CN105190968B - The manufacturing method of electro-chemical element electrode adhesive, electro-chemical element electrode particle complex, electro-chemical element electrode, electrochemical element and electro-chemical element electrode - Google Patents

The manufacturing method of electro-chemical element electrode adhesive, electro-chemical element electrode particle complex, electro-chemical element electrode, electrochemical element and electro-chemical element electrode Download PDF

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CN105190968B
CN105190968B CN201480026238.XA CN201480026238A CN105190968B CN 105190968 B CN105190968 B CN 105190968B CN 201480026238 A CN201480026238 A CN 201480026238A CN 105190968 B CN105190968 B CN 105190968B
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electrode
electro
chemical element
element electrode
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CN105190968A (en
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石井琢也
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Zeon Corp
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Nippon Zeon Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Abstract

The purpose of the present invention is to provide since the productivity for not making slurry therefore electrode when electrode layer is formed is excellent, manufacturing method due to the excellent electro-chemical element electrode adhesive of the thickness and precision of electrode and flexibility that do not need water soluble polymer ingredient as dispersant therefore can realize low resistance, and obtain, the electrode complex for having used it, electrode, electrochemical element and electrochemical element.Electro-chemical element electrode of the present invention with adhesive is 35~80 DEG C by glass transition temperature, the polymer that the volume reference D50 average grain diameters of primary particle are 80~1000nm is formed, its 120 DEG C volatile ingredient is less than 1 weight %, and the adhesive is powdered Composite particle.

Description

Electro-chemical element electrode adhesive, electro-chemical element electrode particle complex, electricity The manufacturing method of chemical component electrode, electrochemical element and electro-chemical element electrode
Technical field
The present invention relates to electro-chemical element electrode adhesive, electro-chemical element electrode particle complex, electrochemistry members The manufacturing method of part electrode, electrochemical element and electro-chemical element electrode.
Background technology
The electrochemical elements such as lithium rechargeable battery, double layer capacitor and lithium-ion capacitor have small-sized, lightweight, Characteristic energy density height and can be repeatedly charged and discharged, efficiently uses such characteristic so that its demand expands rapidly.Lithium Ion secondary battery is because energy density is larger, thus has been used for the mobile fields such as mobile phone, subnotebook PC.It is another Aspect, double layer capacitor because can promptly charge and discharge, therefore the slack storage small electrical for being used as PC etc. Source, in addition, being desirable to application of the double layer capacitor as the accessory power supply of electric vehicle etc..Further, it just efficiently uses For the lithium-ion capacitor of the advantages of lithium rechargeable battery and double layer capacitor, since its energy density, output are close Degree is higher than double layer capacitor, therefore has expanded the purposes that will be applicable in it is suitable for double layer capacitor and with double The performance of electric layer capacitor and the research for failing the purposes for meeting specification.Among these, especially for lithium rechargeable battery, In recent years, not only to its vehicle-mounted application on the way such as mixed power electric car, electric vehicle, even for it in electric power storage Application in terms of purposes is inquired into.
In the raised another aspect of expectation to these electrochemical elements, for these electrochemical elements, with its purposes Expansion and development, further improve also is required for low resistance, high capacity, mechanical property, productive improve etc.. In such a case, for electrode for electrochemical device, the higher manufacturing method of productivity is also required.
Electrode for electrochemical device is typically the electrode activity on the current collector made of laminate electrode active material layer Material layer be by by electrode active material and as needed by use conductive agent using adhesive carry out bond and formed. In electrode for electrochemical device, have using by that will be used containing the coating electrode of electrode active material, adhesive, conductive agent etc. The coating electrode that slurry coating removes the method for solvent and manufacture on the current collector and using heat etc..For example, in patent document 1 In, it describes to use polymer is extruded into membranaceous and polymer particle obtained from being crushed as adhesive, mixing should Adhesive, electrode active material, conductive agent and solvent obtain coating electrode slurry and are coated on the current collector to be applied The scheme of cloth electrode.It should be noted that the polymer particle used in patent document 1 is dried adhesive, does Adhesive.
But for these methods, due to needing for dry polymer film, molten with being removed in slurry from coating electrode The energy of agent, therefore existing causes cost to increase, be difficult to improve productive situation.
Then, it is proposed that the method for manufacturing electrode with slurry without using coating electrode.For example, in patent document 2, making With by the way that dry adhesives or the adhesive being scattered in solvent, electrode active material, the conductive agent comprising carbon material are mixed simultaneously Powder mixture obtained from being dried and form electrode active material layer.In addition, in patent document 3, using general Mixed-powder is in lithium primary battery obtained from carbon dust and adhesive are mixed and then are dried as wet type/crushed Negative terminal surface forms envelope.
In addition, it has been proposed that not only without using coating electrode slurry but also not do not obtain adhesive dispersion in a solvent The method for forming electrode active material layer to electrode material.For example, in patent document 4, being formd using mixed powder Electrode active material layer, the mixed powder are gathered by electrode active material and using the suspension carried out in the presence of conductive agent It is legal and have occurred what compound binder particles were obtained by mixing with conductive agent.
In addition, in patent document 5, Kynoar (PVDF) powder used as dry adhesives as adhesive, The mixed-powder for being obtained by mixing electrode active material, adhesive and conductive agent is set to be attached to current collection body surface by electrostatic coating Face, then, the temperature more than the softening point of adhesive keep these ingredients fusible, thus form electrode activity on the current collector Material layer.
Existing technical literature
Patent document
Patent document 1：International Publication No. 2007/122947
Patent document 2：No. 4687458 bulletins of Japan Patent
Patent document 3：Japanese Unexamined Patent Publication 2010-86738 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2011-14409 bulletins
Patent document 5：Japanese Unexamined Patent Publication 2001-351616 bulletins
Invention content
Problems to be solved by the invention
However, dry adhesives are used as adhesive and mix dry adhesives and electrode active material using by dry type Electrode material obtained from conjunction is come in the case of forming electrode active material layer, if the bonding described in using patent document 1 Agent then can lead to not obtain the electrode with abundant flexibility because the glass transition temperature of adhesive is excessively high.In addition, such as Fruit then is difficult to be formed using the adhesive described in patent document 2 or 5 since the glass transition temperature of adhesive is too low One electrode active material layer.In addition, not recorded using dry adhesives in patent document 3 and 4.
In addition, if using the adhesive used in patent document 5, since the grain size of adhesive is big, connection is electric Bonding point between the active material of pole is few, it is difficult to obtain the electrode with abundant intensity.
The purpose of the present invention is to provide due to do not made when forming electrode layer slurry therefore electrode productivity it is excellent, Due to not needing water soluble polymer ingredient as dispersant therefore can realize low resistance and the thickness essence of the electrode obtained Degree and the excellent electro-chemical element electrode adhesive of flexibility, the electrochemistry for having used the electro-chemical element electrode adhesive Element electrode particle complex, the electro-chemical element electrode and electrification for having used the electro-chemical element electrode particle complex Learn element.It is a further object of the invention to provide the electrochemical element that productivity is excellent, thickness and precision and flexibility are excellent The manufacturing method of electrode.
Solution to the problem
The present inventor has made intensive studies to solve the above-mentioned problems, as a result, it has been found that, by by glass transition temperature Degree and average grain diameter control can reach above-mentioned purpose, so as to complete the present invention in given range.
That is, according to the present invention, it is possible to provide：
(1) a kind of electro-chemical element electrode adhesive is 35~80 DEG C, primary particle by glass transition temperature Volume reference D50 average grain diameters are that the polymer of 80~1000nm is formed, and volatile ingredient of the adhesive at 120 DEG C is less than 1 Weight %, and the adhesive is powdered Composite particle；
(2) it is the grain by the way that the polymer will be dispersed with according to the electro-chemical element electrode adhesive described in (1) The aqueous dispersion of sub- shaped polymer is dried under conditions of less than the minimum film temperature of the particle shaped polymer and is obtained It arrives；
(3) according to the electro-chemical element electrode adhesive described in (1) or (2), it includes at least one in being selected from the group Kind monomeric unit：Conjugated diene monomeric unit, acrylate monomeric units, methacrylate monomers unit, aromatic vinyl Based compound monomeric unit, olefinically unsaturated nitriles monomeric unit, ethylenically unsaturated carboxylic acids monomeric unit, olefinic unsaturated amides list Body unit, multifunctional olefinic type monomers unit；
(4) a kind of electro-chemical element electrode particle complex is by will be in electrode active material and (1)~(3) Obtained from any one of them electro-chemical element electrode carries out dry type mixing with adhesive；
(5) according to the electro-chemical element electrode particle complex described in (4), wherein the electro-chemical element electrode grain The volume reference D50 average grain diameters (Da) of sub- complex and the volume reference D50 average grain diameters (Db) of the electrode active material The ratio between (Da/Db) be 0.5~2；
(6) a kind of electro-chemical element electrode is that lamination includes that the electro-chemical element electrode described in (5) is used on the current collector Made of the electrode active material layer of particle complex；
(7) according to the electro-chemical element electrode described in (6), wherein the electrode active material layer is by that will include institute State electro-chemical element electrode particle complex electrode material be press-formed on the collector obtained from；
(8) a kind of electrochemical element has the electro-chemical element electrode described in (6) or (7)；
(9) a kind of manufacturing method of electro-chemical element electrode comprising：It is 35~80 that glass transition temperature, which will be dispersed with, DEG C, the volume-based average particle size D50 of primary particle be 80~1000nm the aqueous dispersion of spherical particle shaped polymer exist The dry of powdered Composite particle is obtained less than being dried under conditions of the minimum film temperature of the particle shaped polymer Drying process；The powdered Composite particle and electrode active material are subjected to dry type mixing and obtain the mixing of particle complex Process；And the electrode manufacturing process of electrode is manufactured using the particle complex.
The effect of invention
According to the present invention, it is possible to provide due to formed electrode layer when do not make slurry therefore electrode productivity it is excellent, due to Water soluble polymer is not needed as dispersant therefore can realize the thickness and precision and softness of low resistance and the electrode obtained The excellent electro-chemical element electrode adhesive of property, the electro-chemical element electrode for having used the electro-chemical element electrode adhesive With particle complex, the electro-chemical element electrode and electrochemical element of the electro-chemical element electrode particle complex are used. Further, according to the present invention, it is possible to provide the manufacture for the electro-chemical element electrode that productivity is excellent, thickness and precision and flexibility are excellent Method.
