ensure that between collector body when closing sheet material layers Thing, and then complete the present invention.

That is, the present invention is for the purpose of efficiently solving above-mentioned problem, and the use in electrode for secondary battery of the present invention is glued Mixture composite comprises particle shaped polymer (A), hydrophilic organic fiber (B) and water, relative to above-mentioned grain Every 100 mass parts of sub-shaped polymer (A), above-mentioned containing more than 0.01 mass parts and below 20 mass parts Hydrophilic organic fiber (B).So, utilize to contain particle shaped polymer (A) and hydrophilic to fixed-ratio The adhesive composition of organic fiber (B), it is possible to form thixotropy excellence and close material making electrode With the paste compound of the excellent adhesion of collector body during layer.

Here, in the binder composition for secondary battery electrode of the present invention, the most above-mentioned hydrophilic is organic Fiber (B) has hydroxyl.If hydrophilic organic fiber (B) has hydroxyl, then can this bonding of use The thixotropy of the paste compound that agent compositions obtains and make when electrode closes sheet material layers with collector body close Conjunction is excellent.

It addition, in the binder composition for secondary battery electrode of the present invention, the most above-mentioned hydrophilic is organic The fiber diameter of fiber (B) is more than 1nm and below 1000nm.If hydrophilic organic fiber (B) Fiber diameter within the above range, then can make adhesive composition and use this binding agent to combine The storage stability of the paste compound that thing obtains and make when electrode closes sheet material layers with collector body closely sealed Property excellent.

Further, the preferably binder composition for secondary battery electrode of the present invention also comprises cross-linking agent (C), And this cross-linking agent (C) be selected from multi-functional epoxy compound,Isoxazoline compound and carbodiimide compound In at least one.If comprising such cross-linking agent (C), then can make by using the combination of this binding agent The adaptation that the electrode that the paste compound that thing obtains is formed closes between sheet material layers and collector body is the most excellent.

Additionally, in the binder composition for secondary battery electrode of the present invention, gather relative to above-mentioned particle shape Every 100 mass parts of compound (A), containing the above-mentioned cross-linking agent more than 0.01 mass parts and below 10 mass parts (C).If containing cross-linking agent (C) within the above range, then can make adhesive composition and use this to glue The storage stability of the paste compound that mixture composite obtains and make when electrode closes sheet material layers and current collection The adaptation of body is the most excellent.

And then, in the binder composition for secondary battery electrode of the present invention, above-mentioned particle shaped polymer (A) Surface acidity be preferably more than 0.01mmol/g and below 3.5mmol/g.If particle shaped polymer (A) Surface acidity within the above range, then can make by using the paste compound that obtains of adhesive composition The electrode formed closes the excellent adhesion between sheet material layers and collector body.

It addition, the present invention is for the purpose of efficiently solving above-mentioned problem, the use in electrode for secondary battery of the present invention Paste compound comprises particle shaped polymer (A), hydrophilic organic fiber (B), electrode active material and water, Relative to above-mentioned every 100 mass parts of particle shaped polymer (A), containing more than 0.01 mass parts and 20 mass Above-mentioned hydrophilic organic fiber (B) below part.So, to contain particle shaped polymer (A) to fixed-ratio With the paste compound of hydrophilic organic fiber (B), thixotropy is excellent and closes sheet material layers making electrode Time with the excellent adhesion of collector body.

Here, the slurry for secondary battery electrode compositions of the preferred present invention comprises cross-linking agent (C) further, And this cross-linking agent (C) be selected from multi-functional epoxy compound,Isoxazoline compound and carbodiimide compound In at least one.If comprising such cross-linking agent (C), then can make to be formed by paste compound The adaptation that electrode closes between sheet material layers and collector body is the most excellent.

Additionally, it is preferred that the slurry for secondary battery electrode compositions of the present invention comprises water solublity thickening further Agent (D).If comprising water-soluble thickener (D), then can get the excellent stable storing of paste compound Property, it addition, paste compound is coated collector body first-class time workability become good.

It addition, the present invention is for the purpose of efficiently solving above-mentioned problem, the electrode for secondary battery of the present invention The electrode having any of the above-described kind of slurry for secondary battery electrode compositions of use and obtain closes sheet material layers.Electrode The formation closing sheet material layers employs the electrode of any of the above-described kind of slurry for secondary battery electrode compositions, and electrode closes Excellent adhesion between sheet material layers and collector body.

It addition, the present invention is for the purpose of efficiently solving above-mentioned problem, the secondary cell of the present invention just possesses At least one in pole, negative pole, electrolyte and dividing plate, and above-mentioned positive pole and negative pole is above-mentioned secondary electricity Pond electrode.Employing the secondary cell of above-mentioned electrode for secondary battery, the electrode in this electrode closes material Excellent adhesion between layer and collector body.

The effect of invention

According to the present invention, it is possible to provide can be formed thixotropy excellent and make when electrode closes sheet material layers with The binder composition for secondary battery electrode of the paste compound of the excellent adhesion of collector body.

It addition, according to the present invention, it is possible to provide thixotropy excellent and can be formed with collector body closely sealed Property excellent electrode close the slurry for secondary battery electrode compositions of sheet material layers.

Further, according to the present invention, it is possible to provide electrode closes the excellent adhesion between sheet material layers and collector body Electrode for secondary battery.

Additionally, according to the present invention, it is possible to provide possess electrode and close the excellent adhesion between sheet material layers and collector body The secondary cell of electrode.

Accompanying drawing explanation

[Fig. 1] calculate particle shaped polymer Surface acidity time, with electrical conductivity (ms) to add hydrochloric acid Cumulative amount (mmol) mapping and the coordinate diagram that obtains.

Detailed description of the invention

Hereinafter, it is described in detail for embodiments of the present invention.

Here, the binder composition for secondary battery electrode of the present invention is for slurry for secondary battery electrode The preparation of compositions.It addition, the slurry for secondary battery electrode compositions of the present invention is for secondary cell The formation of electrode.And then, the electrode for secondary battery of the present invention can use the secondary battery of the present invention Pole paste compound manufactures.Further, the secondary cell of the present invention employs the secondary electricity of the present invention Pond electrode.

(binder composition for secondary battery electrode)

The binder composition for secondary battery electrode of the present invention comprises particle shaped polymer (A), hydrophilic Organic fiber (B) and water.And then, in the binder composition for secondary battery electrode of the present invention, relatively In every 100 mass parts of particle shaped polymer (A), with the amount more than 0.01 mass parts and below 20 mass parts Containing hydrophilic organic fiber (B).And then, combine according to the binder for secondary battery electrode of the present invention Thing, it is possible to form thixotropy excellent and making when electrode closes sheet material layers the excellent adhesion with collector body Paste compound.

Here, by the binder composition for secondary battery electrode of the present invention is used for paste compound The reason prepared and make the thixotropy of this paste compound improve is still not clear, but can speculate that this thixotropy carries High reason is, in water paste composite, and particle shaped polymer (A) and hydrophilic organic fiber (B) can be interacted by hydrogen bond etc..

More specifically, sent out by hydrogen bond etc. due to particle shaped polymer (A) and hydrophilic organic fiber (B) Raw interaction, these compositions can form network-like imitative cross-linked structure in water paste composite.Enter And, by this imitative cross-linked structure, demonstrate a certain degree of high viscosity at low shear, and on the other hand, Owing to this structure is the most strong, the most under high shear, its imitative cross-linked structure cannot be maintained, network Collapse, thus causes viscosity to reduce, i.e. thixotropy improves.

It addition, by the binder composition for secondary battery electrode of the present invention is used for paste compound When preparing and make to make electrode conjunction sheet material layers, the reason with the adaptation raising of collector body is still not clear, but can be such as Consider lowerly: (i) owing to making thixotropy improve based on above-mentioned imitative cross-linked structure, paste compound by The movement (migration) of particle shaped polymer that when being dried, the thermal convection current of (under low sheraing) causes because of full-bodied go out Now it is inhibited；(ii) when paste compound is dried, hydrophilic organic fiber (B) physically suppresses The movement (migration) of particle shaped polymer (A).I.e., thus it is speculated that due to above-mentioned (i) and/or the reason of (ii), make institute The distribution obtaining the particle shaped polymer (A) in electrode conjunction sheet material layers becomes homogeneous, electrode active material layer and collection Dhering strength between electricity body becomes excellent.

Hereinafter, say for each composition comprised in above-mentioned binder composition for secondary battery electrode Bright.

Particle shaped polymer (A) is in the paste compound shape using the adhesive composition comprising the present invention When becoming electrode, in the electrode manufactured, it is possible to composition (such as, electrode activity contained in holding electrode Material) not from the composition of electrode disengaging.Here, close the feelings of sheet material layers using paste compound to form electrode Under condition, it is however generally that, the particle shaped polymer in electrode conjunction sheet material layers is when impregnated in electrolyte, although inhaling Receive electrolyte and occur swelling, but emboliform shape can be kept, make electrode active material be bonded to one another, Thus prevent electrode active material from coming off from collector body.It addition, electrode also can be closed material by particle shaped polymer The particle (such as, conductive material) beyond electrode active material contained in Ceng also bonds, and has also given play to guarantor Hold the effect that holding electrode closes the intensity of sheet material layers.

It should be noted that described " particle shaped polymer " refers to, it is possible to be scattered in the aqueous mediums such as water Polymer, exist with emboliform form in an aqueous medium.Further, generally, particle shape is polymerized For thing, when being dissolved in the water of 100g by particle shaped polymer 0.5g for 25 DEG C, insoluble component is More than 90 mass %.It addition, in the present invention, described " particle " or " particle shape " refers to utilize scanning The aspect ratio of determination of electron microscopy be 1 less than 10 situation.

[[functional group of hydrogen bond can be formed]]

Here, particle shaped polymer (A) preferably has the functional group that can form hydrogen bond.Particle shaped polymer (A) by having the interaction increasing between the functional group that can form hydrogen bond, and hydrophilic organic fiber (B) By force, the thixotropy that paste compound can be made improve so that make that electrode closes between sheet material layers and collector body close Conjunction improves.As the functional group of the formed hydrogen bond in particle shaped polymer (A), can enumerate: carboxyl, Hydroxyl, sulfonic group, thiol etc..And then, particle shaped polymer (A) preferably has selected from carboxyl, hydroxyl At least one in base, sulfonic group, thiol, further preferably has at least in carboxyl and hydroxyl Person.Additionally, in the case of adhesive composition comprises cross-linking agent described later (C), from electrode active material From the viewpoint of adaptation between layer and collector body, particularly preferred particle shaped polymer (A) has carboxyl With hydroxyl.

Here, carboxyl, hydroxyl, thiol can be by such as making when preparing particle shaped polymer (A) And have ethylenically unsaturated carboxylic acids monomer, have hydroxyl unsaturated monomer, have thiol monomer and Import in particle shaped polymer (A).

It addition, sulfonic group can be made by such as using potassium peroxydisulfate when preparing particle shaped polymer (A) There is sulfonic unsaturated monomer for initiator or use and import in particle shaped polymer (A).

Hereinafter, the unsaturated monomer that for ethylenically unsaturated carboxylic acids monomer, there is hydroxyl, there is sulfonic group Unsaturated monomer and there is the monomer of thiol be described in detail.

Olefinic insatiable hunger as the ethylenically unsaturated carboxylic acids monomeric unit that can form particle shaped polymer (A) And carboxylic acid monomer, olefinic unsaturated monocarboxylic acid and derivant, olefinic unsaturation binary carboxylic can be enumerated Acid and anhydride and their derivant etc..

As the example of olefinic unsaturated monocarboxylic acid, can enumerate: acrylic acid, methacrylic acid, Fructus Crotonis Acid etc..Additionally, the example of the derivant as olefinic unsaturated monocarboxylic acid, can enumerate: 2-ethyl third Olefin(e) acid, iso-crotonic acid, α-acetoxypropen acid, β-trans-aryloxy group acrylic acid, α-chloro-β-E-methoxy Base acrylic acid and β-diaminourea acrylic acid etc..

As the example of olefinic unsaturated dicarboxylic acid, can enumerate: maleic acid, fumaric acid, itaconic acid etc.. Additionally, the example of the anhydride as olefinic unsaturated dicarboxylic acid, can enumerate: maleic anhydride, acrylic acid Acid anhydride, methyl maleic anhydride, dimethyl maleic anhydride etc..Further, as olefinic unsaturated dicarboxylic acid The example of derivant, can enumerate: citraconic acid, dimethyl maleic acid, phenyl maleic acid, chloro Maleic acid, dichloromaleic acid, fluoro maleic acid, maleic acid diphenyl ester, maleic acid nonyl ester, maleic acid last of the ten Heavenly stems Ester, maleic acid dodecyl ester, maleic acid stearyl, maleic acid fluoroalkyl etc..

These can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.Additionally, Among these, from the paste compound employing the adhesive composition that comprises particle shaped polymer (A) From the viewpoint of storage stability, preferably olefinic unsaturated dicarboxylic acid and anhydride thereof and they derive Thing, more preferably itaconic acid.That is, particle shaped polymer (A) preferably comprises the monomeric unit (alkene being derived from itaconic acid Belong to unsaturated carboxylic acid monomer unit).

It should be noted that in the present invention, described " comprising ... monomeric unit " refers to, " single using The polymer that body obtains comprises the construction unit being derived from this monomer ".

In particle shaped polymer (A), the content ratio of ethylenically unsaturated carboxylic acids monomeric unit is preferably 0.1 More than quality %, more than more preferably 0.5 mass %, below preferably 30 mass %, it is more preferably 10 Below quality %, below particularly preferably 5 mass %.By making ethylenically unsaturated carboxylic acids monomeric unit Content ratio is more than 0.1 mass %, it can be ensured that comprise the storage of the paste compound of adhesive composition Stability, improves it addition, electrode can be made to close the adaptation between sheet material layers and collector body.On the other hand, logical Cross the content ratio making ethylenically unsaturated carboxylic acids monomeric unit below 30 mass %, can use bag Close between the electrode active material layer and the collector body that are formed containing the paste compound of adhesive composition Conjunction improves.

As can be formed particle shaped polymer (A) the unsaturated monomer unit with hydroxyl there is hydroxyl The unsaturated monomer of base, can enumerate such as: acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, Hydroxypropyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, methacrylic acid hydroxyl Butyl ester, methacrylic acid 3-chlorine-2-hydroxyl propyl ester, two (ethylene glycol) maleate, two (ethylene glycol) clothing health Acid esters, maleic acid 2-hydroxy methacrylate, maleic acid double (2-hydroxyethyl) ester, fumaric acid 2-hydroxyethyl first Base ester etc..

These monomers can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.Enter And, in these monomers, from the slurry employing the adhesive composition comprising particle shaped polymer (A) From the viewpoint of the storage stability of compositions, preferably acrylic acid 2-hydroxy methacrylate.That is, particle shape polymerization Thing (A) preferably comprises and is derived from the monomeric unit of acrylic acid 2-hydroxy methacrylate and (has the unsaturated monomer list of hydroxyl Unit).

In particle shaped polymer (A), the content ratio of the unsaturated monomer unit with hydroxyl is preferably 0.1 More than quality %, more than more preferably 0.5 mass %, below preferably 10 mass %, it is more preferably 5 Below quality %.By make the content ratio with the unsaturated monomer unit of hydroxyl be 0.1 mass % with On, it can be ensured that employ the storage of the paste compound of the adhesive composition comprising particle shaped polymer (A) Deposit stability, below for 10 mass %, it can be ensured that use and comprise the viscous of particle shaped polymer (A) Mixture composite and adaptation between the electrode active material layer and the collector body that obtain.