Specific implementation mode
Hereinafter, being illustrated with adhesive for the electro-chemical element electrode of the present invention.The electrochemical element electricity of the present invention Pole is characterized in that with adhesive (being also denoted as below " electrode binding agent "), is 35~80 it includes glass transition temperature DEG C, the polymer that the volume reference D50 average grain diameters of primary particle are 80~1000nm, and the adhesive waving at 120 DEG C It sends out ingredient and is less than 1 weight %, which is powdered Composite particle.
It should be noted that in the present specification, " positive active material " refers to the electrode active material of anode, " negative electrode active material " refers to the electrode active material of cathode.In addition, " positive electrode active material layer " refers to setting In the electrode active material layer of anode, " negative electrode active material layer " refers to the electrode active material layer for being set to cathode.
(electro-chemical element electrode adhesive)
The glass transition temperature (Tg) of the electrode binding agent of the present invention is 35~80 DEG C, is preferably 40~75 DEG C, more Preferably 40~70 DEG C, further preferably 40~60 DEG C, particularly preferably 45~55 DEG C.If the glass of electrode binding agent Change transition temperature in the range, then can get soft and fully intensity electrode.In addition, if the vitrifying of electrode binding agent Transition temperature is excessively high, then can become difficult to obtain the electrode with sufficient flexibility.In addition, if the glass of electrode binding agent Glass transition temperature is too low, then since the mobility of aftermentioned particle complex is insufficient, can lead to the thickness of the electrode obtained Precision is spent to be deteriorated.That is, can cause electrode that uneven thickness can occur.
Volume reference D50 average grain diameter (hereinafter also referred to " the primary grains of the primary particle of the electrode binding agent of the present invention Diameter ") it is 80~1000nm, preferably 80~800nm, more preferably 100~500nm, further preferably 130~400nm.Such as The primary particle diameter of fruit electrode binding agent then can fully keep viscous between collector and electrode active material in the range Connect intensity.In addition, if the primary particle diameter of electrode binding agent is excessive, it is aftermentioned in progress since cementability reduces It can lose powder when the flexibility experiment of electrode.In addition, if the primary particle diameter of electrode binding agent is too small, can be used because of electrode Adhesive is difficult to disperse and cementability is caused to reduce.
It should be noted that by the way that the aqueous dispersion of particle shaped polymer that polymerization as described below obtains will be utilized It is dried and electrode binding agent can be obtained, but the primary particle diameter of the particle shaped polymer in the aqueous dispersion is above range. In addition, particle shaped polymer is preferably spherical.
Particle shaped polymer refers to being set as Ls, major diameter is set as Ll and making La=(Ls+ minor axis diameter for spherical shape When the value of (1- (Ll-Ls)/La) × 100 Ll)/2, being set as sphericity (%), sphericity is 80% or more.
Here, minor axis diameter Ls and major diameter Ll is by observing the photo of transmission-type or scanning electron microscope The major diameter (Ll) and minor axis diameter (Ls) of the polymer particle of given quantity such as 10~30 measured are respective flat Mean value.In addition, La is the value that can be found out by calculating La=(Ls+Ll)/2.
In addition, volatile ingredient of the electrode binding agent of the present invention at 120 DEG C is less than 1 weight %.If electrode is used viscous Volatile ingredient of the mixture at 120 DEG C in the range, then electrode binding agent can it is uniformly dispersing, obtain that there is abundant intensity Electrode.In addition, since the mobility of aftermentioned particle complex also becomes good, the good electricity of thickness and precision can be obtained Pole.In addition, if volatile ingredient of the electrode binding agent at 120 DEG C is excessive, due to the electrode when manufacturing particle complex Do not disperseed with adhesive, therefore the electrode with abundant intensity can not be obtained, in addition, the mobility due to particle complex is not filled Point, therefore the thickness and precision of obtained electrode is deteriorated.
In addition, the electrode binding agent of the present invention is with the powder of shape (condensate of ball) made of spherical or multiple chous conjunctions The form of last shape, that is, powdered Composite particle exists.The primary particle of above-mentioned electrode binding agent can also be with separate Particulate forms exist, but be typically by multiple primary particles in the case where keeping its shape by molecular separating force etc. in conjunction with by shape At a particle.In addition, for the particle formed by multiple primary particles, lead to primary particle because of outer force effect sometimes Exist in the form of separate particle.By making the shape of electrode binding agent be shape made of spherical or multiple chous close Shape, it can be ensured that the mobility of particle complex.
The electrode binding agent of the present invention is preferably comprised selected from conjugated diene monomeric unit, (methyl) acrylate monomer list Member, aromatic vinyl compound monomer unit, olefinically unsaturated nitriles monomeric unit, ethylenically unsaturated carboxylic acids monomeric unit, alkene Belong at least one of unsaturated acyl amine monomer units, multifunctional olefinic type monomers unit monomeric unit.It should be noted that at this In specification, " (methyl) acrylic acid " expression " acrylic acid " and " methacrylic acid ".
As the conjugate diene monomer for forming conjugated diene monomeric unit, can enumerate：1,3- butadiene, isoprene, 2, The conjugated diene that the carbon atom numbers such as 3- dimethyl -1,3- butadiene, 1,3- pentadienes are 4 or more.In these, preferably 1,3- fourths Diene.
As (methyl) acrylate monomer of formation (methyl) acrylate monomeric units, can enumerate：Methyl acrylate, Ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, amyl acrylate, third The own ester of olefin(e) acid, heptylacrylate, 2-ethyl hexyl acrylate, 2-EHA, acrylic acid nonyl ester, decyl acrylate, acrylic acid The alkyl acrylates such as lauryl, n-myristyl base ester, stearyl acrylate；Methyl methacrylate, metering system Acetoacetic ester, n propyl methacrylate, isopropyl methacrylate, n-BMA, Tert-butyl Methacrylate, first Base amyl acrylate, hexyl methacrylate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, methacrylic acid 2- ethyl hexyls Ester, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid n-tetradecane base ester, methyl Alkyl methacrylates such as stearyl acrylate etc..Wherein, since the flexibility of electrode can be improved, when making winding battery Can inhibit the stripping of electrode, and used the characteristic (cycle characteristics etc.) of the secondary cell of the electrode excellent, thus preferably with it is non- The alkyl acrylate or alkyl methacrylate that the carbon atom number for the alkyl that carbonyl oxygen atom combines is 4 or more, it is more excellent It is 6 or more and 20 alkyl acrylates or metering system below to select the carbon atom number of the alkyl combined with non-carbonyl oxygen atom Acid alkyl ester.
As the aromatic vinyl compound monomer for forming aromatic vinyl compound monomer unit, can enumerate：Benzene Ethylene, α-methylstyrene, vinyltoluene etc..
As α, the monomer of β-olefinically unsaturated nitriles monomeric unit is formed, as long as the α with itrile group, β-olefinic are unsaturated Compound does not limit then, can enumerate：Acrylonitrile；The alpha-halogenates acrylonitrile such as α-chloro-acrylonitrile, α-bromopropene nitrile；Methacrylonitrile Equal alpha-alkyls acrylonitrile；Etc., preferably acrylonitrile and methacrylonitrile.As α, β-olefinically unsaturated nitriles monomer, can also incite somebody to action Multiple combinations in these use.
As the ethylenically unsaturated carboxylic acids monomer for forming ethylenically unsaturated carboxylic acids monomeric unit, can enumerate：Acrylic acid, methyl Acrylic acid, maleic acid, fumaric acid, itaconic acid etc..
As the olefinic unsaturated acyl amine monomers for forming olefinic unsaturated acyl amine monomer units, can enumerate：(methyl) propylene Amide, N- methylols (methyl) acrylamide, N, N'- dihydroxymethyls (methyl) acrylamide etc..
The multifunctional olefinic with 2 or more olefinic double bonds as the multifunctional ethylenically unsaturated monomer unit of formation is not It is saturated monomer, can be enumerated：The divinyl compounds such as divinylbenzene；Ethylene glycol two (methyl) acrylate, diethylene glycol two Two (methyl) esters of acrylic acid such as (methyl) acrylate, ethylene glycol two (methyl) acrylate；Trimethylolpropane tris (first Base) the trimethyl acrylic esters class such as acrylate；Etc..
For making the method for each monomer polymerization without particularly system limit, but for example it is preferable to use following methods：Use 12 The emulsifiers such as sodium alkyl benzene sulfonate obtain the emulsion polymerization of the latex (aqueous dispersion) of particle shaped polymer, using polyvinyl alcohol Equal dispersants obtain suspension polymerization (also including micro-suspension polymerization) of the aqueous dispersion of particle shaped polymer etc..In these sides In method, since polymerization reactor control is easy, more preferable emulsion polymerization.
In addition, the electrode binding agent of the present invention can be obtained by keeping the polymer obtained from each monomer polymerization dry .That is, by making polymer dry, can obtain (powdered viscous as the electrode binding agent of powdered Composite particle Mixture).For drying means, if will not make the primary particle of particle shaped polymer to each other exceedingly bonding, can be with The state of redisperse is dried, and is not particularly limited, but it can be mentioned, for example：Make the aqueous dispersion of particle shaped polymer The method of spray drying, the method etc. being dried using Rotary Evaporators.In addition, more preferably being steamed using spray drying, rotation After hair instrument is dried, it is dried under vacuum.
As drying temperature, never cause the primary particle of particle shaped polymer to each other exceedingly bonding, can be with The dewatered viewpoint of state of redisperse is set out, preferably shorter than the temperature of the minimum film temperature of particle shaped polymer.If Drying temperature is excessively high, then is difficult to carry out redisperse due to that can cause particle shaped polymer that membranization occurs.
In addition, from that can be made with the state of redisperse, particle shaped polymer is dry, can take into account aftermentioned particle complex Mobility and electrode formed after electrode flexibility from the perspective of, the minimum film temperature of particle shaped polymer is preferably 35~100 DEG C.If the minimum film temperature of particle shaped polymer is excessively high, the flexibility of the electrode obtained can be caused to decline.Separately Outside, it if the minimum film temperature of particle shaped polymer is too low, is difficult in the primary particle mistake for not leading to particle shaped polymer It is made it dry in the case of degree bonding.I.e., it is difficult to make particle shaped polymer and be dried with the state for capableing of redisperse.
Here, minimum film temperature is the minimum temperature for the film that can form above-mentioned particle shaped polymer.Minimum film temperature Such as it can be measured based on JIS K6828-2 (2003), ISO 2115.Specifically, with proper temperature gradient It the aqueous dispersions of coated particle shaped polymer and is dried on the tablets such as iron plate, reaches about 100 μm of thickness, and measure The critical-temperature between the part of membranization and the part that membranization does not occur has occurred.Here, since the part that membranization has occurred becomes It is transparent, and the part that membranization does not occur is in gonorrhoea, therefore can be confirmed by range estimation and the part of membranization has occurred and not send out The boundary of the part of filming.In addition, due to being carried out in the tablet to the aqueous dispersion of coated particle shaped polymer and after drying In the case of rubbing, the part of membranization does not occur to lose powder, accordingly it is also possible to be had occurred according to the presence or absence of picking to confirm The part of membranization and do not occur membranization part boundary.