As can form particle shaped polymer (A), there is having of sulfonic unsaturated monomer unit Sulfonic unsaturated monomer, can enumerate such as: vinyl sulfonic acid, methyl ethylene sulfonic acid, (methyl) Propene sulfonic acid, styrene sulfonic acid, (methyl) acrylic acid-2-sulfonic acid, 2-acrylamide-2-methylpropane Sulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid etc..These monomers can be used alone a kind, it is also possible to It is applied in combination two or more with arbitrary ratio.It should be noted that in this specification, described " (methyl) Acrylic acid " represent acrylic acid and/or methacrylic acid.

In particle shaped polymer (A), the content ratio with sulfonic unsaturated monomer unit is preferably More than 0.1 mass %, more than more preferably 0.5 mass %, below preferably 10 mass %, more preferably It is below 5 mass %.It is 0.1 matter by making the content ratio with sulfonic unsaturated monomer unit Amount more than %, it can be ensured that employ the slurry compositions of the adhesive composition comprising particle shaped polymer (A) The storage stability of thing, below for 10 mass %, it can be ensured that use and comprise particle shaped polymer (A) Adhesive composition and adaptation between the electrode active material layer and the collector body that obtain.

As can be formed particle shaped polymer (A) the monomeric unit with thiol there is thiol Monomer, can enumerate such as: tetramethylolmethane four (3-mercaptobutylate), trimethylolpropane tris (3-sulfydryl Butyrate), trimethylolethane trimethacrylate (3-mercaptobutylate) etc..Wherein, preferred tetramethylolmethane four (3-mercapto Base butyrate).It should be noted that these monomers can be used alone a kind, it is also possible to arbitrarily than Rate is applied in combination two or more.

In particle shaped polymer (A), the content ratio of the monomeric unit with thiol is preferably 0.1 matter More than amount more than %, more preferably 0.5 mass %, below preferably 10 mass %, it is more preferably 5 matter Amount below %.By making the content ratio with the monomeric unit of thiol be more than 0.1 mass %, can Guarantee to employ the stable storing of the paste compound of the adhesive composition comprising particle shaped polymer (A) Property, below for 10 mass %, it can be ensured that use the binding agent group comprising particle shaped polymer (A) Compound and adaptation between the electrode active material layer and the collector body that obtain.

[[functional group can reacted with cross-linking agent (C)]]

It addition, adhesive composition or paste compound in the present invention comprise cross-linking agent described later (C) In the case of, preferred particle shaped polymer (A) has the functional group can reacted with cross-linking agent (C).Particle shape Polymer (A), by having and can react with cross-linking agent (C) and form the functional group of cross-bond, will cross-link In the case of agent (C) is coupled in adhesive composition or paste compound, the electrode obtained can be made to close material Adaptation between layer and collector body improves further.As in particle shaped polymer (A) can be with friendship Connection agent (C) functional group reacted, can enumerate above-mentioned carboxyl, hydroxyl, thiol, and then, except this Beyond a little functional groups, it is also possible to enumerate glycidyl ether etc..

Here, glycidyl ether can have by such as using when preparing particle shaped polymer (A) The unsaturated monomer of glycidyl ether and import in particle shaped polymer (A).

As the unsaturated monomer unit with glycidyl ether that can form particle shaped polymer (A) The unsaturated monomer with glycidyl ether, can enumerate such as: glycidyl acrylate, methyl Glycidyl acrylate etc..Wherein, preferred glycidyl methacrylate.It should be noted that These monomers can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.

[kind of particle shaped polymer (A)]

And then, as particle shaped polymer (A), it is not limited to the official whether with above-mentioned formed hydrogen bond The functional group can rolled into a ball and can react with cross-linking agent (C), it is possible to use such as: diolefinic polymer, Acrylic polymer, fluorine-based polymer, silicon base polymer etc..It should be noted that as particle shape Polymer (A), can be used alone a kind of polymer, it is also possible to arbitrary ratio be applied in combination 2 kinds with Upper polymer.

[[negative pole with particle shaped polymer (A)]]

Here, in the case of the formation that the adhesive composition of the present invention is used for negative pole conjunction sheet material layers, make For particle shaped polymer (A), preferably acrylic polymer, diolefinic polymer.As acrylic compounds Polymer, preferably enumerates and comprises (methyl) acrylate monomeric units and α, alpha, beta-unsaturated nitriles monomeric unit Copolymer (hereinafter referred to as " acrylic acid/unsaturated nitrile copolymer "), as diolefinic polymer, preferably Enumerate the copolymer of aliphatic conjugated diene monomer unit and aromatic vinyl monomer unit (hereinafter referred to as " conjugated diene/aromatic vinyl copolymer "), particularly preferably use conjugated diene/aromatic ethenyl common Polymers.

This is because, have as rigidity is low and the fat that caking property can be improved of the repetitive of softness Race's conjugated diene monomeric unit and polymer dissolubility in the electrolytic solution can be made to reduce thus improve grain The copolymer of the aromatic vinyl monomer unit of sub-shaped polymer (A) stability in the electrolytic solution, special It not can to have given play to the function as particle shaped polymer (A) in negative pole well.

Hereinafter, with conjugated diene/aromatic vinyl copolymer and acrylic acid/unsaturated nitrile copolymer it is The monomer of the example preparation to can be used in negative pole particle shaped polymer (A) illustrates.

-for conjugated diene/aromatic vinyl copolymer preparation monomer-

Conjugated diene/aromatic vinyl copolymer is used as the negative pole situation of particle shaped polymer (A) Under, as the aliphatic conjugated diene monomer of aliphatic conjugated diene monomer unit can be formed, there is no spy Different limit, can use: 1,3-butadiene, 2-methyl isophthalic acid, 3-butadiene, 2,3-dimethyl-1,3-butadiene, Chlorbutadiene, substituted straight chain conjugation pentadiene class, replacement and side chain conjugation hexadiene class etc., its In, preferably 1,3-butadiene.It should be noted that aliphatic conjugated diene monomer can be used alone 1 Kind, it is also possible to it is applied in combination two or more with arbitrary ratio.

At the negative pole as conjugated diene/aromatic vinyl copolymer with in particle shaped polymer (A), fat The content ratio of fat race conjugated diene monomeric unit is preferably more than 10 mass %, more preferably 25 mass % Above, below preferably 50 mass %, it is more preferably below 40 mass %.By making aliphatic be conjugated The content ratio of diene monomer unit is more than 10 mass %, can improve the flexibility of negative pole, it addition, Below for 50 mass %, negative pole can be made to close the adaptation between sheet material layers and collector body good, separately Outward, the resistance to electrolysis of the negative pole formed by the paste compound of the adhesive composition comprising the present invention can be made Fluidity improves.

It addition, as forming the negative pole particle as conjugated diene/aromatic vinyl copolymer The aromatic vinyl monomer of the aromatic vinyl monomer unit of shaped polymer (A), is not particularly limited, Can enumerate: styrene, α-methyl styrene, vinyltoluene, divinylbenzene etc., wherein, preferably Styrene.It should be noted that aromatic vinyl monomer can be used alone a kind, it is also possible to appoint Meaning ratio combine uses two or more.

At the negative pole as conjugated diene/aromatic vinyl copolymer with in particle shaped polymer (A), fragrant The content ratio of fragrant race vinyl monomer unit is preferably more than 40 mass %, more preferably 50 mass % Above, below preferably 80 mass %, it is more preferably below 70 mass %.By making aromatic vinyl The content ratio of base monomeric unit is more than 40 mass %, can make by the binding agent group comprising the present invention The electrolyte resistance of the negative pole that the paste compound of compound is formed improves, below for 80 mass %, The adaptation that negative pole can be made to close between sheet material layers and collector body is good.

Further, as the negative pole of conjugated diene/aromatic vinyl copolymer with particle shaped polymer (A) Preferably comprise 1,3-butadiene unit as aliphatic conjugated diene monomer unit, comprise styrene units make For aromatic vinyl monomer unit (that is, SB).

It addition, as it has been described above, as the negative pole particle shape of conjugated diene/aromatic vinyl copolymer Polymer (A), preferably comprises at least one in carboxyl, hydroxyl, sulfonic group, thiol, grain Sub-shaped polymer (A) preferably with above-mentioned content ratio comprise selected from ethylenically unsaturated carboxylic acids monomeric unit, There is the unsaturated monomer unit of hydroxyl, there is sulfonic unsaturated monomer unit, there is thiol At least one in monomeric unit.Further, particle shaped polymer (A) preferably comprises olefinic unsaturation carboxylic Acid monomer units, have in the unsaturated monomer unit of hydroxyl at least any one, more preferably comprise olefinic Unsaturated carboxylic acid monomer unit and there is both unsaturated monomer unit of hydroxyl.

It addition, as it has been described above, comprise friendship described later at adhesive composition or the paste compound of the present invention In the case of connection agent (C), the negative pole as conjugated diene/aromatic vinyl copolymer is polymerized with particle shape Thing (A) preferably have can react with cross-linking agent (C) functional group (above-mentioned carboxyl, hydroxyl, thiol and Glycidyl ether etc.).

And then, in the range of the effect significantly destroying the present invention, as conjugated diene/aromatic series second Negative pole particle shaped polymer (A) of alkenyl copolymers can also repeat list arbitrarily in above-mentioned comprising in addition Unit.

In particle shaped polymer (A) except aliphatic conjugated diene monomer unit, aromatic ethenyl list Body unit, ethylenically unsaturated carboxylic acids monomeric unit, there is the unsaturated monomer unit of hydroxyl, there is sulfonic acid The unsaturated monomer unit of base, have other monomeric unit beyond the monomeric unit of thiol containing than Example is not particularly limited, but the upper limit is preferably below 6 mass %, more preferably 4 mass % in terms of total amount Below, it is particularly preferably below 2 mass %.

-for acrylic acid/unsaturated nitrile copolymer preparation monomer-

In the case of acrylic acid/unsaturated nitrile copolymer is used as negative pole particle shaped polymer (A), as (methyl) acrylate monomer of (methyl) acrylate monomeric units can be formed, be not particularly limited, Can enumerate: acrylic acid methyl ester., ethyl acrylate, n-propyl, isopropyl acrylate, acrylic acid N-butyl, tert-butyl acrylate, amyl acrylate, Hexyl 2-propenoate, heptylacrylate, propylene are misery Ester, 2-EHA, acrylic acid nonyl ester, decyl acrylate, lauryl acrylate, acrylic acid The alkyl acrylates such as n-tetradecane base ester, stearyl acrylate ester；Methyl methacrylate, metering system Acetoacetic ester, n propyl methacrylate, isopropyl methacrylate, n-BMA, methyl Tert-butyl acrylate, pentylmethacrylate, N-Hexyl methacrylate, metering system heptyl heptylate, methyl 1-Octyl acrylate, 2-Ethylhexyl Methacrylate, nonyl methacrylate, decyl-octyl methacrylate, The methyl-prop such as lauryl methacrylate, methacrylic acid n-tetradecane base ester, stearyl methacrylate Olefin(e) acid Arrcostab etc..Wherein, preferred butyl acrylate.It should be noted that (methyl) acrylate list Body can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.

At the negative pole as acrylic acid/unsaturated nitrile copolymer with in particle shaped polymer (A), (methyl) third The content ratio of olefin(e) acid ester monomeric unit is preferably more than more than 10 mass %, more preferably 20 mass %, It is preferably below below 99.5 mass %, more preferably 98 mass %.By making (methyl) acrylate list The content ratio of body unit is more than 10 mass %, can reduce the internal resistance of secondary cell, by for 99.5 Below quality %, the adaptation that negative pole can be made to close between sheet material layers and collector body is good.

It addition, be polymerized as the negative pole particle shape as acrylic acid/unsaturated nitrile copolymer can be formed The α of thing (A), the α of alpha, beta-unsaturated nitriles monomeric unit, alpha, beta-unsaturated nitriles monomer, it is not particularly limited, can enumerate Acrylonitrile, methacrylonitrile.Wherein, preferred acrylonitrile.

At the negative pole as acrylic acid/unsaturated nitrile copolymer with in particle shaped polymer (A), α, β-insatiable hunger It is preferably more than more than 0.1 mass %, more preferably 0.5 mass % with the content ratio of nitrile monomer unit, It is preferably below below 10 mass %, more preferably 5 mass %.By making 'alpha ', ' bela '-unsaturated nitrile monomer list The content ratio of unit is more than 0.1 mass %, can improve the mechanical strength of particle shaped polymer (A) and glue Knot power, makes negative pole close the adaptation between sheet material layers and collector body well, below for 10 mass %, The flexibility of negative pole, the cracking of suppression negative pole can be improved.

It addition, as it has been described above, as the negative pole of acrylic acid/unsaturated nitrile copolymer with particle shaped polymer (A) Preferably comprise at least one in carboxyl, hydroxyl, sulfonic group, thiol, particle shaped polymer (A) Preferably comprise selected from ethylenically unsaturated carboxylic acids monomeric unit, the insatiable hunger with hydroxyl with above-mentioned content ratio With monomeric unit, there is sulfonic unsaturated monomer unit, have in the monomeric unit of thiol extremely Few one.Further, particle shaped polymer (A) preferably comprises ethylenically unsaturated carboxylic acids monomeric unit, tool Have in the unsaturated monomer unit of hydroxyl at least any one, more preferably at least comprise ethylenically unsaturated carboxylic acids Monomeric unit.

It addition, as it has been described above, the adhesive composition of the present invention or paste compound comprise crosslinking described later In the case of agent (C), as the negative pole particle shaped polymer of conjugated diene/aromatic vinyl copolymer (A) preferably there is functional group's (above-mentioned carboxyl, hydroxyl, thiol and the contracting can reacted with cross-linking agent (C) Water glycerol ether etc.).

And then, in the range of the effect significantly destroying the present invention, common as acrylic acid/unsaturated nitrile Negative pole particle shaped polymer (A) of polymers can also comprise arbitrary repetitive beyond above-mentioned.

In particle shaped polymer (A) except (methyl) acrylate monomeric units, 'alpha ', ' bela '-unsaturated nitrile monomer Unit, ethylenically unsaturated carboxylic acids monomeric unit, there is the unsaturated monomer unit of hydroxyl, there is sulfonic group Unsaturated monomer unit, there is the content ratio of other monomeric unit beyond the monomeric unit of thiol Be not particularly limited, but the upper limit is preferably below 6 mass % in terms of total amount, more preferably 4 mass % with Under, below particularly preferably 2 mass %.

[[positive pole with particle shaped polymer (A)]]

Here, in the case of the formation that the adhesive composition of the present invention is used for positive pole conjunction sheet material layers, make For particle shaped polymer (A), preferably acrylic polymer, more preferably acrylic acid/unsaturated nitrile copolymer.

Hereinafter, to can be used in positive pole particle shaped polymer as a example by acrylic acid/unsaturated nitrile copolymer (A) monomer of preparation illustrates.

-for acrylic acid/unsaturated nitrile copolymer preparation monomer-

In the case of acrylic acid/unsaturated nitrile copolymer is used as positive pole particle shaped polymer (A), as (methyl) acrylate monomer of (methyl) acrylate monomeric units can be formed, be not particularly limited, Those described in the item of " negative pole particle shaped polymer (A) " can be set forth in.Wherein, preferred acrylic acid 2-Octyl Nitrite.It should be noted that (methyl) acrylate monomer can be used alone a kind, it is possible to To be applied in combination two or more with arbitrary ratio.