(electro-chemical element electrode particle complex)
The electro-chemical element electrode of present invention particle complex (hereinafter also referred to " particle complex ") includes above-mentioned electricity Pole adhesive and electrode active material.Particle complex can also include conductive agent as needed.Here, compound in particle In body, electrode binding agent and electrode active material can also exist in the form of separate particle respectively, but be typically Adhere to multiple electrodes adhesive on the surface of electrode active material and forms a particle.In turn, electrode binding agent and electricity The respective independent particle of pole active material and above-mentioned particle, with substantially keep the state of shape by it is multiple in conjunction with and Form offspring.In addition, for the offspring, in the case where being subject to external force, primary particle is sometimes with respective The form of independent particle exists.
(electrode active material)
Electrochemical element as the present invention is the positive active material in the case of lithium rechargeable battery, and energy can be used The active material of enough doping and dedoping lithium ion, is roughly divided into the active material being made of inorganic compound and by organising Close the active material that object is constituted.
As the positive active material being made of inorganic compound, can enumerate：Transition metal oxide, Transition Metal Sulfur The lithium-contained composite metal oxide etc. that compound, lithium and transition metal are formed.As above-mentioned transition metal, can use Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc..
As transition metal oxide, can enumerate：MnO、MnO2、V2O5、V6O13、TiO2、Cu2V2O3, noncrystalline V2O- P2O5、MoO3、V2O5、V6O13Deng, wherein from the viewpoint of cyclical stability and capacity, preferably MnO, V2O5、V6O13、TiO2。 As transient metal sulfide, can enumerate：TiS2、TiS3, noncrystalline MoS2, FeS etc..As lithium-contained composite metal oxide, It can enumerate：Lithium-contained composite metal oxide with layer structure, the lithium-contained composite metal oxide with spinel structure, Lithium-contained composite metal oxide etc. with olivine-type structure.
As the lithium-contained composite metal oxide with layer structure, can enumerate：Cobalt/cobalt oxide (LiCoO containing lithium2)、 Nickel oxide (LiNiO containing lithium2), the lithium composite xoide of Co-Ni-Mn, the lithium composite xoide of Ni-Mn-Al, Ni-Co-Al Lithium composite xoide etc..As the lithium-contained composite metal oxide with spinel structure, can enumerate：LiMn2O4 (LiMn2O4), by a part of Mn Li [Mn made of other transition metal substitutions3/2M1/2]O4(here, M be Cr, Fe, Co, Ni, Cu etc.) etc..As the lithium-contained composite metal oxide with olivine-type structure, can enumerate：LixMPO4(in formula, M tables Show at least one kind of in Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and Mo, 0≤X≤2) shown in Olivine-type lithium phosphate compound.
As organic compound, it can also use such as polyacetylene, gather to electroconductive polymer benzene.Not for electric conductivity The ferrous oxide of foot can be covered to be made by carbon material by carrying out making carbon source material exist when reduction is fired The positive active material of lid uses.In addition it is also possible to carry out substance made of Partial Elements displacement using to these compounds.Just Pole active material may be the mixture of above-mentioned inorganic compound and organic compound.
Positive active material in the case of being lithium-ion capacitor as electrochemical element, as long as can reversibly bear Carry the substance of anion as lithium ion and such as tetrafluoroborate.Specifically, preferably different using the homoatomic of carbon Body can be widely used in the electrode active material used in double layer capacitor.Allotrope as carbon it is specific Example, can enumerate：Activated carbon, polyacene (PAS), carbon whisker, carbon nanotube and graphite etc..
Electrochemical element as the present invention be lithium rechargeable battery in the case of negative electrode active material, such as can be with It enumerates：The carbonaceous materials such as amorphous carbon, graphite, natural graphite, carbonaceous mesophase spherules, pitch-based carbon fiber；The conductions such as polyacene Property macromolecule；The metals such as silicon, tin, zinc, manganese, iron, nickel or their alloy；The oxide or sulfate of above-mentioned metal or alloy； Lithium metal；The lithium alloys such as Li-Al, Li-Bi-Cd, Li-Sn-Cd；Lithium transition-metal nitride；Silicon etc..In addition, living as cathode Property substance, can also use be attached to conductive agent for example, by mechanically modifying method on the surface of the particle of the negative electrode active material and At substance.In addition, negative electrode active material can be used alone, two or more can also be applied in combination with arbitrary ratio.
In addition, as electrochemical element be lithium-ion capacitor in the case of it is preferable to use negative electrode active material, can Enumerate the negative electrode active material formed by above-mentioned carbon.
Typically for the grain size of the particle of electrode active material, it may be considered that wanted to other compositions with electrochemical element Balance between element and suitably select.Wherein, from the viewpoint for improving the battery behaviors such as initial efficiency, part throttle characteristics, cycle characteristics It sets out, the particle volume benchmark D50 average grain diameters of electrode active material are preferably 1~50 μm, more preferably 15~30 μm.
From the capacity that can improve lithium rechargeable battery and can improve electrode flexibility and collector and From the perspective of caking property between electrode active material layer, the content of electrode active material is preferably in electrode active material layer 90~99.9 weight %, more preferably 95~99 weight %.
(conductive agent)
In addition, as in the present invention as needed and the conductive agent that uses, it is preferable to use furnace black, acetylene black (hereinafter, also simple Referred to as " AB ") and the Ketjen black (registration of Akzo Nobel Chemicals Besuroten Fen notes shut up companies Trade mark), carbon nanotube, carbon nanohorn, the conductive carbons such as graphene.In these, more preferable acetylene black.The average grain of conductive agent Diameter is not particularly limited, but from the viewpoint of playing sufficient electric conductivity with less usage amount, preferably compares electrode activity The average grain diameter of substance is small, preferably 0.001~10 μm, more preferably 0.005~5 μm, further preferably 0.01~1 μm.
In the case where adding conductive agent, the usage amount of conductive agent is preferably 1 relative to 100 parts by weight of electrode active material ~10 parts by weight, more preferably 1~5 parts by weight.
(manufacturing method of particle complex)
Particle complex can by by electrode binding agent, electrode active material and conductive agent used as needed into Row dry type mixing and obtain." dry type mixing " designated herein refers to, using mixing machine to electrode binding agent, electrode activity thing Matter and conductive agent used as needed are mixed, specifically, referring to so that solid component concentration when mixing is 99 The mode of weight % or more is mixed.As specific mixed method, can enumerate：By container self-oscillation, rotation or Vibration is come container paddling process being mixed, using shaker mixer (Rocking Mixer), rotary drum mixer etc.；Make With the mixing for being equipped with the blade for stirring, rotating disk or screw rod etc. in the rotary shaft in relative to container horizontally or vertically Machine, i.e. Fast Rotating Cylinder, V-Mixer, ribbon stirrer, pyramid type screw mixer, the mixing of high velocity stream ejector half The mechanical stirring of machine, rotary disk type mixing machine and high speed rotational blade mixing machine etc.；Utilize returning based on compressed gas Rotational gas flow, powder is mixed in a fluidized bed airflow stirring etc..Alternatively, it is also possible to use by these mechanisms individually or Mixing machine made of being applied in combination.Alternatively, it is also possible to after carrying out dry type mixing, using mortar etc. be crushed to break it is solidifying Poly- degree.By carrying out dry type mixing, the dispersion of electro-chemical element electrode particle complex is kept well, in turn, Each physical property such as coating accuracy is improved.
The volume reference of volume reference D50 average grain diameters (Da) and electrode active material of the particle complex of the present invention The ratio between D50 average grain diameters (Db) (Da/Db) is preferably 0.5~2, more preferably 0.8~2.That is, it is preferred that multiple electrodes active material Without Composite.
(electro-chemical element electrode)
The electro-chemical element electrode of the present invention is that the electrode active material layer containing above-mentioned particle complex is stacked in collection Electrode made of on electric body.As the material of collector, it is, for example, possible to use metal, carbon, electroconductive polymer etc., preferably make Use metal.As metal, usually using copper, aluminium, platinum, nickel, tantalum, titanium, stainless steel, other alloys etc..Among these, from conduction It sets out, it is preferable to use copper, aluminum or aluminum alloy in terms of property, proof voltage.In addition, in the case where requiring high proof voltage, it can To be preferably used in the aluminium of high-purity disclosed in Japanese Unexamined Patent Publication 2001-176757 bulletins etc..Collector be film or sheet, Thickness can suitably be selected according to purpose is used, preferably 1~200 μm, more preferably 5~100 μm, further preferably 10~ 50μm。
When by electrode active material layer lamination on the current collector, particle complex can be shaped to sheet and then lamination On the current collector, but preferably the method for direct weighting shaped particle complex on the current collector.As the side being press-formed Method can be enumerated for example：Using the roll-type pressing shaping device for having a pair of rolls, while transmitting collector with roller, utilize The feedways such as screw feeder supply particle complex to roll-type pressing shaping device, thus shaped electrode on the current collector The roller extrusion forming method of active material layer；Particle complex is spread on the current collector, is spread out particle complex using scraper etc. It puts down to adjust thickness, then pressue device is utilized to carry out molding method；In a mold by particle complex filling, and to mold It is pressurizeed and molding method etc..Among these, preferred roller extrusion forming method.Especially since the particle complex of the present invention With high fluidity, therefore it can supplied using constant feeder, make to pass through after powder layer is uniform using scraper etc. Roller is molded, it is possible thereby to improve productivity.
It is close between electrode active material layer and collector from that can make for roll temperature when carrying out roller extrusion forming From the perspective of conjunction property is abundant, preferably 25~200 DEG C, more preferably 50~150 DEG C, further preferably 80~120 DEG C.This Outside, the compacting line pressure between roller when being press-formed as roller, from the homogeneity of the thickness that can improve electrode active material layer Viewpoint is set out, preferably 10~1000kN/m, more preferably 200~900kN/m, further preferably 300~600kN/m.This Outside, shaping speed when roller is press-formed is preferably 0.1~20m/ minutes, more preferably 4~10m/ minutes.
In addition, in order to make the thickness of molding electro-chemical element electrode there is no deviation, the close of electrode active material layer is improved Degree, to seek high capacity, pressurizes after can further carrying out as needed.The method pressurizeed afterwards is carried out preferably by roller Pressurization operation.In roller pressurization operation, by by 2 columned rollers with it is narrow it is spaced and parallel be arranged above and below, make respectively It rotates, and holding electrode therebetween, thus pressurizes in the opposite direction.At this point, as needed, can also two pairs of rollers added The temperature such as heat or cooling are adjusted.