At the positive pole as acrylic acid/unsaturated nitrile copolymer with in particle shaped polymer (A), (methyl) third The content ratio of olefin(e) acid ester monomeric unit is preferably more than more than 50 mass %, more preferably 60 mass %, It is preferably below below 97 mass %, more preferably 95 mass %.By making (methyl) acrylate list The content ratio of body unit is more than 50 mass %, can reduce the internal resistance of secondary cell, by for 97 Below quality %, the adaptation that positive pole can be made to close between sheet material layers and collector body is good.

It addition, be polymerized as the positive pole particle shape as acrylic acid/unsaturated nitrile copolymer can be formed The α of thing (A), the α of alpha, beta-unsaturated nitriles monomeric unit, alpha, beta-unsaturated nitriles monomer, it is not particularly limited, can enumerate Those described in the item of " negative pole with particle shaped polymer (A) ".Wherein, preferred acrylonitrile.

At the positive pole as acrylic acid/unsaturated nitrile copolymer with in particle shaped polymer (A), α, β-insatiable hunger It is preferably more than more than 3 mass %, more preferably 5 mass % with the content ratio of nitrile monomer unit, excellent Elect below below 40 mass %, more preferably 30 mass % as.By making 'alpha ', ' bela '-unsaturated nitrile monomer list The content ratio of unit is more than 3 mass %, can improve mechanical strength and the bonding of particle shaped polymer (A) Power, makes positive pole close the adaptation between sheet material layers and collector body well, below for 40 mass %, and can Improve the flexibility of positive pole, the cracking of suppression positive pole.

It addition, as it has been described above, as the positive pole of acrylic acid/unsaturated nitrile copolymer with particle shaped polymer (A) Preferably comprise at least one in carboxyl, hydroxyl, sulfonic group, thiol, particle shaped polymer (A) Preferably comprise selected from ethylenically unsaturated carboxylic acids monomeric unit, the insatiable hunger with hydroxyl with above-mentioned content ratio With monomeric unit, there is sulfonic unsaturated monomer unit, have in the monomeric unit of thiol extremely Few one.Further, particle shaped polymer (A) preferably comprises ethylenically unsaturated carboxylic acids monomeric unit, tool Have in the unsaturated monomer unit of hydroxyl at least any one, more preferably at least comprise ethylenically unsaturated carboxylic acids Monomeric unit.

It addition, as it has been described above, the adhesive composition of the present invention or paste compound comprise crosslinking described later In the case of agent (C), the positive pole as acrylic acid/unsaturated nitrile copolymer is preferred with particle shaped polymer (A) There is functional group's (above-mentioned carboxyl, hydroxyl, thiol and the (+)-2,3-Epoxy-1-propanol that can react with cross-linking agent (C) Ether etc.).

Here, in the range of the effect significantly destroying the present invention, common as acrylic acid/unsaturated nitrile Positive pole particle shaped polymer (A) of polymers can also comprise arbitrary repetitive beyond above-mentioned.

[manufacture method of particle shaped polymer (A)]

And then, particle shaped polymer (A) such as can be by existing containing the monomer composition of above-mentioned monomer Aqueous solvent is carried out be polymerized to manufacture.

Here, in the present invention, the content ratio of each monomer in monomer composition can be based on particle shape The content ratio of monomeric unit (repetitive) in polymer and determine.

As long as aqueous solvent can make particle shaped polymer (A) then not have with the scattered solvent of particle state It is particularly limited to, generally can be usual more than 80 DEG C, preferably more than 100 DEG C from the boiling point normal pressure, lead to Normal less than 350 DEG C, the aqueous solvent of preferably less than 300 DEG C selects.

Specifically, as aqueous solvent, can enumerate such as: water；The ketone such as DAA, gamma-butyrolacton Class；The alcohols such as ethanol, isopropanol, normal propyl alcohol；Propylene glycol monomethyl ether, methyl cellosolve, ethyl are molten Fine agent, ethylene glycol tertbutyl ether, butyl cellosolve, MMB, ethylene glycol list third The glycol ethers such as base ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl base ether, DPGME Class；The ethers such as 1,3-dioxolanes, 1,4-dioxolanes, oxolane；Etc..Wherein, never have From the viewpoint of the dispersion of flammable, to be readily available particle shaped polymer (A) particle, particularly preferably Water.It should be noted that main solvent can also be used water as, be able to ensure that particle shaped polymer (A) Particle dispersity in the range of mix the aqueous solvent beyond above-mentioned water.

Polymerization is not particularly limited, and such as solution polymerization process, suspension polymerization, body can be used to gather Any means in legal, emulsion polymerization etc..As polymerization, can use such as ionic polymerization, Any means in radical polymerization, active free radical polymerization etc..It should be noted that from being readily obtained High molecular body and polymer can directly obtain being scattered in the state of water, are therefore made without The process of redispersion, the manufacture etc. being used directly for the adhesive composition of the present invention manufactures efficiency Viewpoint is set out, particularly preferred emulsion polymerization.It should be noted that emulsion polymerization can be according to routine side Method is carried out.

It addition, for the emulsifying agent used in polymerization, dispersant, polymerization initiator, reagent and additive in polymerization etc., Can use the most adopted those, its usage amount is also normally used amount.It addition, when polymerization, Seed particles can be used to carry out seeding polymerization.It addition, polymerizing condition can also be according to polymerization and poly- The kind etc. closing initiator arbitrarily selects.

Here, for utilizing the aqueous of the particle of particle shaped polymer (A) that above-mentioned polymerization obtains to divide A prose style free from parallelism, can use such as comprise the hydroxide of alkali metal (such as, Li, Na, K, Rb, Cs), ammonia, Inorganic Ammonium compound (such as NH₄Cl etc.), organic amine compound (such as ethanolamine, diethylamine etc.) etc. PH adjusts to usually more than 5 by alkaline aqueous solution, usually less than 10, be preferably less than 9 model Enclose.Wherein, the pH carried out based on alkali metal hydroxide adjust can make collector body and electrode close sheet material layers it Between adaptation improve, therefore preferably.

[character of particle shaped polymer (A)]

Hereinafter, the character for the particle shaped polymer (A) used in the present invention is described in detail.

[[Surface acidity]]

In the present invention, the Surface acidity of particle shaped polymer (A) refers to, relative to particle shaped polymer (A) The Surface acidity of the every 1g of solid constituent.Here, the Surface acidity of particle shaped polymer (A) available with Under method calculate.

First, preparation comprises the aqueous dispersions (solid component concentration 2%) of particle shaped polymer (A).In profit In the glass container of the capacity 150ml crossed with distilled water wash, the above-mentioned particle shape that comprises adding 50g gathers The aqueous dispersions of compound (A), is arranged at electrical conductivity of solution instrument and is stirred.It should be noted that stir Mix persistently carrying out terminating to the interpolation of hydrochloric acid described later.

So that the electrical conductivity of the aqueous dispersions comprising particle shaped polymer (A) reaches the mode of 2.5～3.0mS The sodium hydrate aqueous solution of 0.1 equivalent is added in the aqueous dispersions comprising particle shaped polymer.Then, After 5 minutes, measure electrical conductivity.Using this value as the electrical conductivity measured when starting.

Further, in this aqueous dispersions comprising particle shaped polymer (A), add the hydrochloric acid of 0.1 equivalent 0.5ml, measures electrical conductivity after 30 seconds.Then, again add the hydrochloric acid 0.5ml of 0.1 equivalent, and Electrical conductivity is measured after 30 seconds.This operation is repeated with the interval of 30 seconds, until comprising particle shape Till the electrical conductivity of the aqueous dispersions of polymer (A) reaches to measure more than electrical conductivity when starting.

The conductivity data that obtains is marked and drawed with electrical conductivity (unit " mS ") as the longitudinal axis (Y coordinate axle), with The cumulative amount (unit " mmol ") of the hydrochloric acid added is in the coordinate diagram of transverse axis (X-coordinate axle).Thus, may be used Obtain the hydrochloric acid content-conductance profile with 3 flex points shown in Fig. 1.X-coordinate by 3 flex points And hydrochloric acid add at the end of X-coordinate start from the side that value is little to be set to successively P1, P2, P3 and P4.For X-coordinate from zero to coordinate P1, from coordinate P1 to coordinate P2, from coordinate P2 to coordinate P3 and the data in 4 intervals of coordinate P3 to coordinate P4, be utilized respectively method of least square and ask Go out near linear L1, L2, L3 and L4.X by near linear L1 Yu the intersection point of near linear L2 Coordinate is set to A1 (mmol), the X-coordinate of near linear L2 with the intersection point of near linear L3 is set to A2 (mmol), the X-coordinate of near linear L3 Yu the intersection point of near linear L4 is set to A3 (mmol).

Surface acidity relative to the every 1g of particle shaped polymer (A) can be by following formula (a), change as hydrochloric acid Calculate value (mmol/g) and obtain.It should be noted that the water relative to the every 1g of particle shaped polymer (A) Acid amount in mutually (present in the aqueous phase of the aqueous dispersions comprising particle the shaped polymer amount of acid, i.e. phase For the acid amount of the every 1g of solid constituent of particle shaped polymer, the also referred to as " water of particle shaped polymer (A) In mutually acid amount ") by following formula (b), as hydrochloric acid conversion value (mmol/g) and obtain.It addition, such as Shown in following formula (c), the total acid content relative to the every 1g of the particle shaped polymer (A) being dispersed in water is formula (a) And the summation of formula (b).

A () is relative to the Surface acidity=A2-A1 of the every 1g of particle shaped polymer (A)

Sour amount=A3-A2 in (b) aqueous phase relative to the every 1g of particle shaped polymer (A)

C () is relative to the total acid base unit weight=A3-A1 of the every 1g of the particle shaped polymer (A) being dispersed in water

The Surface acidity of particle shaped polymer (A) is preferably more than 0.01mmol/g, is more preferably More than 0.05mmol/g, particularly preferably more than 0.1mmol/g, preferably below 1.0mmol/g, more It is preferably below 0.5mmol/g, more preferably below 0.38mmol/g, is even more preferably Below 0.3mmol/g, particularly preferably below 0.2mmol/g.

By making Surface acidity be more than 0.01mmol/g, particle shaped polymer (A) can be improved relative to water Wettability, thus, particle shaped polymer (A) can be made preferably to disperse in water, paste compound Storage stability improves.It addition, by the wettability improving particle shaped polymer (A), slurry can be improved The coating of feed composition, such that it is able to produce the few electrode of defect to close sheet material layers, therefore can improve two The low temperature output characteristics of primary cell.Additionally, the Surface acidity of particle shaped polymer (A) is 0.01mmol/g Time above, the surface tension of the aqueous dispersions comprising particle shaped polymer reduces, and can improve and comprise particle The aqueous dispersions of shaped polymer is for electrode active material and the wettability of collector body.Thus, can suppress by Paste compound coats migration during collector body, and that can improve that electrode closes between sheet material layers and collector body is close Conjunction property, can improve the cycle characteristics of secondary cell simultaneously.

On the other hand, it is below 1.0mmol/g by making the Surface acidity of particle shaped polymer (A), can Improve so that electrode closes the adaptation between sheet material layers and collector body.

For the Surface acidity of particle shaped polymer (A), can be polymerized by such as changing constituent particle shape The kind of the monomeric unit of thing (A) and ratio and polymerization thereof are controlled.

More specifically, such as, by adjusting kind and the ratio thereof of ethylenically unsaturated carboxylic acids monomeric unit, Surface acidity can be efficiently controlled.Generally, in ethylenically unsaturated carboxylic acids monomer, if using monomer A part in the many ethylenically unsaturated carboxylic acids monomer (itaconic acid etc.) of carboxyl number, then exist and easily make table The tendency that acid amount in face rises.

[[character of other particle shaped polymer (A)]]

The metal ingredient content (Na content and the summation of K content) of particle shaped polymer (A) is preferably Below 10000ppm, more preferably below 7000ppm, particularly preferably below 5000ppm.Pass through The metal ingredient content making particle shaped polymer (A) is below 10000ppm, employs particle shape possessing In the secondary cell of the electrode of polymer (A), it is inhibited by preserving the gas caused for a long time, because of This can make the preservation characteristics of secondary cell improve.It should be noted that Na, K are owing to use contains Their polymerization initiator or use the alkali adjusted for the pH of particle shaped polymer (A) etc. and be mixed into 's.

It should be noted that the metal ingredient content of particle shaped polymer (A) can use this specification Assay method described in embodiment measures.

The number average bead diameter of particle shaped polymer (A) is preferably more than 50nm, more preferably more than 70nm, It is preferably below 500nm, more preferably below 400nm.It addition, the standard deviation of number average bead diameter is excellent Elect below 30nm, more preferably below 15nm as.By making number average bead diameter and standard deviation above-mentioned Scope, can make the intensity of the electrode obtained and flexibility good.It should be noted that particle shaped polymer (A) number average bead diameter can be easily determined by by transmission electron microscopy.Particles size and distribution can root Quantity and particle diameter thereof according to seed particles are controlled by.

Hydrophilic organic fiber (B) is not dissolve in the adhesive composition, paste compound of the present invention The aqueous medium that uses as disperse medium, the electrolyte of secondary cell, in these aqueous mediums, electrolysis Liquid also is able to keep the fiber of its shape.It addition, hydrophilic organic fiber due in terms of electrochemistry also Stable, therefore in the use of secondary cell, also stably can exist in electrode closes sheet material layers.Need Bright, in the present invention, the aspect ratio that described " fiber " refers to utilize scanning electron microscope to measure is Those of more than 10.It addition, in the present invention, hydrophilic organic fiber refers to for " hydrophilic ", organic fibre Dimension has the functional group that can form hydrogen bond.Sense as the formed hydrogen bond in hydrophilic organic fiber Group, can enumerate hydroxyl, carboxyl, amino etc..

It addition, generally, for hydrophilic organic fiber (B), be 25 DEG C by hydrophilic organic fiber (B), time during 0.5g is dissolved in the water of 100g, insoluble component is more than 90 mass %.

As concrete hydrophilic organic fiber (B), can enumerate: by cellulose, chitin, chitosan The fiber constituted Deng polysaccharide, the fiber being made up of the synthesis macromolecule with the functional group that can form hydrogen bond (such as, polyester fiber, polyacrylonitrile fibre, aramid fibre, polyamide-imide fiber, Polyimide fiber etc.) etc..It should be noted that cellulose includes at least hydroxyl as forming hydrogen bond Functional group, chitin is including at least hydroxyl as forming the functional group of hydrogen bond, and chitosan includes at least Hydroxyl and amino are as the functional group that can form hydrogen bond.These can be used alone a kind, it is also possible to by 2 Plant combination of the above to use.

From the viewpoint of closing, from making the electrode formed by paste compound, the layer that sheet material layers becomes excellent, preferably should Paste compound has good thixotropy.To this end, in paste compound, the organic fibre of preferred hydrophilic Dimension (B) and particle shaped polymer (A) form suitable imitative cross-linked structure.And then, have to strengthen hydrophilic Interaction between organic fiber (B) and particle shaped polymer (A), hydrophilic organic fiber (B) is preferably tool There are the organic fiber of hydroxyl, more preferably cellulose.

It addition, the fiber diameter of hydrophilic organic fiber (B) is preferably more than 1nm, is more preferably More than 10nm, particularly preferably more than 20nm, preferably below 1000nm, more preferably 100nm Below, more preferably below 70nm, particularly preferably below 50nm.By making hydrophilic have The fiber diameter of organic fiber (B) is more than 1nm, and hydrophilic organic fiber (B) is not susceptible to cohesion, The dispersibility of fiber can be substantially ensured that, it is possible to make the paste compound of the adhesive composition comprising the present invention Storage stability improve.On the other hand, by making the fiber diameter of hydrophilic organic fiber (B) For below 1000nm, it is possible to substantially ensure that the dispersibility of fiber, without causing hydrophilic organic fiber (B) the thickest, it is possible to make the storage stability of the paste compound of the adhesive composition comprising the present invention carry High.Further, it is below 1000nm by the fiber diameter making hydrophilic organic fiber (B), fine Tie up solution fully tangle, excellent dispersion, therefore, it is possible to make that electrode closes between sheet material layers and collector body is closely sealed Property improve.

It should be noted that in the present invention, described " fiber diameter " can be as utilizing scanning electron The meansigma methods of the minor axis of optional 100 fibers of measurement microscope and obtain.

The average fiber length of hydrophilic organic fiber (B) is preferably more than 50 μm, more preferably 60 μm Above, it is particularly preferably more than 70 μm, below preferably 1000 μm, below more preferably 500 μm, Below particularly preferably 200 μm.It is 50 μm by the average fiber length making hydrophilic organic fiber (B) Above, owing to fiber has enough length, therefore, it is possible to suppression comprises the binding agent of the present invention aptly The migration being dried middle particle shaped polymer (A) of the paste compound of compositions, it is possible to make electrode activity thing Adaptation between matter layer and collector body improves.On the other hand, by making hydrophilic organic fiber (B) Average fiber length is below 1000 μm, it can be ensured that comprise the slurry group of the adhesive composition of the present invention The dispersibility of the fiber in compound, it is possible to make the storage stability of paste compound improve.

It should be noted that in the present invention, described " average fiber length " can be as utilizing scanning electron The meansigma methods of the major diameter of optional 100 fibers of measurement microscope and obtain.

Further, the aspect ratio (average fiber length/fiber diameter) of hydrophilic organic fiber (B) is excellent Elect more than 100, more preferably more than 500, particularly preferably more than 1000, preferably 10000 as Below, more preferably less than 7500, particularly preferably less than 5000.By making hydrophilic organic fiber (B) aspect ratio is in above-mentioned scope, it can be ensured that the dispersibility of fiber in paste compound, it is possible to make slurry The storage stability of feed composition improves.

In the adhesive composition of the present invention, relative to every 100 mass parts of particle shaped polymer (A), contain The hydrophilic organic fiber (B) having below more than 0.01 mass parts and 20 mass parts is necessary, preferably contains Have more than 0.1 mass parts, more preferably contain more than 2 mass parts, particularly preferably containing more than 5 mass parts, Preferably comprise below 15 mass parts, more preferably contain below 8 mass parts, particularly preferably containing 7 mass Below Fen.In adhesive composition, the content of hydrophilic organic fiber (B) is relative to particle shaped polymer (A) When every 100 mass parts are less than 0.01 mass parts, it is impossible to obtain the slurry using this adhesive composition to obtain The good thixotropy of feed composition and the inhibition of metastasis effect of particle shaped polymer (A), it is impossible to guarantee electricity The adaptation between sheet material layers and collector body is closed in pole.On the other hand, the content phase of hydrophilic organic fiber (B) When 100 mass parts every for particle shaped polymer (A) are more than 20 mass parts, particle shaped polymer (A) holds Easily influence each other with hydrophilic organic fiber (B) and condense, it is impossible to guaranteeing the storage of paste compound Stability.It addition, the content of hydrophilic organic fiber (B) is relative to every 100 matter of particle shaped polymer (A) Amount part is if it exceeds 20 mass parts, then compared to particulate polymer (A), the more weak hydrophilic of cohesive force has The amount excess of organic fiber (B), its result, electrode can be caused to close the dhering strength between sheet material layers and collector body Reduce.

<cross-linking agent (C)>

In order to make the electrode formed by the paste compound of the adhesive composition comprising the present invention close sheet material layers Adaptation between (particularly negative pole conjunction sheet material layers) and collector body improves, preferably the binding agent combination of the present invention Thing comprises cross-linking agent (C).Its reason can be speculated as: by comprising cross-linking agent (C), particle shaped polymer (A), hydrophilic organic fiber (B) can by heating etc. and form cross-linked structure.

That is, for comprising the paste compound of the adhesive composition of the present invention, by such as at collector body On implement heating etc. in order to be dried and process, the particle shape polymerization comprised in paste compound can be made Thing (A) and hydrophilic organic fiber (B) form cross-linked structure by cross-linking agent (C).Its result, based on grain Sub-shaped polymer (A) to each other, between particle shaped polymer (A) and hydrophilic organic fiber (B), Yi Jiqin Aqueous organic fiber (B) crosslinking to each other, available elastic modelling quantity, tensile break strength, stress delay With etc. little (i.e. excellent water resistance) friendship of mechanical property, dissolubility excellent in adhesion and in water Connection structure.Thereby it is assumed that, if the adhesive composition containing cross-linking agent (C) will be used to obtain Paste compound for the formation of electrode of secondary cell, then be able to ensure that electrode close sheet material layers and collector body it Between high adhesion.

Here, cross-linking agent (C) as long as have with particle shaped polymer (A) and hydrophilic organic fiber (B), Specifically refer to they in the compound of functional group that reacts of the functional group that comprises then there is no special limit Fixed, the most every 1 molecule preferably has the compound of more than 2 reactive functional groups.Here, hand over Reactive functional groups in connection agent (C) refers to, it is possible to particle shaped polymer (A) and hydrophilic organic fiber (B) functional group that functional group's (hydroxyl, carboxyl, amino etc.) contained in reacts, can enumerate such as: Epoxy radicals (including glycidyl, glycidyl ether),Oxazoline base, carbodiimide, hydroxyl etc..

Specifically, as cross-linking agent (C), can enumerate such as: there is epoxy radicals as reactive functional Group multi-functional epoxy compound, haveOxazoline base is as reactive functional groupsIsoxazoline compound, There is the carbodiimide carbodiimide compound as reactive functional groups.

Hereinafter, for multi-functional epoxy compound,Isoxazoline compound, carbodiimide compound are carried out in detail Describe in detail bright.

[multi-functional epoxy compound]

Multi-functional epoxy compound is the compound in every 1 molecule with more than 2 epoxy radicals.Further, As multi-functional epoxy compound, the most every 1 molecule has preferably less than 6, is more preferably less than The compound of 4 above-mentioned reactive functional groups.By making the number of the reactive functional groups in every 1 molecule (as the meansigma methods of the multi-functional epoxy compound that cross-linking agent (C) uses), in above-mentioned scope, is possible to prevent to send out The raw sedimentation caused by the cohesion of each composition, so that it is guaranteed that the storage stability of paste compound.

It should be noted that as multi-functional epoxy compound, the most such as: the many (+)-2,3-Epoxy-1-propanols of aliphatic Polyfunctional glycidyl ether's compounds such as ether, aromatic series polyglycidyl ether, diglycidyl ether.This is Due to, every 1 molecule has polyfunctional glycidyl ether's compound of more than 2 glycidyl ethers by The most excellent in the affinity with electrolyte, therefore in the case of using as cross-linking agent (C), manufacture The fluid injection of electrolyte during secondary cell is improved especially.

[Isoxazoline compound]

As long as isoxazoline compound has in the molecule thereofOxazoline base and can being polymerized at particle shape Between thing (A), between particle shaped polymer (A) and hydrophilic organic fiber (B) and hydrophilic organic fiber (B) cross-linked compound forming cross-linked structure between is then not particularly limited.Further, asOxazoline Compound, the most such as molecule have more than 2The compound of oxazoline base.It should be noted thatPartly or entirely can also being replaced by other group of the hydrogen atom of oxazoline base.As in such molecule There are more than 2The compound of oxazoline base, can enumerate such as: have 2 in moleculeOxazoline base Compound be (divalentIsoxazoline compound), containThe polymer of oxazoline base (containsOxazoline based polyalcohol).

[[divalentIsoxazoline compound]]

As divalentIsoxazoline compound, can enumerate such as: 2,2'-double (2-Oxazoline), the double (4-of 2,2'- Methyl-2-Oxazoline), the double (4,4-dimethyl-2-of 2,2'-Oxazoline), the double (4-ethyl-2-of 2,2'-Oxazoline), 2,2'- Double (4,4'-diethyl-2-Oxazoline), double (the 4-propyl group 2-of 2,2'-Oxazoline), the double (4-butyl-2-of 2,2'-Oxazoline), Double (4-hexyl-the 2-of 2,2'-Oxazoline), the double (4-phenyl-2-of 2,2'-Oxazoline), the double (4-cyclohexyl-2-of 2,2'-Azoles Quinoline), the double (4-benzyl-2-of 2,2'-Oxazoline) etc..Wherein, go out from the viewpoint forming more upright and more outspoken cross-linked structure Send out, the double (2-of preferably 2,2'-Oxazoline).

[[containOxazoline based polyalcohol]]

ContainAs long as oxazoline based polyalcohol containsThe polymer of oxazoline base is then not particularly limited.Need Illustrate, in this manual, containOxazoline based polyalcohol does not include above-mentioned divalentOxazoline Compound.

It addition, containOxazoline based polyalcohol can be by such as making containing shown in below formula (I)Oxazoline base list Body and other monomer carry out copolymerization and synthesize.

[chemical formula 1]

[in formula, R¹、R²、R³And R⁴Represent hydrogen atom, halogen atom, alkyl, optionally independently of one another There is the aryl of substituent group or optionally there is the aralkyl of substituent group, R⁵Represent there is addition polymerization not The non-annularity organic group of saturated bond]

In formula (I), as halogen atom, can enumerate such as: fluorine atom, chlorine atom, bromine atoms, atomic iodine Deng.Wherein, preferably fluorine atom and chlorine atom.

In formula (I), as alkyl, can enumerate such as: the alkyl of carbon number more than 1 and less than 8.Its In, the preferably alkyl of carbon number more than 1 and less than 4.

In formula (I), optionally there is the aryl of substituent group, can enumerate such as: optionally there is halogen atom etc. The aryl etc. of substituent group.As aryl, can enumerate such as: phenyl, tolyl, xylyl, biphenyl The aryl etc. of the carbon numbers more than 6 and less than 18 such as base, naphthyl, anthryl, phenanthryl.And then, as Optionally there is the aryl of substituent group, the most optionally there is the carbon number more than 6 and less than 12 of substituent group Aryl.

In formula (I), as the above-mentioned aralkyl optionally with substituent group, can enumerate such as: optionally there is halogen The aralkyl etc. of the substituent groups such as atom.As aralkyl, can enumerate such as: benzyl, phenylethyl, first The aralkyl etc. of the carbon numbers more than 7 and less than 18 such as base benzyl, naphthyl methyl.And then, as appointing Choosing has the aralkyl of substituent group, the most optionally has the carbon number more than 7 and less than 12 of substituent group Aralkyl.

In formula (I), as having the non-annularity organic group of addition polymerization unsaturated bond, can enumerate such as: The thiazolinyl etc. of the carbon numbers more than 2 and less than 8 such as vinyl, pi-allyl, isopropenyl.Wherein, excellent Select vinyl, pi-allyl and isopropenyl.

As containing shown in formula (I)Oxazoline base monomer, can enumerate such as: 2-vinyl-2-Oxazoline, 2- Vinyl-4-methyl-2-Oxazoline, 2-vinyl-4-ethyl-2-Oxazoline, 2-vinyl-4-propyl group 2-Azoles Quinoline, 2-vinyl-4-butyl-2-Oxazoline, 2-vinyl-5-methyl-2-Oxazoline, 2-vinyl-5-ethyl -2-Oxazoline, 2-vinyl-5-propyl group 2-Oxazoline, 2-vinyl-5-butyl-2-Oxazoline, 2-isopropyl alkene Base-2-Oxazoline, 2-isopropenyl-4-methyl-2-Oxazoline, 2-isopropenyl-4-ethyl-2-Oxazoline, 2-isopropenyl-4-propyl group 2-Oxazoline, 2-isopropenyl-4-butyl-2-Oxazoline, 2-isopropenyl-5- Methyl-2-Oxazoline, 2-isopropenyl-5-ethyl-2-Oxazoline, 2-isopropenyl-5-propyl group 2-Oxazoline, 2-isopropenyl-5-butyl-2-Oxazoline etc..Wherein, from industrial can easily obtain from the standpoint of, Preferably 2-isopropenyl-2-Oxazoline.These containOxazoline base monomer can be used alone a kind, it is also possible to It is applied in combination two or more with arbitrary ratio.

And then, as can be used in containingOther monomer of the synthesis of oxazoline based polyalcohol, as long as can The known monomer of copolymerization is then not particularly limited, and preferably enumerates such as (methyl) acrylic monomers, (first Base) acrylate monomer and fragrance same clan monomer etc..

[carbodiimide compound]

As long as carbodiimide compound has formula (1) :-N=C=N-in the molecule ... the carbon shown in (1) Di-imidogen and can between particle shaped polymer (A), particle shaped polymer (A) organic with hydrophilic The cross-linked compound between fiber (B) and forming cross-linked structure between hydrophilic organic fiber (B) does not then have There is particular restriction.Further, as such cross-linking agent (C) with carbodiimide, preferably arrange Illustrate such as: there is the compound of more than 2 carbodiimides, specifically refer to that there is formula (2) :-N=C=N-R¹... (2) [in formula (2), R¹Represent the organic group of divalent] shown in repetitive Poly-carbodiimide and/or modified poly-carbodiimide.It should be noted that in this specification, described modification Poly-carbodiimide refers to, by making reactive compounds described later carry out reacting relative to poly-carbodiimide and The resin obtained.

[[synthesis of poly-carbodiimide]]

The synthetic method of poly-carbodiimide is not particularly limited, such as, can exist by making organic multiple isocyanate Promote the catalyst (hereinafter referred to as " carbodiimidization catalyst ") of the carbodiimidization reaction of NCO In the presence of carry out reaction to synthesize poly-carbodiimide.It addition, have the repetitive shown in formula (2) (carbodiimide is low for the oligomer that poly-carbodiimide can also obtain by making organic multiple isocyanate react Polymers) with can and the monomer of this oligomer copolymerization carry out copolymerization and synthesize.

It should be noted that as the organic multiple isocyanate used in the synthesis of this poly-carbodiimide, excellent Select organic diisocyanate.

As the organic diisocyanate used in the synthesis of poly-carbodiimide, can enumerate such as in Japan Organic diisocyanate described in JP 2005-49370 publication.Wherein, as cross-linking agent (C), From the viewpoint of the storage stability of the adhesive composition and paste compound that comprise poly-carbodiimide, Particularly preferably 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI).Organic diisocyanate is permissible It is used alone a kind, it is also possible to be applied in combination two or more with arbitrary ratio.

Alternatively, it is also possible to using while above-mentioned organic diisocyanate, use have more than 3 different The organic multiple isocyanate of cyanic acid ester group (3 officials can organic multiple isocyanate) above, by stoichiometry 3 officials of excess can above organic multiple isocyanate and 2 officials can above multi-functional containing active hydrogenation conjunction Thing is reacted and obtains terminal isocyanate prepolymer (following, can above organic many by above-mentioned 3 officials Isocyanates and above-mentioned end isocyanate prepolymer are referred to as that " 3 officials can above organic multiple isocyanate Class ").As such 3 officials can above organic multiple isocyanate class, such as Japanese Unexamined Patent Publication can be enumerated Those described in 2005-49370 publication.3 officials can above organic multiple isocyanate class can be independent Use a kind, it is also possible to use two or more with arbitrary ratio combine.Synthesis with regard to poly-carbodiimide is anti- In Ying, 3 officials can be for the usage amount of above organic multiple isocyanate class, relative to organic diisocyanate Every 100 mass parts are usually below 40 mass parts, below preferably 20 mass parts.