(electrochemical element)
The electro-chemical element electrode obtained as described above is used in anode and cathode extremely by the electrochemical element of the present invention Few one, and it is further equipped with partition board and electrolyte.As electrochemical element, it can be mentioned, for example lithium rechargeable battery, lithium from Sub-capacitor etc..
(partition board)
As partition board, the micropore comprising the vistanexes such as polyethylene, polypropylene, aromatic polyamide resin can be used Film or non-woven fabrics；Include the porous resin coating etc. of inorganic ceramic powder.As concrete example, can enumerate：By polyolefins The microporous membrane that (polyethylene, polypropylene, polybutene, polyvinyl chloride) and the resins such as their mixture or copolymer are formed； By polyethylene terephthalate, polycyclic alkene, polyether sulfone, polyamide, polyimides, polyimide amide, Nomex, The microporous membrane that the resins such as polycyclic alkene, nylon, polytetrafluoroethylene (PTFE) are formed；Weave polyolefins fiber made of material or its Non-woven fabrics；The aggregation etc. of insulating properties material particle.Among these, due to can be thinned the film thickness of partition board entirety, increase lithium from Active material ratio in sub- secondary cell, to improve the capacity of per unit volume, therefore preferably by the resin of polyolefins The microporous membrane of formation.
For the thickness of partition board, from the sight that can reduce the internal resistance caused by partition board in lithium rechargeable battery From the perspective of point and workability when manufacturing lithium rechargeable battery are excellent, preferably 0.5~40 μm, more preferably 1 ~30 μm, further preferably 1~25 μm.
(electrolyte)
As the electrolyte of lithium rechargeable battery, such as it may be used at dissolving supporting electrolyte in nonaqueous solvents and forms Nonaqueous electrolytic solution.As supporting electrolyte, it is preferred to use lithium salts.As lithium salts, can enumerate for example：LiPF6、LiAsF6、 LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、 (C2F5SO2) NLi etc..Wherein, preferably it is easily dissolved in solvent and shows the LiPF of high dissociation degree6、LiClO4、CF3SO3Li。 These can be used alone, two or more can also be applied in combination with arbitrary ratio.Use the higher support electricity of degree of dissociation Solving matter, then lithium ion conductivity is higher, therefore, can adjust lithium ion conductivity according to the type of supporting electrolyte.
For the concentration of the supporting electrolyte in electrolyte, preferably according to the type of supporting electrolyte, with 0.5~ The concentration of 2.5mol/L uses.The concentration of supporting electrolyte is too low or excessively high in the presence of the possibility for causing ionic conductance degree to reduce Property.
As nonaqueous solvents, it is not particularly limited as long as being the solvent that can dissolve supporting electrolyte.As non-aqueous The example of agent can be enumerated：Dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), the carbonates such as butylene carbonate (BC), methyl ethyl carbonate (MEC)；The esters such as gamma-butyrolacton, methyl formate；1,2- bis- The ethers such as Ethyl Methyl Ether, tetrahydrofuran；The sulfur-containing compounds class such as sulfolane, dimethyl sulfoxide；Used also as supporting electrolyte Ionic liquid etc..Wherein, since the potential range that dielectric constant is high, stablizes is wide, preferred carbonates.Nonaqueous solvents can be with It is used alone a kind, two or more can also be applied in combination with arbitrary proportion.Usually, the more low then lithium ion of the viscosity of nonaqueous solvents Conductivity is higher, and the solubility of the more high then supporting electrolyte of dielectric constant is higher, but the two is in the pass of compromise (trade off) System, therefore lithium ion conductivity can be adjusted according to the type of solvent, mixing ratio and used.In addition, nonaqueous solvents can group Close solvent made of use or entirety are replaced using all or part of hydrogen by fluorine.
In addition, additive can also be contained in electrolyte.As additive, for example,：Vinylene carbonate (VC) carbonats compounds such as；The sulfur-containing compounds such as glycol sulfite (ES)；Fluoroethylene carbonate (FEC) etc. is containing fluorination Close object.Additive can be used alone a kind, can also use two or more with arbitrary ratio combine.
It should be noted that the electrolyte as lithium-ion capacitor, can use and can be used for lithium ion with above-mentioned The same electrolyte of electrolyte of secondary cell.
(manufacturing method of electrochemical element)
As the specific manufacturing method of the electrochemical elements such as lithium rechargeable battery, lithium-ion capacitor, such as can be with It is listed below method：Across partition board overlap anode and cathode, and by its according to cell shapes curling, bending etc. after be put into battery hold Device injects electrolyte to battery case and seals.Further, can also expansion alloy be put into as needed；Fuse, PTC The overcurrent preventing elements such as element；Lead plate etc., to prevent the pressure rise of inside battery, cross charge and discharge.Lithium ion secondary The shape of battery can be the arbitrary shape in Coin shape, coin shape, piece type, cylinder type, square, platypelloid type etc..Battery is held For the material of device, as long as the material of moisture intrusion inside battery can be hindered, it is not particularly limited in made of metal, aluminium etc. Laminated material etc..
Electro-chemical element electrode adhesive according to the present embodiment, the productivity of electrode is excellent, obtained electrode Thickness and precision and flexibility are good.Further, since the electro-chemical element electrode of the present invention is without using dispersions such as carboxymethyl celluloses Agent, therefore the resistance for the electrochemical element that can be reduced.
In addition, by making the glass transition temperature of electrode binding agent in given range, even obtained particle Complex is that mobility is also ensured in small particle, therefore can ensure the thickness and precision of electrode.Further, by making electrochemistry The glass transition temperature of element electrode adhesive is in given range, it can be ensured that the intensity and softness of obtained electrode Property.
In addition, due to not using slurry when obtaining particle complex, the spent energy of manufacture can be reduced.Into One step is easy due to operating continuously, can improve yield rate.
Embodiment
Hereinafter, the present invention is concretely demonstrated in conjunction with the embodiments, but the present invention is not limited to realities as shown below Example is applied, can arbitrarily be changed in the range of no more than the range of the gist of the invention and its equalization to implement.It needs to illustrate , in the following description, " % " and " part " of expression amount is then weight basis unless otherwise specified.
In Examples and Comparative Examples, being proceed as follows electrode binding agent respectively, (cathode adhesive or anode are used Adhesive) glass transition temperature (Tg) measurement, the volume reference D50 average grain diameters (primary particle diameter) of primary particle survey Fixed, the volume reference D50 average grain diameters (Da) of particle complex and electrode active material volume reference D50 average grain diameters (Db) measurement, electrode binding agent 120 DEG C of volatile ingredients measure, the measurement of the minimum film temperature of electrode binding agent and The measuring shape of electrode binding agent.
<Glass transition temperature>
The glass transition temperature (Tg) of electrode binding agent uses differential scanning calorimeter (Nanotechnology companies DSC6220SII processed), be based on JIS K 7121:1987 are determined.
<The measurement of primary particle diameter>
Add the electrode binding of Examples and Comparative Examples manufacture respectively into 1% aqueous solution of sodium n-alkylbenzenesulfonate Agent (cathode adhesive 1~12, positive electrode binder 1~13), it is decentralized using ultrasonic wave progress, it is then based on utilization Particle diameter distribution is accumulated obtained from Coulter Counter LS230 (Coulter corporation particle size determinations device) to be measured, it will It is equivalent to volume reference D50 average grain diameter (primary particle diameter) of the grain size as electrode binding agent of its 50% accumulated value.
<The measurement of Da and Db>
Based on utilization laser diffraction/scattering formula particle size distribution device (Microtrac MT3200II；Day machine fills) To dry type accumulation particle size distribution measuring Examples and Comparative Examples in the volume reference D50 of particle complex that manufactures it is average The volume reference D50 average grain diameters (Db) of the electrode active material used in grain size (Da) and Examples and Comparative Examples, find out Than (Da/Db).
<The measurement of 120 DEG C of volatile ingredients>
The powdered cathode adhesive manufactured in Examples and Comparative Examples is respectively put into the baking oven for being set as 120 DEG C 1~12, powdered positive electrode binder 1~13, the every 10 minutes measurement for carrying out binder wt, reaches in weight change and is less than It terminates and measures at the time of 0.1%.By played at this time from initial stage weight measure terminate when until the weight rate (ratio of reduction Example) it is used as 120 DEG C of volatile ingredients.
<Minimum film temperature>
Use minimum film temperature measuring apparatus (MFFTB90；RHOPOINT corporations), tried according to ISO2115 It tests.
<Measuring shape>
Powdered electrode adhesive is observed using SEM, it is random to take out 30, the particle observed in image, it finds out each Average minor axis diameter, the average major axis diameter of particle, and calculate average spherical degree.It is 80% or more by average spherical degree at this time Situation is considered as particle of spherical, the average spherical degree less than 80% and is considered as non-spherical.
In addition, in Examples and Comparative Examples, it is special that it has been proceed as follows electrode precision, the flexibility of electrode and rate respectively The evaluation of property.
<Electrode precision>
For the direction 10cm, MD on the directions TD (transverse direction) of the electrode active material layer made in Examples and Comparative Examples 10cm on (longitudinal direction), determine equably taken on the directions TD 3 points, equably take in the MD direction 3 points, total 9 points of film It is thick.When being set as A by the average value of the film thickness, the farthest thickness of distance average is set as B, thickness of electrode is calculated using following formula Deviation.
Thickness of electrode deviation precision (%)=(| A-B |) × 100/A
As electrode precision, evaluated using benchmark below.As a result as shown in table 1 and table 2.The value is smaller Indicate that mouldability is more excellent.
A：Less than 4%
B：4% less than 9%
C：9% less than 15%
D：15% or more
E：There is hole on electrode
<The flexibility of electrode>
The electro-chemical element electrode made in Examples and Comparative Examples is cut into 1cm × 8cm, wrap around diameter 3mm, The metal bar of 4mm, 5mm have been proceed as follows evaluation for the crackle of generation.As a result as shown in table 1 and table 2.The fewer table of crackle Show that flexibility is more excellent, that is, indicates that pole strength is more excellent.
A：There is no crackle on the metal bar of diameter 3mm
B：There is no crackle on the metal bar of diameter 4mm, but there are crackles on the metal bar of diameter 3mm
C：There are crackles on the metal bar of diameter 5mm
<Speed characteristic>
Lithium rechargeable battery for the lamination pack type made in Examples and Comparative Examples, after injecting electrolytic solution, 5 hours are stood, it is 3.65V to charge to cell voltage by the constant flow method of 0.2C in 25 DEG C of atmospheres, then heats to 60 DEG C, 12 hours maturation process are carried out, it is 3.00V to be discharged to cell voltage by the constant flow method of 0.2C in 25 DEG C of atmospheres.