Further, when synthesizing poly-carbodiimide, it is also possible to add organic single-isocyanate as desired. By adding organic single-isocyanate, can contain 3 officials at organic multiple isocyanate can above organic many In the case of isocyanates, suitably limit the molecular weight of the poly-carbodiimide of gained, it addition, by inciting somebody to action Organic diisocyanate is applied in combination with organic single-isocyanate, can obtain the poly-carbon two of molecular weight Imines.As such organic single-isocyanate, such as Japanese Unexamined Patent Publication 2005-49370 public affairs can be enumerated Those described in report.Organic single-isocyanate can be used alone a kind, it is also possible to arbitrary ratio It is applied in combination two or more.With regard in the synthetic reaction of poly-carbodiimide organic single-isocyanate usage amount and Whether speech, also rely on the molecular weight required by the poly-carbodiimide of gained, use 3 officials can above organic Polyisocyanates etc., but relative to whole organic multiple isocyanates (organic diisocyanate and 3 official's energy Above organic multiple isocyanate class) every 100 mass parts of composition, usually below 40 mass parts, preferably It is below 20 mass parts.

It addition, as carbodiimidization catalyst, phospholene (phospholene) compound, gold can be enumerated Belong to carbonyl complex, the acetylacetonate complex of metal, phosphate ester.Their concrete example is respectively such as Japanese Unexamined Patent Publication 2005-49370 publication is disclosed.Carbodiimidization catalyst can be used alone 1 Kind, it is also possible to use two or more with arbitrary ratio combine.The usage amount phase of carbodiimidization catalyst For whole organic isocyanates, (organic single-isocyanate, organic diisocyanate and 3 officials can above Organic multiple isocyanate class) every 100 mass parts of composition, usually more than 0.001 mass parts, it is preferably More than 0.01 mass parts, below usual 30 mass parts, it is preferably below 10 mass parts.

The carbodiimidization reaction of organic multiple isocyanate can be in solvent-free lower enforcement, it is also possible to suitably Solvent in implement.As the solvent implemented in a solvent in the case of synthetic reaction, as long as can dissolve The poly-carbodiimide or the carbodiimide oligomer that generate because of heating in synthetic reaction are then not particularly limited, Can enumerate halogenated hydrocarbon solvent, ether solvent, ketones solvent, aromatic hydrocarbon solvent, amide solvent, Polar non-solute, acetate esters solvent.Their concrete example is respectively at such as Japanese Unexamined Patent Publication 2005-49370 publication is disclosed.These solvents can be used alone a kind, it is also possible to arbitrarily Ratio combine uses two or more.For the usage amount of the solvent in the synthetic reaction of poly-carbodiimide, Be make the concentration of whole organic isocyanate composition be more than usual 0.5 mass %, preferably 5 mass % with Above, the amount below usual 60 mass %, below preferably 50 mass %.Whole organic isocyanide in solvent If the concentration of acid esters composition is too high, then there is the poly-carbodiimide causing generating or carbodiimide oligomer The hidden danger of gelation is there is in synthetic reaction, it addition, the whole organic isocyanate compositions in solvent If concentration is too low, then response speed can be caused slack-off, productivity declines.

The temperature of the carbodiimidization reaction of organic multiple isocyanate can be according to organic isocyanate composition, carbon The kind of diimine catalyst and suitably select, but usually more than 20 DEG C and less than 200 DEG C.Entering When the carbodiimidization of row organic multiple isocyanate reacts, for organic isocyanate composition, can be instead Whole amount is added before should, or, it is also possible to add its part or complete the most continuously or by stages Portion.It addition, in the present invention, it is also possible to the carbodiimidization at organic multiple isocyanate react from just The suitable stage of reaction in phase to later stage adds the compound that can react with NCO, closes The terminal isocyanate group of poly-carbodiimide, thus regulate the molecular weight of the poly-carbodiimide of gained.It addition, Can also add in the later stage that the carbodiimidization of organic multiple isocyanate reacts, thus by poly-for gained carbon two The molecular weight control of imines is in set-point.As such compound that can react with NCO, Can enumerate such as: the alcohols such as methanol, ethanol, isopropanol, Hexalin；Dimethylamine, diethylamine, benzylamine Deng amine.

It addition, as the alcohol of preferably more than 2 yuan, can making with the monomer of carbodiimide oligomer copolymerization The oligomer obtained as monomer with the alcohol of more than 2 yuan and ester thereof, such as: ethylene glycol, propylene glycol etc. 2 yuan of alcohol or polyoxyalkylene, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, Polyethylene glycol monoacrylate, polypropylene glycol mono acrylic ester.

By such as utilizing known method to make two ends of strand have 2 yuan of alcohol and the carbon two of hydroxyl Imines oligomer copolymerization, can synthesize and have poly-carbodiimide and be derived from the monomeric unit of 2 yuan of alcohol Poly-carbodiimide.So, have at the poly-carbodiimide as cross-linking agent (C) and be derived from the alcohol of more than 2 yuan Monomeric unit, preferably have and be derived from the monomeric unit of 2 yuan of alcohol in the case of, can improve by employing bag The electrode that the paste compound of the adhesive composition containing this poly-carbodiimide is formed is relative to electrolyte Wettability, makes to possess the fluid injection of electrolyte in the manufacture of the secondary cell of this negative pole and improves.It addition, such as The alcohol that really copolymerization is above-mentioned, then can make the water solublity of poly-carbodiimide increase, and meanwhile, poly-carbodiimide exists Water can occur (take the surrounding of hydrophobic carbodiimide by hydrophilic glycol chain from micellization The structure covered), therefore can improve chemical stability.

Above-mentioned poly-carbodiimide as a solution or is used with the form of solid isolated from solution Preparation in the adhesive composition of the present invention.As the method that poly-carbodiimide is separated from solution, Can enumerate such as: it is inactive bad for being added to by poly-Carbodiimide solution relative to this poly-carbodiimide In solvent, and to produce precipitate or grease filters or decant, thus carry out separating/collecting Method；The method being carried out by spray drying separating/collecting；Utilize and be used at different temperatures Changes in solubility in the solvent of the synthesis of the poly-carbodiimide of gained and the method that carries out separating/collecting, i.e. Can separate out by reducing system temperature just synthesizing the poly-carbodiimide being dissolved in afterwards in this solvent In the case of, by filtering the method etc. separating from its dirty solution/collecting that waits, further, it is also possible to Carry out appropriately combined for these separation/collection methods.The gel that utilizes of the poly-carbodiimide in the present invention oozes The polystyrene conversion number-average molecular weight (hereinafter referred to as " Mn ") that chromatography (GPC) is obtained thoroughly is usually 400 Above, it is preferably 1, more than 000, particularly preferably 2, more than 000, usually 500, less than 000, It is preferably less than 200,000, particularly preferably less than 100,000.

[[synthesis of modified poly-carbodiimide]]

Then, the synthetic method for modified poly-carbodiimide illustrates.Modified poly-carbodiimide can pass through At least one making reactive compounds and the poly-carbodiimide with the repetitive shown in formula (2) At least one in the presence of suitable catalyst or under conditions of there is not catalyst, enter under proper temperature Row reaction (hereinafter referred to as " modified-reaction ") synthesizes.

Reactive compounds for the synthesis of modified poly-carbodiimide refers to, its molecule has 1 with Poly-carbodiimide has the group (hereinafter referred to as " reactive group ") of reactivity and has it further The compound of its functional group.This reactive compounds can be aromatic compound, aliphatic compound or Alicyclic compound, it addition, the ring structure in aromatic compound and alicyclic compound can be carbocyclic ring It can also be heterocycle.As the reactive group in reactive compounds, for there is the group of activation hydrogen i.e. Can, include, for example carboxyl or primary amino radical or secondary amino group.And then, in the molecule of reactive compounds In addition to there is 1 reactive group, it is also possible to there is other functional group further.As reactivity Other functional group that compound is had, it is possible to comprise and there is the poly-carbodiimide of promotion and/or modified poly-carbon In the group of the effect of the cross-linking reaction of diimine, reactive compounds 1 molecule the 2nd is later (that is, be different from above-mentioned reactive group other) above-mentioned group with activation hydrogen, such as, removes Beyond acid anhydride and tertiary amino, can enumerate the carboxyl illustrated as having the group of activation hydrogen and Primary amino radical or secondary amino group etc..As these other functional groups, can deposit in reactive compounds 1 molecule Group identical or different more than 2.

As reactive compounds, can enumerate such as described in Japanese Unexamined Patent Publication 2005-49370 publication Compound.Wherein, preferably trimellitic anhydride, nicotinic acid.Reactive compounds can be used alone a kind, Can also be used two or more with arbitrary ratio combine.

The usage amount of reactive compounds in the modified-reaction of the poly-carbodiimide of synthesis modification, can basis The modified physical property required by poly-carbodiimide of poly-carbodiimide, the kind of reactive compounds, gained etc. and Suitably regulation, but preferably make reactive group the leading to relative to poly-carbodiimide in reactive compounds The ratio of the repetitive shown in formula (2) 1 mole is more than 0.01 mole, further preferred 0.02 mole Above, preferably less than 1 mole, the amount of further preferred less than 0.8 mole.Aforementioned proportion is less than 0.01 Mole time, the storage stability that may cause comprising the paste compound of modified poly-carbodiimide declines.Separately On the one hand, when aforementioned proportion is more than 1 mole, the characteristic that poly-carbodiimide may be caused intrinsic is impaired.

It addition, in modified-reaction, the reactive group in reactive compounds is logical with poly-carbodiimide The reaction of the repetitive shown in formula (2) is carried out quantitatively, has the usage amount phase with this reactive compounds The functional group joined is directed in modified poly-carbodiimide.Modified-reaction also is able to reality under condition of no solvent Execute, but preferably implement in suitable solvent.As long as such solvent is relative to poly-carbodiimide and anti- Answering property compound is nonactive and can then be not particularly limited, the solvent that they dissolve as it Example, can enumerate and can be used in the ether solvent of synthesis of above-mentioned poly-carbodiimide, amide solvent, ketone Kind solvent, aromatic hydrocarbon solvent, polar non-solute etc..These solvents can be used alone a kind, Can also be used two or more with arbitrary ratio combine.It addition, can use in modified-reaction poly- During the solvent used during the synthesis of carbodiimide, it is also possible to directly use the poly-carbon being synthesized into by it Diimine solution.For the usage amount of the solvent in modified-reaction, every relative to the total amount of reaction raw materials 100 mass parts, usually more than 10 mass parts, are preferably more than 50 mass parts, and usually 10,000 Below mass parts, it is preferably below 5,000 mass parts.The temperature of modified-reaction can according to poly-carbodiimide, The kind of reactive compounds and suitably select, but usually more than-10 DEG C, usually less than 100 DEG C, It is preferably less than 80 DEG C.The Mn of the poly-carbodiimide of modification in the present invention is usually more than 500, preferably It is 1, more than 000, more preferably 2, more than 000, usually 1, less than 000,000, it is preferably Less than 400,000, more preferably less than 200,000.

[character etc. of cross-linking agent (C)]

Here, cross-linking agent (C) is preferably water solublity.It is water solublity by making cross-linking agent (C), is possible to prevent In the adhesive composition, paste compound of aqueous, cross-linking agent (C) exists unevenly, so that gained Electrode closes sheet material layers and forms suitable cross-linked structure.Therefore, it can the electrode in guaranteeing gained secondary cell While closing the adaptation between sheet material layers and collector body, make resistance to water and the electrical characteristic (initial stage of electrode Coulombic efficiency, initial stage resistance, cycle characteristics etc.) improve.

Here, in this manual, cross-linking agent (C) refers to for " water solublity ": will be relative to ion exchange water Every 100 mass parts are added cross-linking agent 1 mass parts (with solid component meter) and are stirred and the mixing that obtains Thing, adjust to the scope of temperature more than 20 DEG C and less than 70 DEG C and pH be more than 3 and 12 with Under in condition in the range of (use NaOH aqueous solution and/or HCl/water solution adjust pH) at least One condition and during by the sieve of 250 mesh, do not remain in the matter of the solid constituent of the residue on sieve by sieving Measure and be less than 50 mass % relative to the solid constituent of the cross-linking agent added.It should be noted that i.e. The mixture making above-mentioned cross-linking agent and water is the emulsion state being separated into two-phase in the case of standing, as long as Meet above-mentioned definition, i.e. think that this cross-linking agent is water solublity.It should be noted that from making cross-linked structure Form reaction to carry out well, make above-mentioned electrode close the viewpoint that the adaptation between sheet material layers and collector body improves Setting out, the mixture of the most above-mentioned cross-linking agent and water is not separated into two-phase (in single-phase water-soluble state), i.e. More preferably cross-linking agent is single-phase water dissolubility.

It addition, for being the reason that water miscible reason is identical with above-mentioned preferred cross-linking agent, cross-linking agent (C) Water-soluble rate be preferably more than more than 80 mass %, more preferably 90 mass %.It should be noted that 100 mass parts every relative to ion exchange water are being added cross-linking agent by described " the water-soluble rate " of cross-linking agent (C) 1 mass parts (solid constituent a great deal of) and be stirred and the mixture that obtains adjust to 25 DEG C, pH7 also Make its 250 mesh sieve by time, will not by sieve and remain in the matter of the solid constituent of the residue on sieve In the case of amount is considered as X mass % relative to the ratio of the solid constituent quality of the cross-linking agent added, by Following formula defines.

Water-soluble rate=(100-X) quality %

And then, in the adhesive composition of the present invention, as cross-linking agent (C), it is preferably selected from many officials Energy epoxide,At least one in isoxazoline compound, carbodiimide compound, more preferably carbon Diimine compounds, particularly preferably water-soluble carbodiimide compound.Carbodiimide compound and many officials Energy epoxide,Isoxazoline compound compares excellent heat stability, therefore by using carbodiimidization Compound as cross-linking agent (C), can make the adhesive composition of the present invention, paste compound storage steady Qualitative excellence.Further, since carbodiimide compound has the heat stability of excellence, therefore viscous in preparation Situation about reacting with water when mixture composite, paste compound etc. and lose is the most less, itself as a result, it is possible to Improve the electrode obtained and close the adaptation between sheet material layers and collector body.

Additionally, by using water-soluble carbodiimide compound, as set forth above, it is possible to prevent in aqueous In adhesive composition, paste compound, the water-soluble carbodiimide compound as cross-linking agent (C) is uneven Ground exists, so that the adaptation that electrode closes between sheet material layers and collector body improves further.

In the adhesive composition of the present invention, relative to every 100 mass parts of particle shaped polymer (A), hand over More than content preferably 0.001 mass parts of connection agent (C), more than more preferably 0.01 mass parts, enter one Step is preferably more than 0.5 mass parts, more than particularly preferably 5 mass parts, preferably 20 mass parts with Under, below more preferably 15 mass parts, below particularly preferably 10 mass parts.By making binding agent group In compound, the content of cross-linking agent (C) is 0.001 mass relative to every 100 mass parts of particle shaped polymer (A) More than Fen, the electrode formed by the paste compound comprising adhesive composition can be made to close sheet material layers and current collection Adaptation between body improves, below for 20 mass parts, it can be ensured that the storage of paste compound Stability and thixotropy.

The adhesive composition of the present invention can be by such as obtaining relative to making monomer composition be polymerized The aqueous dispersions of particle shaped polymer (A) adds hydrophilic organic fiber (B), water and sends out not destroying Add other compositions arbitrary such as above-mentioned cross-linking agent (C) in the range of bright effect to prepare.

(slurry for secondary battery electrode compositions)

The slurry for secondary battery electrode compositions of the present invention comprises particle shaped polymer (A), hydrophilic has Organic fiber (B), electrode active material and water.Further, the slurry for secondary battery electrode combination of the present invention In thing, relative to every 100 mass parts of particle shaped polymer (A), containing more than 0.01 mass parts and 20 Hydrophilic organic fiber (B) below mass parts.And then, the slurry for secondary battery electrode group of the present invention The thixotropy of compound is excellent, and this paste compound can be utilized to suppress particle shaped polymer (A) Migrating, the electrode forming the excellent adhesion with collector body closes sheet material layers.

Here, particle shaped polymer (A) contained in the slurry for secondary battery electrode compositions of the present invention, Hydrophilic organic fiber (B) and arbitrary cross-linking agent (C), can make with identical mixing ratio respectively With the material identical with described in the item at the binder composition for secondary battery electrode of the invention described above Material.

Electrode active material is the thing given and accepted carrying out electronics in the electrode (positive pole, negative pole) of secondary cell Matter.Hereinafter, with the electrode active material (positive electrode active material used in the electrode of lithium rechargeable battery Matter, negative electrode active material) as a example by illustrate.

[positive active material]

As the positive active material coordinated in the paste compound of the present invention, it is not particularly limited, can make Use known positive active material.

Specifically, as positive active material, it is possible to use containing the compound of transition metal, such as: The metal composite oxide etc. of transition metal oxide, transient metal sulfide, lithium and transition metal.Need Be noted that as transition metal, such as, can enumerate: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc..

Here, as transition metal oxide, such as can enumerate: MnO, MnO₂、V₂O₅、V₆O₁₃、 TiO₂、Cu₂V₂O₃, noncrystalline V₂O-P₂O₅, noncrystalline MoO₃, noncrystalline V₂O₅, noncrystalline V₆O₁₃ Deng.

As transient metal sulfide, can enumerate: TiS₂、TiS₃, noncrystalline MoS₂, FeS etc..

As lithium and the metal composite oxide of transition metal, can enumerate and there is the multiple containing lithium of layer structure Close metal-oxide, have spinel structure lithium-contained composite metal oxide, have olivine-type knot The lithium-contained composite metal oxide etc. of structure.

As having the lithium-contained composite metal oxide of layer structure, such as, can enumerate: the cobalt oxide containing lithium Compound (LiCoO₂), nickel oxide (LiNiO containing lithium₂), the lithium-contained composite oxide (Li (Co of Co-Ni-Mn Mn Ni)O₂), the lithium-contained composite oxide of Ni-Mn-Al, the lithium-contained composite oxide of Ni-Co-Al, LiMaO₂With Li₂MbO₃Solid solution etc..It should be noted that being combined containing lithium as Co-Ni-Mn Oxide, can enumerate Li [Ni_0.5Co_0.2Mn_0.3]O₂、Li[Ni_1/3Co_1/3Mn_1/3]O₂Deng.It addition, make For LiMaO₂With Li₂MbO₃Solid solution, such as can enumerate: xLiMaO₂·(1-x)Li₂MbO₃Deng. Here, x represents the number of satisfied 0 ＜ x ＜ 1, Ma represents the mistake of more than a kind that oxidation state is 3+ Crossing metal, Mb represents the transition metal of more than a kind that oxidation state is 4+.As such solid solution Body, can enumerate Li [Ni_0.17Li_0.2Co_0.07Mn_0.56]O₂Deng.

It should be noted that in this manual, " oxidation state " refers to the above-mentioned " transition of more than a kind Metal " average oxidation state, can be calculated by the mole of transition metal and atomicity.Such as, It is by the Ni of 50mol% at " transition metal of more than a kind "²⁺Mn with 50mol%⁴⁺Situation about constituting Under, the oxidation state of " transition metal of more than a kind " is (0.5) × (2+)+(0.5) × (4+)=3+.

As having the lithium-contained composite metal oxide of spinel structure, such as, can enumerate: LiMn2O4 (LiMn₂O₄), LiMn2O4 (LiMn₂O₄) part Mn by the compound of other transition metal substitution. As concrete example, LiNi can be enumerated_0.5Mn_1.5O₄Deng Li_s[Mn_2-tMc_t]O₄.Here, Mc represents flat Equal oxidation state is the transition metal of more than a kind of 4+.As the concrete example of Mc, can enumerate Ni, Co, Fe, Cu, Cr etc..It addition, t represents the number of satisfied 0 ＜ t ＜ 1, s represents satisfied 0≤s≤1 Number.It should be noted that as positive active material, it is also possible to use with Li_1+xMn_2-xO₄(0 ＜ X ＜ 2) represent lithium excess spinel compound etc..

As having the lithium-contained composite metal oxide of olivine-type structure, such as, can enumerate: olivine Type LiFePO4 (LiFePO₄), olivine-type lithium manganese phosphate (LiMnPO₄) etc. with Li_yMdPO₄Represent Olivine-type lithium phosphate compound.Here, Md represents the transition of more than a kind that oxidation state is 3+ Metal, such as, can enumerate Mn, Fe, Co etc..It addition, y represents the number of satisfied 0≤y≤2.Separately Outward, just with Li_yMdPO₄For the olivine-type lithium phosphate compound represented, its Md can be partly By other metal replacement.As replaceable metal, such as, can enumerate: Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and Mo etc..

In these, from the viewpoint of the high capacity of lithium rechargeable battery, LiMn is preferably used₂O₄、 LiNiO₂, lithium-contained composite oxide (Li (the Co Mn Ni) O of Co-Ni-Mn₂), olivine-type LiFePO4 (LiFePO₄), olivine-type lithium manganese phosphate (LiMnPO₄), lithium excess spinel compound, Li[Ni_0.17Li_0.2Co_0.07Mn_0.56]O₂、LiNi_0.5Mn_1.5O₄Deng as positive active material, more preferably make With olivine-type LiFePO4 (LiFePO₄), lithium-contained composite oxide (Li (the Co Mn of Co-Ni-Mn Ni)O₂)、Li[Ni_0.17Li_0.2Co_0.07Mn_0.56]O₂, lithium excess spinel compound as positive electrode active material Matter.Additionally, from the viewpoint of the output characteristics and high-temperature cycle of lithium rechargeable battery, especially Lithium-contained composite oxide (Li (the Co Mn Ni) O of preferably Co-Ni-Mn₂)。

Here, the use level of positive active material, particle diameter are not particularly limited, can be with use in the past Positive active material is identical.

[negative electrode active material]

As the negative electrode active material coordinated in the paste compound of the present invention, it is not particularly limited, can make Use known negative electrode active material.And then, as the negative electrode active material of lithium rechargeable battery, generally Use can occlusion and the material of releasing lithium.As can occlusion and release lithium material, can enumerate such as: Carbons negative electrode active material, metal class negative electrode active material and the negative electrode active that they are combined Material etc..

[[carbons negative electrode active material]]

Here, described carbons negative electrode active material, refer to embed (also referred to as " adulterating ") lithium, with carbon As the active substance of main framing, as carbons negative electrode active material, such as carbonaceous material and stone can be enumerated Ink material.

Carbonaceous material be by by carbon precursor 2000 DEG C of heat treated below so that its carbonization and obtain , the material of degree of graphitization low (i.e. crystallinity is low).It should be noted that heat treatment temperature during carbonization The lower limit of degree is not particularly limited, but can be such as more than 500 DEG C.

It addition, as carbonaceous material, can enumerate such as: easily change the knot of carbon according to heat treatment temperature Easy the to be graphitic carbon of structure, the difficult graphite with the structure close with non crystalline structure with glassy carbon as representative Property carbon etc..

Here, as easy graphitic carbon, can enumerate such as: make with the tar asphalt obtained by oil or coal Material with carbon element for raw material.As concrete example, can enumerate: coke, carbonaceous mesophase spherules (MCMB), in Between asphalt phase based carbon fiber, thermal decomposition gas-phase growth of carbon fibre etc..

It addition, as difficult graphitic carbon, can enumerate such as: phenolic resin fired body, polypropylene nitrile carbon Fiber, quasi-isotropic carbon, furfuryl alcohol resin fired body (PFA), hard carbon etc..

Graphite material obtains by easy graphitic carbon being carried out heat treatment more than 2000 DEG C, There is the material of the high crystalline close to graphite.It should be noted that the upper limit of heat treatment temperature does not has It is particularly limited to, can be such as less than 5000 DEG C.

It addition, as graphite material, can enumerate such as: native graphite, Delanium etc..

Here, as Delanium, can enumerate such as: by comprise easy graphitic carbon carbon mainly at 2800 DEG C Heat treatment carried out above and obtain Delanium, by MCMB at 2000 DEG C of heat treatments carried out above Graphitization MCMB that obtains, by mesophase pitch based carbon fiber at 2000 DEG C of heat treatments carried out above The graphitized intermediate-phase pitch-based carbon fiber etc. obtained.

[[metal class negative electrode active material]]

Described metal class negative electrode active material is the active substance comprising metal, it is common that refer to wrap in the structure Containing embedding the element of lithium and embedding the theoretical capacity of per unit mass in the case of lithium be The active substance of more than 500mAh/g.As metal class active substance, can use such as: lithium metal, Can be formed lithium alloy elemental metals (such as, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn, Ti etc.) and alloy and their oxide, sulfide, Nitride, silicide, carbide, phosphide etc..

And then, in metal class negative electrode active material, preferably comprise active substance (the silicon class negative pole work of silicon Property material).It reason for this is that, by using silicon class negative electrode active material, can realize lithium ion secondary electricity The high capacity in pond.

As silicon class negative electrode active material, can enumerate such as: silicon (Si), the alloy comprising silicon, SiO, SiO_x、 Conductive carbon cladding is utilized containing Si material or to utilize conductive carbon to carry out Composite with containing Si material Compound compound etc. containing Si material Yu conductive carbon.It should be noted that these silicon class negative electrode active materials Matter can be used alone a kind, it is also possible to two or more is applied in combination.

As comprising the alloy of silicon, can enumerate such as: comprise the transition metal such as silicon, aluminum and ferrum, go forward side by side One step comprises the alloy composite of the rare earth element such as stannum and yttrium.

SiO_xIt is containing SiO and SiO₂In at least one and containing the compound of Si, x is usually 0.01 less than 2.Further, SiO_xMay utilize the dismutation reaction of such as silicon monoxide (SiO) and formed. Specifically, can by SiO optionally being carried out in the presence of the polymer such as polyvinyl alcohol heat treatment, Make silicon generate with silicon dioxide, thus prepare SiO_x.It should be noted that heat treatment can incited somebody to action After SiO is optionally pulverized and mixed with polymer, at the gas comprising organic gas and/or steam In atmosphere, the temperature in more than 900 DEG C, preferably more than 1000 DEG C is carried out.

As the compound compound containing Si material Yu conductive carbon, can enumerate such as: be pulverized and mixed following The chemical combination that thing carries out heat treatment in such as comprising the atmosphere of organic gas and/or steam and obtains Thing, described crushed mixture is the polymer such as SiO and polyvinyl alcohol and optionally and material with carbon element Crushed mixture.Furthermore it is also possible to utilize following method to obtain: by employing organic gas etc. The method that the surface of the particle of SiO is coated with by chemical vapor deposition method；Utilize mechanochemical reaction by SiO's Particle carries out the known methods such as the method for compound particle (pelletize) with graphite or Delanium.

Here, particle diameter, specific surface area for negative electrode active material are not particularly limited, can be with in the past The negative electrode active material used is identical.

It should be noted that in the paste compound of the present invention, 100 matter every relative to electrode active material Amount part, the content of particle shaped polymer (A) is preferably more than 0.2 mass parts, more preferably 0.5 mass parts Above, it is particularly preferably more than 1 mass parts, below preferably 10 mass parts, is more preferably 6 mass Below part, below particularly preferably 2 mass parts.By making the content of particle shaped polymer (A) be relative More than every 100 mass parts 0.2 mass parts of electrode active material, can improve with electrode active material, The caking property of collector body.It addition, by below for 10 mass parts, in the slurry group by using the present invention When the electrode that compound obtains is applicable to secondary cell, can suppress by particle shaped polymer (A) cause right The obstruction of the migration of charge carrier (for the situation of lithium rechargeable battery, for lithium ion), thus subtract The internal resistance of little secondary cell.

<water-soluble thickener (D)>

The paste compound of the present invention preferably comprises water-soluble thickener (D).If paste compound comprises Water-soluble thickener (D), then can get the excellent storage stability of paste compound, it addition, will slurry Feed composition coat collector body first-class time workability good.

Here, in this manual, thickening agent refers to for " water solublity ": will be every relative to ion exchange water 100 mass parts are added water-soluble thickener (D) 1 mass parts (solid constituent a great deal of) and are stirred and obtain The mixture arrived, adjust to the scope of temperature more than 20 and less than 70 DEG C and pH more than 3 and In condition in the range of less than 12 (using NaOH aqueous solution and/or HCl/water solution to adjust pH) At least one and during by the sieve of 250 mesh, do not remain in the solid constituent of the residue on sieve by sieving Quality relative to the solid constituent of the thickening agent added less than 50 mass %.It should be noted that Even if the mixture of above-mentioned thickening agent and water is the emulsion state being separated into two-phase in the case of standing, only Meet above-mentioned definition, i.e. think that this thickening agent is water solublity.

As water-soluble thickener (D), it is not particularly limited, but in order to make to coat paste compound Workability when collector body is first-class is good, can use such as: carboxymethyl cellulose, methylcellulose, hydroxyl Propyl methocel, hydroxyethylmethyl-cellulose, polyvinyl alcohol, polycarboxylic acids, their salt etc..Its In, as polycarboxylic acids, polyacrylic acid, polymethylacrylic acid, alginic acid etc. can be enumerated.These water solublity increase Thick dose (D) can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.And then, In these, in order to make to coat paste compound collector body first-class time workability improve further, excellent Select carboxymethyl cellulose, polyacrylic acid or their salt.Further, in order to ensure electrode active material Layer and collector body between adaptation, the paste compound of the present invention preferably comprise carboxymethyl cellulose or its Salt (hereinafter also referred to as " carboxymethyl cellulose (salt) ").It should be noted that the water solublity enumerated here Thickening agent has water solublity, is different from clearly and does not has water miscible hydrophilic organic fiber (B).

In the paste compound of the present invention, 100 mass parts every relative to electrode active material, water solublity increases The content of thick dose (D) is preferably more than more than 0.1 mass parts, more preferably 0.2 mass parts, particularly preferably It is more than 0.5 mass parts, below preferably 20 mass parts, below more preferably 10 mass parts, especially It is preferably below 5 mass parts.By making the use level of water-soluble thickener (D) within the above range, can So that the viscosity that paste compound is under high shear reaches appropriately sized, so that paste compound is coated with Workability when collector body is first-class is good.