Then, in 25 DEG C of atmospheres, charging has been carried out with 4.2V, 0.2C rate, has been carried out with 0.2C and 2.0C rates Electric discharge.At this point, discharge capacity when by each discharge rate is defined as C0.2(discharge capacity when 0.2C), C2.0(when 2.0C Discharge capacity), it finds out with Δ C=C2.0/C0.2When the Capacitance Shift Rate that indicates of discharge capacity × 100 (%), and according to following Benchmark evaluated.As a result as shown in table 1 and table 2.The value of Capacitance Shift Rate Δ C is higher, indicates discharging-rate performance (speed characteristic) is more excellent.
A：Δ C is 83% or more
B：Δ C is 82% less than 83%
C：Δ C is 80% less than 82%
D：Δ C is less than 80%
<Embodiment 1>
(manufacture of cathode particle shaped polymer 1)
78 parts of styrene (hereinafter also referred to as " ST "), 1,3- butadiene are added into the 5MPa pressure vessels with blender 19 parts of (hereinafter also referred to as " BD "), 3 parts of itaconic acid (hereinafter also referred to as " IA "), two sulphur of alkyl diphenyl ether as emulsifier Hydrochlorate (DOWFAX (registered trademark) 2A1, Dow Chemical corporations) is with solid constituent when 0.4 part of gauge, ion exchange water 150 parts, as 0.3 part of the tert-dodecylmercaotan (hereinafter also referred to as " TDM ") of chain-transferring agent and as polymerization initiator 0.5 part of potassium peroxydisulfate, carry out adequately stir after, be heated up to 75 DEG C with causes polymerize.Reach 96% in polymerisation conversion Moment is cooled down, and is stopped reaction, has been obtained 1 (styrene-butadiene copolymer of cathode particle shaped polymer；Also simple below Referred to as " SBR ") aqueous dispersion.The minimum film temperature of cathode particle shaped polymer 1 is 55 DEG C, glass transition temperature (Tg) it is 50 DEG C, primary particle diameter 132nm.
(drying of particle shaped polymer and broken)
Moisture is removed in the aqueous dispersion of particle shaped polymer 1 from above-mentioned cathode in 40 DEG C using Rotary Evaporators, so It is made it dry under conditions of 40 DEG C, 0.6kPa using vacuum drier afterwards.Then, dried cathode is crushed using mortar to use Particle shaped polymer 1 has obtained powdered cathode adhesive 1.120 DEG C of powdered cathode adhesive 1 are volatilized into It is divided into 0.1%.
(manufacture of particle complex)
By the artificial graphite (average grain diameter as negative electrode active material：24.5 μm, graphite layers away from (be based on X-ray diffraction The face interval (d values) in (002) face that method measures)：0.354nm) 98.8 parts and above-mentioned cathode are changed with adhesive with solid constituent 1.2 parts of gauge is calculated, is mixed 10 minutes using Henschel mixer (three wells, three pond corporation), makes cathode adhesive attachment in negative Pole active material, has obtained particle complex.
(manufacture of cathode)
Particle complex obtained above is supplied using constant feeder (Nikka corporations " Nikka spray K-V ") To compacting roller (100 DEG C of roll temperature, the compacting to roll squeezer (HIRANO GIKENKOGYO corporations " shearing asperities hot-rolling ") Line presses 500kN/m).The copper foil of 20 μm of inserting thickness between compacting roller, keeps the above-mentioned particle supplied from constant feeder compound Body is attached on copper foil, is press-formed within 1.5m/ minutes with shaping speed, and the cathode with negative electrode active material has been obtained.
(manufacture of anode slurry and anode)
To LiCoO as a positive electrode active material2The Kynoar as positive electrode binder is added in 92 parts (PVDF；Kureha Chemical corporations " KF-1100 ") and solid content is made to reach 2 parts, then, acetylene black is added 6 parts of (Denki Kagaku Kogyo kabushiki's system " HS-100 "), 20 parts of N-Methyl pyrrolidone, are mixed using planetary-type mixer, Anode slurry is obtained.The anode is coated on to the aluminium foil of 18 μm of thickness with slurry, after 120 DEG C 30 minutes dry, is carried out Roll-in has obtained the anode of 60 μm of thickness.
(preparation of partition board)
By the polypropylene partition board (wide 65mm, long 500mm, 25 μm of thickness, manufactured using dry process, the porosity 55%) of single layer It is punched to 5 × 5cm2Square.
(manufacture of lithium rechargeable battery)
As the outer packing of battery, aluminium housing material is prepared.Anode obtained above is punched to 4 × 4cm2Just It is rectangular, it is configured in a manner of so that the surface on current collection side is contacted with aluminium housing material.In addition, it is obtained above just The partition board of square obtained above is configured on the face of the positive electrode active material layer of pole.Then, cathode obtained above is cut At 4.2 × 4.2cm2Square, by make the surface of negative electrode active material layer side towards partition board in a manner of configure on partition board.Into One step is filled with the LiPF of containing 2.0% vinylene carbonate, a concentration of 1.0M6Solution.The LiPF6The solvent of solution is The mixed solvent (EC/EMC=3/7 (volume ratio)) of ethylene carbonate (EC) and methyl ethyl carbonate (EMC).In turn, in order to by aluminium The opening of packaging material seals, and is sealed in 150 DEG C and seals aluminium outer packing, and the lithium ion secondary electricity of laminated-type has been manufactured Pond (laminated-type battery).
<Embodiment 2>
(manufacture of cathode particle shaped polymer 2)
74.5 parts of styrene, 22.5 parts of 1,3- butadiene, itaconic acid 3 are added into the 5MPa pressure vessels with blender Part, as emulsifier alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) with solid Body ingredient works as 0.4 part of gauge, 150 parts of ion exchange water, as 0.3 part of the tert-dodecylmercaotan of chain-transferring agent and as poly- 0.5 part of the potassium peroxydisulfate of initiator is closed, is carried out after adequately stirring, is heated up to 75 DEG C to cause polymerization.It is reached in polymerisation conversion It is cooled down at the time of to 96%, stops reaction, obtained the aqueous dispersion of cathode particle shaped polymer 2.Particle shape polymerize The minimum film temperature of object 2 is 40 DEG C, and glass transition temperature (Tg) is 40 DEG C, primary particle diameter 135nm.
(drying of particle shaped polymer and broken)
Moisture is removed in the aqueous dispersion of particle shaped polymer 2 from above-mentioned cathode in 25 DEG C using Rotary Evaporators, so It is made it dry under conditions of 25 DEG C, 0.6kPa using vacuum drier afterwards.Then, dried cathode is crushed using mortar to use Particle shaped polymer 2 has obtained powdered cathode adhesive 2.120 DEG C of powdered cathode adhesive 2 are volatilized into It is divided into 0.1%.
Other than having used above-mentioned cathode adhesive 2, carried out similarly to Example 1 cathode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 3>
(manufacture of cathode particle shaped polymer 3)
85 parts of styrene is added into the 5MPa pressure vessels with blender, 12 parts of 1,3- butadiene, 3 parts of itaconic acid, makees For emulsifier alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) with solid at Divide and draws when 0.4 part of gauge, 150 parts of ion exchange water, as 0.3 part of the tert-dodecylmercaotan of chain-transferring agent and as polymerization 0.5 part of the potassium peroxydisulfate of agent is sent out, is carried out after adequately stirring, is heated up to 75 DEG C to cause polymerization.Reach in polymerisation conversion It is cooled down at the time of 96%, stops reaction, obtained the aqueous dispersion of cathode particle shaped polymer 3.Cathode particle shape The minimum film temperature of polymer 3 is 88 DEG C, and glass transition temperature (Tg) is 70 DEG C, primary particle diameter 134nm.
(drying of particle shaped polymer and broken)
Moisture is removed in the aqueous dispersion of particle shaped polymer 3 from above-mentioned cathode in 60 DEG C using Rotary Evaporators, so It is made it dry under conditions of 60 DEG C, 0.6kPa using vacuum drier afterwards.Then, dried cathode is crushed using mortar to use Particle shaped polymer 3 has obtained powdered cathode adhesive 3.120 DEG C of powdered cathode adhesive 3 are volatilized into It is divided into 0.1%.
Other than having used above-mentioned cathode adhesive 3, carried out similarly to Example 1 cathode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 4>
(manufacture of cathode particle shaped polymer 4)
78 parts of styrene is added into the 5MPa pressure vessels with blender, 19 parts of 1,3- butadiene, 3 parts of itaconic acid, makees For emulsifier alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) with solid at Divide and draws when 2.0 parts of gauge, 150 parts of ion exchange water, as 0.3 part of the tert-dodecylmercaotan of chain-transferring agent and as polymerization 0.5 part of the potassium peroxydisulfate of agent is sent out, is carried out after adequately stirring, is heated up to 75 DEG C to cause polymerization.Reach in polymerisation conversion It is cooled down at the time of 96%, stops reaction, obtained the aqueous dispersion of cathode particle shaped polymer 4.Cathode particle shape The minimum film temperature of polymer 4 is 53 DEG C, and glass transition temperature (Tg) is 50 DEG C, primary particle diameter 80nm.
(drying of particle shaped polymer and broken)
Moisture is removed in the aqueous dispersion of particle shaped polymer 4 from above-mentioned cathode in 40 DEG C using Rotary Evaporators, so It is made it dry under conditions of 40 DEG C, 0.6kPa using vacuum drier afterwards.Then, dried cathode is crushed using mortar to use Particle shaped polymer 4 has obtained powdered cathode adhesive 4.120 DEG C of powdered cathode adhesive 4 are volatilized into It is divided into 0.4%.
Other than having used above-mentioned cathode adhesive 4, carried out similarly to Example 1 cathode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 5>
(manufacture of cathode particle shaped polymer 5)
210 parts of ion exchange water is added into the 5MPa pressure vessels with blender, is heated to 75 DEG C while stirring, and will 1.96% 25.5 parts of persulfate aqueous solution is added to reactor.Then, to unlike those described above other with blender In 5MPa pressure vessels be added 78 parts of styrene, 19 parts of 1,3- butadiene, 3 parts of itaconic acid, as the alkyl diphenyl ether of emulsifier Disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) is using solid constituent when 0.4 part of gauge, as chain 26 parts of 0.3 part of the tert-dodecylmercaotan of transfer agent and ion exchange water, are stirred it emulsification, to be prepared for monomer Mixed liquor.Then, in the state of making the monomer mixed solution stirring and emulsifying, through 3.5 hours with constant speed, which is mixed It closes liquid and is added to the reactor for having fed 210 parts of ion exchange water and persulfate aqueous solution, make its reaction until polymerization turns Rate reaches 95%, has obtained the aqueous dispersion of cathode particle shaped polymer 5.The minimum system of cathode particle shaped polymer 5 Film temperature is 56 DEG C, and glass transition temperature (Tg) is 50 DEG C, primary particle diameter 304nm.