In the paste compound of the present invention, relative to every 100 mass parts of particle shaped polymer (A), water-soluble Property thickening agent (D) content be preferably more than more than 10 mass parts, more preferably 30 mass parts, especially It is preferably more than 50 mass parts, below preferably 200 mass parts, below more preferably 150 mass parts, Below particularly preferably 100 mass parts.By making the use level of water-soluble thickener (D) in above-mentioned scope In, paste compound viscosity under high shear can be made to reach appropriately sized, so that by slurry compositions Thing coat collector body first-class time workability good.

In the slurry for secondary battery electrode compositions of the present invention in addition to mentioned component, it is also possible to contain The compositions such as conductive material, supporting material, levelling agent, electrolysis additive.It should be noted that this In the case of bright slurry for secondary battery electrode compositions is anode of secondary battery paste compound, should Paste compound preferably comprises the conductive materials such as acetylene black.

As long as the composition that cell reaction will not be impacted by these other compositions is then not particularly limited, Known material, such as International Publication No. 2012/115096th number, Japanese Unexamined Patent Publication 2012-204303 can be used Those described in number publication.These compositions can be used alone a kind, it is also possible to combines with arbitrary ratio Use two or more.

The paste compound of the present invention can by above-mentioned each composition is optionally carried out partial pre-mix it After be scattered in and prepare as in the aqueous medium of disperse medium, it is also possible to by comprising particle shape in preparation After polymer (A), hydrophilic organic fiber (B) and the adhesive composition of water, this binding agent is combined Thing and electrode active material and be optionally dispersed in water-soluble thickener (D) etc. as dispersion be situated between Prepared by the aqueous medium of matter.It should be noted that in order to make production become easy, the slurry of the present invention Feed composition can be by comprising particle shaped polymer (A), hydrophilic organic fiber (B) and water in preparation After adhesive composition, this adhesive composition and electrode active material etc. are dispersed in and are situated between as dispersion Prepared by the aqueous medium of matter.Specifically, preferably by using ball mill, sand mill, bead mill Machine, pigment dispersion machine, grater, ultrasonic dispersing machine, homogenizer, planetary-type mixer, FILMIX Deng mixer prepared by aqueous dispersions and hydrophilic organic fiber (B) mixing of particle shaped polymer (A) After adhesive composition, add electrode active material further and optionally add aqueous medium etc. and go forward side by side Row mixing, prepares paste compound.

Here, as aqueous medium, generally use water but it also may use the water-soluble of arbitrary compound Liquid, a small amount of organic media and the mixed solution etc. of water.It addition, the solid component concentration of paste compound can To be set to make the homodisperse concentration of each composition, such as more than 30 mass % and below 90 mass %, More than more preferably 40 mass % and below 80 mass %.Further, above-mentioned each composition and aqueous medium Mixing generally can more than room temperature and the scope of less than 80 DEG C is carried out more than 10 minutes and a few hours with Under.

(electrode for secondary battery)

The electrode for secondary battery of the present invention can use the slurry for secondary battery electrode compositions of the present invention Manufacture.

It addition, the electrode for secondary battery of the present invention possesses collector body and forms electrode on the current collector Closing sheet material layers, electrode closes sheet material layers and can be obtained by the slurry for secondary battery electrode compositions of the present invention.This The electrode of bright electrode for secondary battery closes the excellent adhesion between sheet material layers and collector body.

It should be noted that the electrode for secondary battery of the present invention can manufacture via following operation: such as, Above-mentioned slurry for secondary battery electrode compositions is coated the operation (painting process) on collector body；Will The slurry for secondary battery electrode compositions coated on collector body is dried, thus forms electricity on the current collector The operation (drying process) of sheet material layers is closed in pole；And optionally electrode is closed the work that sheet material layers heats further Sequence (heating process).In the case of paste compound comprises cross-linking agent (C), such as, by back tender The heat applied in sequence, the heat applied in heating process, can make to obtain by the cross-linking reaction of cross-linking agent (C) With carry out.That is, close in sheet material layers at electrode, particle shaped polymer (A), hydrophilic organic fiber (B), with And optional water-soluble thickener (D) can form the cross-linked structure connected by cross-linking agent (C), utilizing should Cross-linked structure, can make electrode close the adaptation between sheet material layers and collector body and improve.It addition, utilize this friendship Connection structure, can make the electrical characteristic of the secondary cells such as cycle characteristics improve.

[painting process]

Coat the method on collector body as by above-mentioned slurry for secondary battery electrode compositions, there is no spy Different restriction, can use known method.Specifically, as coating process, scraper plate method, leaching can be used Stain method, inverse roller method, direct roller method, intagliotype, extrusion molding, spread coating etc..At this point it is possible to by slurry Compositions only coats the one side of collector body, it is also possible to coat two sides.Collector body before being dried after coating On the thickness of slurry film, the thickness of sheet material layers can be closed according to the electrode being dried to obtain and suitably set.

Here, as the collector body of paste compound to be coated, can use and there is electric conductivity and there is electricity The material of chemical durability.Specifically, as collector body, can use such as by ferrum, copper, aluminum, nickel, The collector body that rustless steel, titanium, tantalum, gold, platinum etc. are made.Wherein, as the collector body for positive pole, Particularly preferably aluminium foil (aluminum), as the collector body for negative pole, particularly preferred Copper Foil.It should be noted that Above-mentioned material can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.

[drying process]

As the method that the paste compound on collector body is dried, it is not particularly limited, can use known Method, such as can enumerate utilize warm braw, hot blast, being dried of low wet wind, be vacuum dried, utilize red The seasoning of the irradiation of outside line, electron beam etc..By the paste compound being dried in this wise on collector body, Electrode can be formed on the current collector and close sheet material layers, thus obtain possessing collector body and the secondary of electrode conjunction sheet material layers Electrode for cell.It should be noted that in the case of paste compound comprises cross-linking agent (C), utilize The heat applied when being dried by paste compound, the cross-linking reaction by cross-linking agent (C) is carried out.

It should be noted that can also use moulding press or roll squeezer etc. that electrode is closed after drying process Sheet material layers implements pressurized treatments.By pressurized treatments, that can improve that electrode closes between sheet material layers and collector body is close Conjunction property.

It addition, in the case of paste compound comprises cross-linking agent (C), preferably forming electrode conjunction sheet material layers Afterwards, enforcement heating process is so that cross-linking reaction is carried out, so that cross-linked structure is the most abundant.This heating Operation preferably more than 80 DEG C and less than 160 DEG C carry out more than 1 hour and less than 20 hours degree.

(secondary cell)

The secondary cell of the present invention possesses positive pole, negative pole, electrolyte and dividing plate, and above-mentioned positive pole and negative pole In the electrode for secondary battery that at least one is the present invention, electrode in this electrode closes sheet material layers and collector body Between excellent adhesion.It addition, the secondary cell of the present invention is used due to the secondary cell possessing the present invention Electrode, the therefore excellent electrical characteristic such as cycle characteristics.

As it has been described above, the electrode for secondary battery of the present invention can be used as at least one in positive pole and negative pole. I.e., it is possible to be the electrode of the most extremely present invention of the secondary cell of the present invention, negative pole be negative known to other Pole, it is also possible to be the electrode that negative pole is the present invention of the secondary cell of the present invention, the most extremely known to other Positive pole, and then, it is also possible to be positive pole and the negative pole both of which of the secondary cell of the present invention be the present invention Electrode.

As electrolyte, it is usable in solvent dissolving the electrolyte of electrolyte.

Here, as solvent, it is possible to use the organic solvent of electrolyte can be dissolved.Specifically, make For solvent, such as in the case of secondary cell is lithium rechargeable battery, it is possible to use in carbonic acid Asia second In the alkyl carbonate esters solvents such as ester, propylene carbonate, gamma-butyrolacton add 2,5-dimethyl-tetrahydrofuran, Oxolane, diethyl carbonate, Ethyl methyl carbonate, dimethyl carbonate, methyl acetate, dimethoxy second The solvent that the viscosity such as alkane, dioxolanes, methyl propionate, methyl formate adjust solvent and obtain.

As electrolyte, such as in the case of secondary cell is lithium rechargeable battery, it is possible to use lithium Salt.As lithium salts, such as, can use in those described in Japanese Unexamined Patent Publication 2012-204303 publication. In these lithium salts, from the viewpoint of being easily dissolved in organic solvent and showing high degree of dissociation, as Electrolyte, preferably LiPF₆、LiClO₄、CF₃SO₃Li。

As dividing plate, such as in the case of secondary cell is lithium rechargeable battery, it is possible to use in day Those described in this JP 2012-204303 publication.In these, from the film that can make dividing plate entirety Thick thinning, thus can improve the ratio of electrode active material in lithium rechargeable battery thus improve every From the viewpoint of the capacity of unit volume, preferably (polyethylene, polypropylene, poly-by the resin of TPO Butylene, polrvinyl chloride) micro-porous film that formed.

The secondary cell of the present invention such as can manufacture by the following method: across dividing plate overlapping positive pole and Negative pole, and optionally it is crimped according to cell shapes, puts into battery case, to electricity after bending etc. Pond container injects electrolyte and seals.In order to prevent the pressure of the inside of secondary cell from raising, cross discharge and recharge Deng generation, it is also possible to the overcurrent such as electric fuse, PTC-element is set as desired and prevents element, swollen Swollen alloy, lead plate etc..The shape of secondary cell can be such as Coin shape, coin shape, flap-type, circle Arbitrary shape in cartridge type, square, platypelloid type etc..

Embodiment

Hereinafter, the present invention is specifically explained in conjunction with the embodiments, but the present invention is not limited to these Embodiment.It should be noted that in the following description, " % " and " part " of expression amount is as long as no especially Illustrate, be then quality criteria.

The Surface acidity of particle shaped polymer is calculated according to above-mentioned method and has been measured.Need explanation , in the mensuration of Surface acidity, as electrical conductivity of solution instrument, employ electrical conductivity of solution instrument (capital All Electronics Industry Company's system: CM-117, use cell type: K-121), as the hydroxide of 0.1 equivalent Sodium and the hydrochloric acid of 0.1 equivalent, employ medicine system pure with light respectively: the material that reagent is superfine.It addition, it is close The fiber diameter of aqueous organic fiber and average fiber length, the Na content of particle shaped polymer and K content is utilized respectively following methods and is determined.

Additionally, the thixotropy of the storage stability of paste compound, paste compound, negative pole close sheet material layers with Dhering strength between collector body is utilized respectively following methods and is evaluated.

Scanning electron microscope (S-2400, company of Hitachi system) is used to determine the organic fibre of hydrophilic The fiber diameter of dimension, average fiber length.

In platinum crucible, weigh particle shaped polymer, after utilizing burner to carry out heating ashing, utilize electricity Stove has carried out heating ashing.Gained calcination utilizes sulphuric acid and nitric acid carry out heat resolve, and utilizes dilute Nitric acid carries out heating for dissolving, has carried out constant volume.For this solution, ICP ICP Atomic Emission Spectrophotometer method is utilized to survey Determine Na, K amount, and calculate the solid constituent relative to particle shaped polymer Na content (ppm) and K content (ppm).It should be noted that as ICP emission spectrophotometer, employ SII Nano Technology company SPS4000.

After at room temperature being stood by the paste compound of preparation, Brookfield viscometer (rotating speed 60rpm) is utilized to survey Determine initial stage viscosity (η 0).Then, after measuring initial stage viscosity, the most at room temperature stand 24 hours, Similarly determine the viscosity after 24 hours (η 1).

(| η 0-η 1 |)/η 1 × 100 (%) is utilized to calculate the degree of viscosity B coefficent, and carry out according to following benchmark Evaluate.Viscosity B coefficent is the least, then it represents that storage stability is the most excellent.

A: viscosity B coefficent is less than 5.0%

B: viscosity B coefficent is 5.0% less than 10.0%

C: viscosity B coefficent is 10.0% less than 20.0%

D: viscosity B coefficent is 20.0% less than 30.0%

E: viscosity B coefficent is more than 30.0%

For the paste compound of preparation, Brookfield viscometer is at room temperature utilized to determine gluing under 6rpm Viscosity (η 60) under degree (η 6) and 60rpm.Calculate ratio of viscosities (TI value) with η 6/ η 60, and according to Lower benchmark is evaluated.TI value is the biggest, then it represents that thixotropy is the most excellent.

A:TI value is more than 3.0

B:TI value is less than 3.0 and is more than 2.8

C:TI value is less than 2.8 and is more than 2.6

D:TI value is less than 2.6 and is more than 2.4

E:TI value is less than 2.4

The secondary battery cathode of making is cut into long 100mm, the oblong-shaped of wide 10mm, as Test film, makes to have that negative pole closes sheet material layers closes sheet material layers surface mount adhesive tape (JIS at negative pole face-down The adhesive tape of regulation in Z1522), measure one end of collector body vertically with draw speed Stress (wherein, adhesive tape is fixed in testing stand) when stretching and peel off for 50mm/ minute.Carry out 3 Secondary mensuration, obtains its meansigma methods, using this meansigma methods as peel strength, and carries out according to following benchmark Evaluate.The value of peel strength is the biggest, then it represents that the adaptation that negative pole closes between sheet material layers and collector body is the most excellent.

A: peel strength is more than 5.0N/m

B: peel strength is that 4.5N/m is less than 5.0N/m

C: peel strength is that 4.0N/m is less than 4.5N/m

D: peel strength is that 3.0N/m is less than 4.0N/m

E: peel strength is less than 3.0N/m

(use material)

Secondary battery negative pole adhesive composition in below example and comparative example and secondary electricity In the preparation of pond negative pole paste compound, employ following particle shaped polymer (A), hydrophilic has Organic fiber (B), cross-linking agent (C) and water-soluble thickener (D).

[particle shaped polymer (A)]

Be prepared for as described below particle shaped polymer A1 and particle shaped polymer A2 (be have carboxyl+ Conjugated diene/the aromatic vinyl copolymer of hydroxyl) and particle shaped polymer A3 (there is carboxyl Acrylic acid/unsaturated nitrile copolymer).

(1) particle shaped polymer A1:

The styrene as aromatic vinyl monomer is added in the 5MPa pressure vessel of belt stirrer (ST) 65 parts, as the 1,3-butadiene (BD) 33 parts of aliphatic conjugated diene monomer, as olefinic insatiable hunger With 1 part of the itaconic acid (IA) of carboxylic acid monomer, as the acrylic acid 2-hydroxyl of the unsaturated monomer with hydroxyl Ethyl ester (2-HEA) 1 part, as the tertiary lauryl mercaptan 0.3 part of molecular weight regulator, as emulsifying agent Dodecylbenzene sodium sulfonate 5 parts, as the ion exchange water 150 parts of solvent and draw as polymerization Send out the potassium peroxydisulfate 1 part of agent, after being sufficiently stirred for, be heated up to 55 DEG C to cause polymerization.

Reach moment of 95.0% cools down in monomer consumption, terminates reaction.To thus obtained bag Aqueous dispersion containing polymer adds 5% sodium hydrate aqueous solution, by pH regulator to 8.Then, logical Cross heating decompression distillation and carry out the removing of unreacted monomer.It is then cooled to less than 30 DEG C, Arrive the aqueous dispersions of particle shaped polymer A1.The Surface acidity of particle shaped polymer A1 is 0.1mmol/g, Na content be 1000ppm, K content be 3000ppm.

(2) particle shaped polymer A2:

Using the quantitative change more 62 parts of the styrene (ST) as aromatic vinyl monomer, will be as olefinic The quantitative change in the itaconic acid (IA) of unsaturated carboxylic acid monomer more 4 parts, in addition, with particle shaped polymer A1 has similarly obtained the aqueous dispersions of particle shaped polymer A2.

The Surface acidity of particle shaped polymer A2 be 0.38mmol/g, Na content be 11000ppm, K Content is 3000ppm.Wherein, compared with particle shaped polymer A1, Na content rise, and this be by The necessary amount of 5% sodium hydrate aqueous solution in time regulating pH rises.

(3) particle shaped polymer A3

To equipped with the reactor of agitator adds the butyl acrylate as (methyl) acrylate monomer (BA) 96.0 parts, as ethylenically unsaturated carboxylic acids monomer methacrylic acid (MAA) 2.0 parts, as α, β- The acrylonitrile of unsaturated nitrile monomer 2.0 parts, the dodecylbenzene sodium sulfonate 0.3 part as emulsifying agent, work For Ammonium persulfate. 0.3 part, the ion exchange water 300 parts of polymerization initiator, after being sufficiently stirred for, it is heated up to 70 DEG C and carried out reaction in 3 hours, further heat up to 80 DEG C of ripenings 3 hours, thus make reaction complete Become.Thereafter, it is cooled to less than 30 DEG C, obtains the aqueous dispersions of particle shaped polymer A3.Particle shape The Surface acidity of polymer A 3 be 0.25mmol/g, Na content be 7000ppm, K content be 1000ppm.

[hydrophilic organic fiber (B)]

(1) hydrophilic organic fiber B1:

Employ BiNFi-s (registered trade mark) as cellulose fibre (Sugino Machine company system). Fiber diameter is 20nm, average fiber length is 67000nm, aspect ratio is 3350.

(2) hydrophilic organic fiber B2:

Employ Celish (registered trade mark) KY-100G (Daicel company system) as cellulose fibre.Flat Equal fibre diameter is 70nm, average fiber length is 100000nm, aspect ratio is 1430.

[cross-linking agent (C)]

Cross-linking agent C1: poly-carbodiimide (Nisshinbo Chemical company system, goods name: CARBODILITE (registered trade mark) SV-02, single-phase water dissolubility)

Cross-linking agent C2: multi-functional epoxy compound (Nagase ChemteX system, goods name: EX-313, Functional group number 3/every 1 molecule (every 1 molecule have 2 epoxy radicals and the compound of 1 hydroxyl and Every 1 molecule has the mixture of the compound of 3 epoxy radicals), single-phase water dissolubility)

Double (the 2-of cross-linking agent C3:2,2'-Oxazoline) (Tokyo chemical conversion industrial group system, single-phase water dissolubility)

[water-soluble thickener (D)]

The sodium salt of CMC1: carboxymethyl cellulose (Nippon Paper Chemicals company system, goods name: MAC350HC, viscosity 3500mPa s of degree of etherification falling 0.81% aqueous solution)

PAA1: polyacrylic acid (Aldrich system, weight average molecular weight 450,000)

(embodiment 1)

The particle shaped polymer A1 as particle shaped polymer (A) is put into solid in planetary-type mixer Body composition meter 100 parts, as the hydrophilic organic fiber B1 of hydrophilic organic fiber (B) with solid constituent Count 5 parts, as the cross-linking agent C1 of cross-linking agent (C) with solid component meter 5 parts (above as secondary battery cathode Pole adhesive composition), put into further as negative electrode active material as carbons active substance Native graphite (Nippon Carbon company system, goods name: N98) 7407 parts, as water-soluble thickener (D) 1% aqueous solution of CMC1 is with solid component meter 74.1 parts (every relative to negative electrode active material 100 Mass parts is 1 part).Then, in the way of making solid component concentration reach 52%, ion exchange water is added And mix, it is prepared for containing particle shaped polymer A1, hydrophilic organic fiber B1, cross-linking agent C1, CMC1, the secondary battery negative pole paste compound of negative electrode active material.

Use the secondary battery negative pole paste compound of preparation to the storage stability of paste compound and Thixotropy is evaluated.Result is as shown in table 1.

Utilize unfilled corner wheel coating machine that above-mentioned secondary battery negative pole paste compound is coated on thickness The Copper Foil (collector body) of 20 μm is upper and makes coating amount reach 8.8mg/cm²～9.2mg/cm².It is coated with The Copper Foil of this secondary battery negative pole paste compound passes in the baking oven of 80 DEG C with the speed of 0.3m/ minute Send 2 minutes, then transmit 2 minutes in the baking oven of 120 DEG C, thus make the paste compound on Copper Foil It is dried, has obtained the former film of negative pole.

Then, the compacting of former for thus obtained negative pole film roll squeezer is reached to closing sheet material layers density 1.44g/cm³～1.55g/cm³, then in order to remove moisture and promote further crosslinking and at vacuum condition Under, the environment of 120 DEG C is placed 10 hours, obtained being formed with negative pole on the current collector and closed the negative of sheet material layers Pole.

The negative pole of use, the adaptation that anticathode closes between sheet material layers and collector body is evaluated.Knot Fruit is as shown in table 1.

The LiCoO as positive active material is added in planetary-type mixer₂100 parts, conduct conduction The acetylene black of material 2 parts (electrochemically industry (strain) system " HS-100 "), as positive pole binding agent PVDF (Kynoar, (strain) Kureha Chemical system " KF-1100 ") 2 parts and make total solid Body constituent concentration reaches the N-Methyl pyrrolidone of 67%, and mixes, and is just being prepared for secondary cell Pole paste compound.

Utilize unfilled corner wheel coating machine that the anode of secondary battery paste compound obtained is coated on thickness On the aluminium foil of 20 μm and be dried, make coating amount reach 17.5mg/cm²～18.4mg/cm².Need Illustrating, this is dried by aluminium foil was transmitted 2 points with the speed of 0.5m/ minute in the baking oven of 60 DEG C Clock is carried out.Then, carry out 2 minutes heat treated in 120 DEG C, obtain the former film of positive pole.

Former for the positive pole obtained film roll squeezer carries out the conjunction sheet material layers density after suppressing and make compacting reach 3.40g/cm³～3.50g/cm³, then, in order to remove moisture and under vacuum, in the environment of 120 DEG C Place 3 hours, obtained being formed with positive pole on the current collector and closed the positive pole of sheet material layers.

Polypropylene dividing plate (wide 65mm, long 500mm, thick 25 μm of monolayer are prepared；Utilize dry type Method manufactures；The porosity 55%), and it is die-cut into the square shape of 5cm × 5cm.It addition, as electricity The outer package in pond, has prepared aluminum housing material.

Then, the positive pole of making is cut into the oblong-shaped of 3.8cm × 2.8cm, so that the table on current collection side The mode that face contacts with aluminum housing material configures.Then, the positive pole at positive pole closes and joins on the face of sheet material layers Put the dividing plate of above-mentioned square shape.And then, the negative pole of making is cut into the rectangular of 4.0cm × 3.0cm Shape, is arranged in its surface closing sheet material layers side by negative pole on dividing plate in the way of dividing plate.Then, to Wherein fill the LiPF of concentration 1.0M as electrolyte₆(solvent is ethylene carbonate (EC)/carbonic acid to solution The mixed solvent of methyl ethyl ester (EMC)=3/7 (volume ratio), and containing the vinylene carbonate 2 as additive Volume % (solvent ratio)).Further, for the opening of sealed aluminum packaging material, the heat-sealing of 150 DEG C is carried out And aluminum outer package is sealed, manufacture the lithium rechargeable battery of laminated units type.

(embodiment 2,3)

Except make hydrophilic organic fiber B1 use level be respectively with solid component meter 1 part, 8 parts with Outward, secondary battery negative pole paste compound, negative pole, positive pole, lithium have been manufactured similarly to Example 1 Ion secondary battery.And then, evaluated similarly to Example 1.Result is as shown in table 1.

(embodiment 4)

In addition to replacing hydrophilic organic fiber B1 to employ hydrophilic organic fiber B2, with reality Execute example 1 and similarly manufacture secondary battery negative pole paste compound, negative pole, positive pole, lithium ion secondary Battery.And then, evaluated similarly to Example 1.Result is as shown in table 1.

(embodiment 5～7)

Except make cross-linking agent C1 use level be respectively with solid component meter 0 part, 0.5 part, 10 parts with Outward, secondary battery negative pole paste compound, negative pole, positive pole, lithium have been manufactured similarly to Example 1 Ion secondary battery.And then, evaluated similarly to Example 1.Result is as shown in table 1.

(embodiment 8,9)

In addition to replacing cross-linking agent C1 to employ cross-linking agent C2, cross-linking agent C3 respectively, with enforcement Example 1 has similarly manufactured secondary battery negative pole paste compound, negative pole, positive pole, lithium ion secondary electricity Pond.And then, evaluated similarly to Example 1.Result is as shown in table 1.

(embodiment 10,12)

In addition to replacing particle shaped polymer A1 to employ particle shaped polymer A2, A3 respectively, Secondary battery negative pole paste compound, negative pole, positive pole, lithium ion are manufactured similarly to Example 1 Secondary cell.And then, evaluated similarly to Example 1.Result is as shown in table 1.

(embodiment 11)

In addition to replacing employing PAA1 as the CMC1 of water-soluble thickener (D), with enforcement Example 1 has similarly manufactured secondary battery negative pole paste compound, negative pole, positive pole, lithium ion secondary electricity Pond.And then, evaluated similarly to Example 1.Result is as shown in table 1.

(comparative example 1)

In addition to not using hydrophilic organic fiber B1 and cross-linking agent C1, similarly to Example 1 Secondary battery negative pole paste compound, negative pole, positive pole, lithium rechargeable battery are manufactured.And then, Evaluated similarly to Example 1.Result is as shown in table 1.

(comparative example 2)

Except not using cross-linking agent C1 and making the use level of hydrophilic organic fiber B1 for solid constituent Beyond counting 50 parts, manufactured similarly to Example 1 secondary battery negative pole paste compound, negative pole, Positive pole, lithium rechargeable battery.And then, evaluated similarly to Example 1.Result such as table 1 Shown in.

(comparative example 3)

In addition to not using particle shaped polymer A1 and cross-linking agent C1, make similarly to Example 1 Secondary battery negative pole paste compound, negative pole, positive pole, lithium rechargeable battery are made.And then, with Embodiment 1 is similarly evaluated.Result is as shown in table 1.

(comparative example 4)

In addition to not using hydrophilic organic fiber B1, manufacture secondary electricity similarly to Example 1 Pond negative pole paste compound, negative pole, positive pole, lithium rechargeable battery.And then, same with embodiment 1 Evaluated sample.Result is as shown in table 1.

(comparative example 5)

In addition to making the use level of hydrophilic organic fiber B1 for solid component meter 25 parts, with enforcement Example 1 has similarly manufactured secondary battery negative pole paste compound, negative pole, positive pole, lithium ion secondary electricity Pond.And then, evaluated similarly to Example 1.Result is as shown in table 1.

As shown in Table 1, particle shaped polymer (A) and hydrophilic organic fiber (B) are employed with specific ratios Embodiment 1～12, it can be ensured that the excellent thixotropy of paste compound, and, available excellence Negative pole close the adaptation between sheet material layers and collector body.

On the other hand, the comparative example 1 of hydrophilic organic fiber (B) and 4 and employ and be more than is not used The comparative example 2 and 5 of the hydrophilic organic fiber (B) of specified rate, fail to make the thixotropy of paste compound and Negative pole closes the adaptation between sheet material layers and collector body and improves.It addition, do not use particle shaped polymer (A) Comparative example 3, never produces the problem that particle shaped polymer migrates, but owing to not existing as bonding The particle shaped polymer of agent function, the adaptation that therefore negative pole closes between sheet material layers and collector body becomes pole Difference.

Particularly, from the embodiment 1～3 of table 1, by the amount of change hydrophilic organic fiber (B), The storage stability of paste compound, the thixotropy of paste compound and negative pole can be made to close sheet material layers and collection Adaptation between electricity body is the best.

It addition, from the embodiment 1,4 of table 1, by changing the average of hydrophilic organic fiber (B) Fibre diameter, can make the storage stability of paste compound and negative pole close between sheet material layers and collector body Adaptation is the best.

It addition, from the embodiment 1,5～7 of table 1, by changing the presence or absence of cross-linking agent (C) and joining Resultant, can make the storage stability of paste compound, the thixotropy of paste compound and negative pole close material Adaptation between layer and collector body is the best.

Further, from the embodiment 1,8,9 of table 1, by the kind of change cross-linking agent (C), Storage stability and the negative pole that can make paste compound close the adaptation between sheet material layers and collector body more Well.

Additionally, from the embodiment 1,10,12 of table 1, by change particle shaped polymer (A) Composition or the Surface acidity of regulation particle shaped polymer (A), can make negative pole close sheet material layers and collector body it Between adaptation the best.

It addition, except negative electrode active material being changed to the LiCoO as positive active material₂, do not join Close cross-linking agent, coordinated 2 parts as the acetylene black of conductive material beyond, with embodiment 1～4,10～12 Secondary battery negative pole paste compound be prepared as the anode of secondary battery slurry group of aqueous Compound.And then, for these positive pole paste compounds, to slurry in the same manner as negative pole paste compound The storage stability of feed composition, the thixotropy of paste compound and formed by this paste compound The dhering strength that positive pole closes between sheet material layers and collector body is evaluated.Commenting of each positive pole paste compound Valency is identical with corresponding negative pole paste compound respectively.

Industrial applicibility

Claims

1. a binder composition for secondary battery electrode, it comprises: particle shaped polymer (A), parent Aqueous organic fiber (B) and water,

Relative to described every 100 mass parts of particle shaped polymer (A), containing more than 0.01 mass parts and 20 Described hydrophilic organic fiber (B) below mass parts.

Binder composition for secondary battery electrode the most according to claim 1, wherein, described Hydrophilic organic fiber (B) has hydroxyl.

Binder composition for secondary battery electrode the most according to claim 1 and 2, wherein, The fiber diameter of described hydrophilic organic fiber (B) is more than 1nm and below 1000nm.

4. according to the binder composition for secondary battery electrode according to any one of claims 1 to 3, It also comprises cross-linking agent (C), and this cross-linking agent (C) is at least one in lower group: multi-functional epoxyization Compound,Isoxazoline compound and carbodiimide compound.

Binder composition for secondary battery electrode the most according to claim 4, wherein, relatively In described every 100 mass parts of particle shaped polymer (A), containing more than 0.01 mass parts and 10 mass parts with Under described cross-linking agent (C).

6. according to the binder composition for secondary battery electrode according to any one of Claims 1 to 5, Wherein, the Surface acidity of described particle shaped polymer (A) be more than 0.01mmol/g and 3.5mmol/g with Under.

7. a slurry for secondary battery electrode compositions, it comprises particle shaped polymer (A), hydrophilic Organic fiber (B), electrode active material and water,

Slurry for secondary battery electrode compositions the most according to claim 7, it also comprises crosslinking Agent (C), this cross-linking agent (C) is at least one in lower group: multi-functional epoxy compound,Oxazoline Compound and carbodiimide compound.

9., according to the slurry for secondary battery electrode compositions described in claim 7 or 8, it also comprises Water-soluble thickener (D).

10. an electrode for secondary battery, it has two used according to any one of claim 7～9 Primary cell slurry composition for electrode and the electrode that obtains closes sheet material layers.

11. 1 kinds of secondary cells, it possesses: positive pole, negative pole, electrolyte and dividing plate,

At least one in described positive pole and negative pole is the electrode for secondary battery described in claim 10.