(drying of particle shaped polymer and broken)
Moisture is removed in the aqueous dispersion of particle shaped polymer 5 from above-mentioned cathode in 40 DEG C using Rotary Evaporators, so It is made it dry under conditions of 40 DEG C, 0.6kPa using vacuum drier afterwards.Then, dried cathode is crushed using mortar to use Particle shaped polymer 5 has obtained powdered cathode adhesive 5.120 DEG C of powdered cathode adhesive 5 are volatilized into It is divided into 0.1%.
Other than having used above-mentioned cathode adhesive 5, carried out similarly to Example 1 cathode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 6>
(manufacture of cathode particle shaped polymer 6)
210 parts of ion exchange water is added into the 5MPa pressure vessels with blender, is heated to 75 DEG C while stirring, and will 1.96% 25.5 parts of persulfate aqueous solution is added to reactor.Then, to unlike those described above other with blender In 5MPa pressure vessels be added 78 parts of styrene, 19 parts of 1,3- butadiene, 3 parts of itaconic acid, as the alkyl diphenyl ether of emulsifier Disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) is using solid constituent when 0.2 part of gauge, as chain 26 parts of 0.3 part of the tert-dodecylmercaotan of transfer agent and ion exchange water, are stirred it emulsification, to be prepared for monomer Mixed liquor.Then, in the state of making the monomer mixed solution stirring and emulsifying, through 3.5 hours with constant speed, be added into Material has the reactor of 210 parts of ion exchange water and persulfate aqueous solution, its reaction is made to obtain until polymerisation conversion reaches 95% The aqueous dispersion of cathode particle shaped polymer 6 is arrived.The minimum film temperature of cathode particle shaped polymer 6 is 56 DEG C, glass Glass transition temperature (Tg) is 50 DEG C, primary particle diameter 625nm.
(drying of particle shaped polymer and broken)
Moisture is removed in the aqueous dispersion of particle shaped polymer 6 from above-mentioned cathode in 40 DEG C using Rotary Evaporators, so It is made it dry under conditions of 40 DEG C, 0.6kPa using vacuum drier afterwards.Then, dried cathode is crushed using mortar to use Particle shaped polymer 6 has obtained powdered cathode adhesive 6.120 DEG C of powdered cathode adhesive 6 are volatilized into It is divided into 0.1%.
Other than having used above-mentioned cathode adhesive 6, carried out similarly to Example 1 cathode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 7>
Moisture is removed in the aqueous dispersion of particle shaped polymer 1 from above-mentioned cathode in 40 DEG C using Rotary Evaporators, so Afterwards, it other than not made it dry under conditions of 40 DEG C, 0.6kPa using vacuum drier, carries out similarly to Example 1 The drying of particle shaped polymer and broken, has obtained powdered cathode adhesive 7.Powdered cathode adhesive 7 120 DEG C of volatile ingredients are 0.8%.
Other than having used above-mentioned cathode adhesive 7, carried out similarly to Example 1 cathode manufacture and lithium from The manufacture of sub- secondary cell.
<Comparative example 1>
(manufacture of cathode particle shaped polymer 7)
70 parts of styrene is added into the 5MPa pressure vessels with blender, 27 parts of 1,3- butadiene, 3 parts of itaconic acid, makees For emulsifier alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) with solid at Divide and draws when 0.4 part of gauge, 150 parts of ion exchange water, as 0.3 part of the tert-dodecylmercaotan of chain-transferring agent and as polymerization 0.5 part of the potassium peroxydisulfate of agent is sent out, is carried out after adequately stirring, is heated up to 75 DEG C to cause polymerization.Reach in polymerisation conversion It is cooled down at the time of 96%, stops reaction, obtained the aqueous dispersion of cathode particle shaped polymer 7.Cathode particle shape The minimum film temperature of polymer 7 is 27 DEG C, and glass transition temperature (Tg) is 30 DEG C, primary particle diameter 130nm.
(drying of particle shaped polymer and broken)
Moisture is removed in the aqueous dispersion of particle shaped polymer 7 from above-mentioned cathode in 20 DEG C using Rotary Evaporators, so It is made it dry under conditions of 20 DEG C, 0.6kPa using vacuum drier afterwards.Then, dried cathode is crushed using mortar to use Particle shaped polymer 7 has obtained the slightly higher powdered cathode adhesive 8 of coherency.Powdered cathode adhesive 8 120 DEG C of volatile ingredients are 0.1%.
Other than having used above-mentioned cathode adhesive 8, carried out similarly to Example 1 cathode manufacture and lithium from The manufacture of sub- secondary cell.
<Comparative example 2>
(manufacture of cathode particle shaped polymer 8)
94 parts of styrene, 3 parts of 1,3- butadiene, 3 parts of itaconic acid, conduct are added into the 5MPa pressure vessels with blender The alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) of emulsifier is with solid constituent When 0.4 part of gauge, 150 parts of ion exchange water and as 0.5 part of the potassium peroxydisulfate of polymerization initiator, adequately stirred Afterwards, 75 DEG C are heated up to cause polymerization.It is cooled down at the time of polymerisation conversion reaches 96%, stops reaction, born The aqueous dispersion of pole particle shaped polymer 8.The minimum film temperature of cathode particle shaped polymer 8 is 120 DEG C, and vitrifying turns Temperature (Tg) is 100 DEG C, primary particle diameter 135nm.
(drying of particle shaped polymer and broken)
Moisture is removed in the aqueous dispersion of particle shaped polymer 8 from above-mentioned cathode in 80 DEG C using Rotary Evaporators, so It is made it dry under conditions of 80 DEG C, 0.6kPa using vacuum drier afterwards.Then, dried cathode is crushed using mortar to use Particle shaped polymer 8 has obtained powdered cathode adhesive 9.
Other than having used above-mentioned cathode adhesive 9, carried out similarly to Example 1 cathode manufacture and lithium from The manufacture of sub- secondary cell.
<Comparative example 3>
(manufacture of cathode particle shaped polymer 9)
Relative to the cathode aqueous dispersion of particle shaped polymer 1, with the weight for being 100 parts relative to 10 parts of polymer weight Amount utilizes emulsion dispersion device (Milder MDN303V than addition toluene；Pacific Ocean machine work corporation) it is carried out with 15000rpm Emulsification.Then, solvent is removed from the emulsion using Rotary Evaporators, has obtained the water of cathode particle shaped polymer 9 Dispersion.The minimum film temperature of cathode particle shaped polymer 9 is 53 DEG C, and glass transition temperature (Tg) is 50 DEG C, primary Grain size is 3020nm.
(drying of particle shaped polymer and broken)
Moisture is removed in the aqueous dispersion of particle shaped polymer 9 from above-mentioned cathode in 40 DEG C using Rotary Evaporators, so It is made it dry under conditions of 40 DEG C, 0.6kPa using vacuum drier afterwards.Then, dried cathode is crushed using mortar to use Particle shaped polymer 9 has obtained powdered cathode adhesive 10.120 DEG C of volatilizations of powdered cathode adhesive 10 Ingredient is 0.1%.
Other than having used above-mentioned cathode adhesive 10, manufacture and the lithium of cathode have been carried out similarly to Example 1 The manufacture of ion secondary battery.
<Comparative example 4>
Using Rotary Evaporators when removing moisture from aqueous dispersion of the above-mentioned cathode with particle shaped polymer 1 for 40 DEG C, Stop the removing of moisture in midway, obtains powdered cathode adhesive 11.Powdered cathode is with the 120 of adhesive 11 DEG C volatile ingredient is 2%.
Other than having used above-mentioned cathode adhesive 11, manufacture and the lithium of cathode have been carried out similarly to Example 1 The manufacture of ion secondary battery.
<Comparative example 5>
Moisture is removed in the aqueous dispersion of particle shaped polymer 1 from above-mentioned cathode in 60 DEG C using Rotary Evaporators, so It is made it dry under conditions of 60 DEG C, 0.6kPa using vacuum drier afterwards.Then, the cathode through membranization is crushed using mortar With particle shaped polymer 1, is then further crushed until average grain diameter reaches 5000nm or so, obtained using jet mill Powdered cathode adhesive 12.120 DEG C of volatile ingredients of powdered cathode adhesive 12 are 0.1%.
Other than having used above-mentioned cathode adhesive 12, manufacture and the lithium of cathode have been carried out similarly to Example 1 The manufacture of ion secondary battery.
<Embodiment 8>
(the anode manufacture of particle shaped polymer 1)
To being equipped in the reactor of mechanical agitator and condenser, in nitrogen atmosphere, ion exchange water 210 is fed Part, be heated to 70 DEG C while stirring, and by 1.96% persulfate aqueous solution 25.5 parts be added to reactor.Then, to installation Have in the other container unlike those described above of mechanical agitator, in nitrogen atmosphere, addition butyl acrylate is (below also referred to as For " BA ") 20 parts, 77.5 parts of ethyl methacrylate (hereinafter also referred to as " EMA "), methacrylic acid (hereinafter also referred to as " MAA ") 2.4 parts, 0.1 part of allyl methacrylate (hereinafter also referred to as " AMA "), as emulsifier concentration 30% alkane Yl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) works as gauge 1.0 with solid constituent 22.7 parts of part and ion exchange water, are stirred it emulsification, to be prepared for monomer mixed solution.Then, keep the monomer mixed In the state of closing liquid stirring and emulsifying, through 2.5 hours with constant speed, which is added to and has fed ion exchange The reactor of 210 parts of water and persulfate aqueous solution makes its reaction until polymerisation conversion reaches 95%, has obtained positive using grain 1 (acrylic polymer of sub- shaped polymer；Hereinafter also referred to as " acrylic compounds ") aqueous dispersion.In addition, anode particle The minimum film temperature of shaped polymer 1 is 45 DEG C, and glass transition temperature (Tg) is 40 DEG C, primary particle diameter 310nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 1 Carry out spray drying granulation, and using vacuum drier under conditions of 30 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 1.120 DEG C of volatile ingredients of powdered positive electrode binder 1 are 0.1%.
(manufacture of particle complex)
For as a positive electrode active material (111) 92.5 parts of NMC, as conductive agent 6 parts of acetylene black and it is above-mentioned just Pole adhesive is mixed 10 minutes with solid constituent 1.5 parts of gauge of conversion using Henschel mixer (three wells, three pond corporation), So that positive electrode binder is attached to positive active material, obtains particle complex.
(positive manufacture)
Particle complex obtained above is supplied using constant feeder (Nikka corporations " Nikka spray K-V ") To compacting roller (100 DEG C of roll temperature, the compacting to roll squeezer (HIRANO GIKENKOGYO corporations " shearing asperities hot-rolling ") Line presses 500kN/m).The aluminium foil of 20 μm of inserting thickness between compacting roller, keeps the above-mentioned particle supplied from constant feeder compound Body is attached on aluminium foil, is press-formed within 1.5m/ minutes with shaping speed, and the anode with positive active material has been obtained.
(manufacture of negative paste and cathode)
By the artificial graphite (average grain diameter as negative electrode active material：24.5 μm, graphite layers away from (be based on X-ray diffraction The face interval (d values) in (002) face that method measures)：0.354nm) 96 parts, styrene butadiene copolymers latex (BM-400B) is with solid 1.5% aqueous solution (DN-800H of 3.0 parts of gauge of body ingredient conversion, carboxymethyl cellulose：Daicel chemical industrial companies system) with Then the 1.0 parts of mixing of solid constituent conversion amount add ion exchange water and solid component concentration are made to reach 50%, carry out mixing point It dissipates, has obtained negative paste.The negative paste is applied to the copper foil of 18 μm of thickness, dries 30 minutes in 120 DEG C, then Roll-in is carried out, the cathode of 50 μm of thickness has been obtained.
(preparation of partition board)
By the polypropylene partition board (wide 65mm, long 500mm, 25 μm of thickness, manufactured using dry process, the porosity 55%) of single layer It is punched to 5 × 5cm2Square.
(manufacture of lithium rechargeable battery)
As the outer packing of battery, aluminium housing material is prepared.Anode obtained above is punched to 4 × 4cm2Just It is rectangular, it is configured in a manner of so that the surface on current collection side is contacted with aluminium housing material.In addition, it is obtained above just The partition board of square obtained above is configured on the face of the positive electrode active material layer of pole.Then, cathode obtained above is cut At 4.2 × 4.2cm2Square, by make the surface of negative electrode active material layer side towards partition board in a manner of configure on partition board.Into One step is filled with the LiPF of containing 2.0% vinylene carbonate, a concentration of 1.0M6Solution.The LiPF6The solvent of solution is The mixed solvent (EC/EMC=3/7 (volume ratio)) of ethylene carbonate (EC) and methyl ethyl carbonate (EMC).In turn, in order to by aluminium The opening of packaging material seals, and is sealed in 150 DEG C and seals aluminium outer packing, and the lithium ion secondary electricity of laminated-type has been manufactured Pond (laminated-type battery).
<Embodiment 9>
(the anode manufacture of particle shaped polymer 2)
To being equipped in the reactor of mechanical agitator and condenser, 210 parts of ion exchange water is fed in nitrogen atmosphere, Be heated to 70 DEG C while stirring, and by 1.96% persulfate aqueous solution 25.5 parts be added to reactor.Then, organic to installing In the other container unlike those described above of tool blender, in nitrogen atmosphere, 12 parts of butyl acrylate of addition, methacrylic acid 85.5 parts of ethyl ester, 2.4 parts of methacrylic acid, 0.1 part of allyl methacrylate, as emulsifier concentration 30% alkyl two Phenylate disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) with solid constituent when 1.0 parts of gauge and 22.7 parts of ion exchange water, is stirred it emulsification, to be prepared for monomer mixed solution.Then, make the monomer mixed solution In the state of stirring and emulsifying, through 2.5 hours with constant speed, which is added to and has fed ion exchange water The reactor of 210 parts and persulfate aqueous solution makes its reaction obtain anode particle until polymerisation conversion reaches 95% The aqueous dispersion of shaped polymer 2.In addition, the minimum film temperature of anode particle shaped polymer 2 is 52 DEG C, glass transition temperature It is 50 DEG C to spend (Tg), primary particle diameter 319nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 2 Carry out spray drying granulation, and using vacuum drier under conditions of 40 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 2.120 DEG C of volatile ingredients of powdered positive electrode binder 2 are 0.1%.
Other than having used above-mentioned positive electrode binder 2, carried out similarly to Example 8 anode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 10>
(the anode manufacture of particle shaped polymer 3)
To being equipped in the reactor of mechanical agitator and condenser, 210 parts of ion exchange water is fed in nitrogen atmosphere, Be heated to 70 DEG C while stirring, and by 1.96% persulfate aqueous solution 25.5 parts be added to reactor.Then, organic to installing In the other container unlike those described above of tool blender, in nitrogen atmosphere, 6 parts of butyl acrylate of addition, methacrylic acid 91.5 parts of ethyl ester, 2.4 parts of methacrylic acid, 0.1 part of allyl methacrylate, as emulsifier concentration 30% alkyl two Phenylate disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) with solid constituent when 1.0 parts of gauge and 22.7 parts of ion exchange water, is stirred it emulsification, to be prepared for monomer mixed solution.Then, make the monomer mixed solution In the state of stirring and emulsifying, through 2.5 hours with constant speed, which is added to and has fed ion exchange water The reactor of 210 parts and persulfate aqueous solution makes its reaction obtain anode particle until polymerisation conversion reaches 95% The aqueous dispersion of shaped polymer 3.In addition, the minimum film temperature of anode particle shaped polymer 3 is 65 DEG C, glass transition temperature It is 60 DEG C to spend (Tg), primary particle diameter 331nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 3 Carry out spray drying granulation, and using vacuum drier under conditions of 40 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 3.120 DEG C of volatile ingredients of powdered positive electrode binder 3 are 0.1%.
Other than having used above-mentioned positive electrode binder 3, carried out similarly to Example 8 anode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 11>
(the anode manufacture of particle shaped polymer 4)
To being equipped in the reactor of mechanical agitator and condenser, fed in nitrogen atmosphere 210 parts of ion exchange water, Alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, the DOW Chemical companies of concentration 30% as emulsifier System) 0.5 part of gauge worked as with solid constituent, be heated to 70 DEG C while stirring, and by 1.96% persulfate aqueous solution 25.5 parts add Add to reactor.Then, to being equipped in the other container unlike those described above of mechanical agitator, in nitrogen atmosphere, add Add 20 parts of butyl acrylate, 77.5 parts of ethyl methacrylate, 2.4 parts of methacrylic acid, 0.1 part of allyl methacrylate, Alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, the DOW Chemical companies of concentration 30% as emulsifier Make) 22.7 parts of 0.5 part of gauge and ion exchange water are worked as with solid constituent, emulsification is stirred to it, it is mixed to be prepared for monomer Close liquid.Then, in the state of making the monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, by the monomer mixed solution It is added to the reactor for having fed 210 parts of ion exchange water and persulfate aqueous solution, makes its reaction until polymerisation conversion Reach 95%, has obtained the positive aqueous dispersion with particle shaped polymer 4.In addition, the anode minimum system of particle shaped polymer 4 Film temperature is 43 DEG C, and glass transition temperature (Tg) is 40 DEG C, primary particle diameter 139nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 4 Carry out spray drying granulation, and using vacuum drier under conditions of 30 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 4.120 DEG C of volatile ingredients of powdered positive electrode binder 4 are 0.1%.
Other than having used above-mentioned positive electrode binder 4, carried out similarly to Example 8 anode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 12>
(the anode manufacture of particle shaped polymer 5)
To being equipped in the reactor of mechanical agitator and condenser, fed in nitrogen atmosphere 210 parts of ion exchange water, Alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, the DOW Chemical companies of concentration 30% as emulsifier System) 0.8 part of gauge worked as with solid constituent, be heated to 70 DEG C while stirring, and by 1.96% persulfate aqueous solution 25.5 parts add Add to reactor.Then, to being equipped in the other container unlike those described above of mechanical agitator, in nitrogen atmosphere, add Add 20 parts of butyl acrylate, 77.5 parts of ethyl methacrylate, 2.4 parts of methacrylic acid, 0.1 part of allyl methacrylate, Alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, the DOW Chemical companies of concentration 30% as emulsifier Make) 22.7 parts of 0.8 part of gauge and ion exchange water are worked as with solid constituent, emulsification is stirred to it, it is mixed to be prepared for monomer Close liquid.Then, in the state of making the monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, by the monomer mixed solution It is added to the reactor for having fed 210 parts of ion exchange water and persulfate aqueous solution, makes its reaction until polymerisation conversion Reach 95%, has obtained the positive aqueous dispersion with particle shaped polymer 5.In addition, the anode minimum system of particle shaped polymer 5 Film temperature is 43 DEG C, and glass transition temperature (Tg) is 40 DEG C, primary particle diameter 100nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 5 Carry out spray drying granulation, and using vacuum drier under conditions of 30 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 5.120 DEG C of volatile ingredients of powdered positive electrode binder 5 are 0.1%.
Other than having used above-mentioned positive electrode binder 5, carried out similarly to Example 8 anode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 13>
(the anode manufacture of particle shaped polymer 6)
To being equipped in the reactor of mechanical agitator and condenser, 210 parts of ion exchange water is fed in nitrogen atmosphere, Be heated to 70 DEG C while stirring, and by 1.96% persulfate aqueous solution 25.5 parts be added to reactor.Then, organic to installing In the other container unlike those described above of tool blender, in nitrogen atmosphere, 20 parts of butyl acrylate of addition, methacrylic acid 77.5 parts of ethyl ester, 2.4 parts of methacrylic acid, 0.1 part of allyl methacrylate, as emulsifier concentration 30% alkyl two Phenylate disulfonate (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) with solid constituent when 0.4 part of gauge and 22.7 parts of ion exchange water, is stirred it emulsification, to be prepared for monomer mixed solution.Then, make the monomer mixed solution In the state of stirring and emulsifying, through 2.5 hours with constant speed, which is added to and has fed ion exchange water The reactor of 210 parts and persulfate aqueous solution makes its reaction obtain anode particle until polymerisation conversion reaches 95% The aqueous dispersion of shaped polymer 6.In addition, the minimum film temperature of anode particle shaped polymer 6 is 48 DEG C, glass transition temperature It is 40 DEG C to spend (Tg), primary particle diameter 625nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 6 Carry out spray drying granulation, and using vacuum drier under conditions of 30 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 6.120 DEG C of volatile ingredients of powdered positive electrode binder 6 are 0.1%.
Other than having used above-mentioned positive electrode binder 6, carried out similarly to Example 8 anode manufacture and lithium from The manufacture of sub- secondary cell.
<Embodiment 14>
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 1 Spray drying granulation is carried out, particle has been obtained.Then, in addition to not made under conditions of 30 DEG C, 0.6kPa using vacuum drier Except obtained particle drying, the drying of particle shaped polymer is carried out similarly to Example 8, has been obtained powdered anode and has been used Adhesive 7.120 DEG C of volatile ingredients of powdered positive electrode binder 7 are 0.8%.
Other than having used above-mentioned positive electrode binder 7, carried out similarly to Example 8 anode manufacture and lithium from The manufacture of sub- secondary cell.
<Comparative example 6>
(the anode manufacture of particle shaped polymer 7)
To being equipped in the reactor of mechanical agitator and condenser, 210 parts of ion exchange water is fed in nitrogen atmosphere, Be heated to 70 DEG C while stirring, and by 1.96% persulfate aqueous solution 25.5 parts be added to reactor.Then, organic to installing In the other container unlike those described above of tool blender, in nitrogen atmosphere, 27.6 parts of butyl acrylate of addition, metering system 70.0 parts of acetoacetic ester, 2.4 parts of methacrylic acid, 0.1 part of allyl methacrylate, as emulsifier concentration 30% alkyl Diphenyl oxide disulfonates (DOWFAX (registered trademark) 2A1, DOW Chemical corporations) with solid constituent when 1.0 parts of gauge, And 22.7 parts of ion exchange water, emulsification is stirred to it, to be prepared for monomer mixed solution.Then, the monomer is made to mix In the state of liquid stirring and emulsifying, through 2.5 hours with constant speed, which is added to and has fed ion exchange water The reactor of 210 parts and persulfate aqueous solution makes its reaction obtain anode particle until polymerisation conversion reaches 95% The aqueous dispersion of shaped polymer 7.In addition, the minimum film temperature of anode particle shaped polymer 7 is 27 DEG C, glass transition temperature It is 30 DEG C to spend (Tg), primary particle diameter 307nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 7 Carry out spray drying granulation, and using vacuum drier under conditions of 25 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 8.120 DEG C of volatile ingredients of powdered positive electrode binder 8 are 0.1%.
Other than having used above-mentioned positive electrode binder 8, carried out similarly to Example 8 anode manufacture and lithium from The manufacture of sub- secondary cell.
<Comparative example 7>
(the anode manufacture of particle shaped polymer 8)
To being equipped in the reactor of mechanical agitator and condenser, 210 parts of ion exchange water is fed in nitrogen atmosphere, Be heated to 70 DEG C while stirring, and by 1.96% persulfate aqueous solution 25.5 parts be added to reactor.Then, organic to installing In the other container unlike those described above of tool blender, in nitrogen atmosphere, 22.5 parts of ethyl methacrylate of addition, methyl 75.0 parts of methyl acrylate (hereinafter also referred to as " MMA "), 0.1 part of allyl methacrylate, is made 2.4 parts of methacrylic acid For alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, the DOW Chemical companies of the concentration 30% of emulsifier Make) 22.7 parts of 1.0 parts of gauge and ion exchange water are worked as with solid constituent, emulsification is stirred to it, it is mixed to be prepared for monomer Close liquid.Then, in the state of making the monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, by the monomer mixed solution It is added to the reactor for having fed 210 parts of ion exchange water and persulfate aqueous solution, makes its reaction until polymerisation conversion Reach 95%, has obtained the positive aqueous dispersion with particle shaped polymer 8.In addition, the anode minimum system of particle shaped polymer 8 Film temperature is 115 DEG C, and glass transition temperature (Tg) is 100 DEG C, primary particle diameter 280nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 8 Carry out spray drying granulation, and using vacuum drier under conditions of 80 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 9.120 DEG C of volatile ingredients of powdered positive electrode binder 9 are 0.1%.
Other than having used above-mentioned positive electrode binder 9, carried out similarly to Example 8 anode manufacture and lithium from The manufacture of sub- secondary cell.
<Comparative example 8>
(the anode manufacture of particle shaped polymer 9)
To being equipped in the reactor of mechanical agitator and condenser, 831 parts of ion exchange water is added in nitrogen atmosphere (DOWFAX (registered trademark) 2A1, DOW Chemical are public with the alkyl diphenyl ether disulfonate of the concentration 30% as emulsifier Department makes) 10 parts of gauge is worked as with solid constituent, and add 6 parts of butyl acrylate, 91.5 parts of ethyl methacrylate, methacrylic acid 2.4 parts, 0.1 part of allyl methacrylate, emulsification is stirred to the monomer mixed solution.It is heated to when being stirred to it 60 DEG C, 1.96% persulfate aqueous solution is added to reactor for 51 parts.It is reacted until polymerisation conversion reaches 98%, is obtained The positive aqueous dispersion with particle shaped polymer 9 is arrived.In addition, the minimum film temperature of anode particle shaped polymer 9 is 42 DEG C, glass transition temperature (Tg) is 60 DEG C, primary particle diameter 50nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 9 Carry out spray drying granulation, and using vacuum drier under conditions of 40 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 10.120 DEG C of volatile ingredients of powdered positive electrode binder 10 are 0.1%.
Other than having used above-mentioned positive electrode binder 10, manufacture and the lithium of anode have been carried out similarly to Example 8 The manufacture of ion secondary battery.
<Comparative example 9>
(the anode manufacture of particle shaped polymer 10)
The aqueous dispersion that particle shaped polymer 1 is used relative to anode, with the weight for being 100 parts relative to 10 parts of polymer weight Amount utilizes emulsion dispersion device (Milder MDN303V than addition toluene；Pacific Ocean machine work corporation) it is carried out with 15000rpm Emulsification.Then, solvent is removed from the emulsion using Rotary Evaporators, has obtained the positive water with particle shaped polymer 10 Dispersion.The minimum film temperature of anode particle shaped polymer 10 is 53 DEG C, and glass transition temperature (Tg) is 40 DEG C, primary Grain size is 3050nm.
(drying of particle shaped polymer)
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 9 Carry out spray drying granulation, and using vacuum drier under conditions of 40 DEG C, 0.6kPa, so as to get particle drying, obtain Powdered positive electrode binder 11.120 DEG C of volatile ingredients of powdered positive electrode binder 11 are 0.1%.
Other than having used above-mentioned positive electrode binder 11, manufacture and the lithium of anode have been carried out similarly to Example 8 The manufacture of ion secondary battery.
<Comparative example 10>
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 30 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 1 Spray drying granulation is carried out, gained particle is not dried in vacuo, has obtained powdered positive electrode binder 12.It is powdered Positive electrode binder 12 120 DEG C of volatile ingredients be 2%.
Other than having used above-mentioned positive electrode binder 12, manufacture and the lithium of anode have been carried out similarly to Example 8 The manufacture of ion secondary battery.
<Comparative example 11>
In spray dryer (great river original chemical industry machine corporation), the sprayer (diameter of rotating circular disk mode is used 65mm), setting speed 25,000rpm, hot blast temperature are 40 DEG C, use above-mentioned anode the aqueous dispersion of particle shaped polymer 1 Carry out spray drying granulation, and using vacuum drier under conditions of 70 DEG C, 0.6kPa, so as to get particle drying.Then, The anode particle shaped polymer 1 through membranization is crushed using mortar, is then further crushed until flat using jet mill Equal grain size reaches 5000nm or so, has obtained powdered positive electrode binder 13.The 120 of powdered positive electrode binder 13 DEG C volatile ingredient is 0.1%.
As shown in table 1 and table 2, the electrode that is manufactured using the particle complex comprising following electrode binding agent Electrode precision, flexibility it is good, in turn, the speed characteristic using the lithium rechargeable battery of the electrode is good, the electrode With adhesive by glass transition temperature be 35~80 DEG C, the volume reference D50 average grain diameters of primary particle are 80~1000nm Polymer formed, the volatile ingredient at 120 DEG C be less than 1 weight %, and the adhesive be powdered Composite particle.

Claims (8)

  1. It is by by electro-chemical element electrode adhesive and electrode active 1. a kind of electro-chemical element electrode particle complex Property substance carry out dry type mixing obtained from, the electro-chemical element electrode adhesive by glass transition temperature be 35~80 DEG C, the polymer that the volume reference D50 average grain diameters of primary particle are 80~1000nm formed,
    Volatile ingredient of the adhesive at 120 DEG C is less than 1 weight %,
    The adhesive is the powdered Composite particle of shape made of spherical or multiple chous close.
  2. 2. electro-chemical element electrode particle complex according to claim 1, wherein the electro-chemical element electrode is used Adhesive is the aqueous dispersion of the particle shaped polymer by that will be dispersed with the polymer less than the particle shaped polymer Minimum film temperature under conditions of be dried obtained from.
  3. 3. electro-chemical element electrode particle complex according to claim 1 or 2, wherein the electrochemical element electricity Pole adhesive includes at least one of to be selected from the group monomeric unit：Conjugated diene monomeric unit, acrylate monomeric units, Methacrylate monomers unit, aromatic vinyl compound monomer unit, olefinically unsaturated nitriles monomeric unit, olefinic insatiable hunger With carboxylic monomer unit, olefinic unsaturated acyl amine monomer units, multifunctional olefinic type monomers unit.
  4. 4. electro-chemical element electrode particle complex according to claim 1 or 2, wherein the electro-chemical element electrode With the volume reference D50 average grain diameters Da of the particle complex and volume reference D50 average grain diameters Db of the electrode active material The ratio between Da/Db be 0.5~2.
  5. 5. a kind of electro-chemical element electrode is the electro-chemical element electrode that lamination includes described in claim 4 on the current collector Made of electrode active material layer with particle complex.
  6. 6. electro-chemical element electrode according to claim 5, wherein the electrode active material layer is by that will include institute State electro-chemical element electrode particle complex electrode material be press-formed on the collector obtained from.
  7. 7. a kind of electrochemical element has electro-chemical element electrode described in claim 5 or 6.
  8. 8. a kind of manufacturing method of electro-chemical element electrode comprising：
    Drying process：It will be dispersed with that glass transition temperature is 35~80 DEG C, the volume-based average particle size D50 of primary particle is The aqueous dispersion of the spherical particle shaped polymer of 80~1000nm is in the minimum film temperature less than the particle shaped polymer Under conditions of be dried and obtain the powdered Composite particle of shape made of spherical or multiple chous close；
    Mixed processes：It is compound that the powdered Composite particle and electrode active material progress dry type mixing are obtained into particle Body；And
    Electrode manufacturing process：Electrode is manufactured using the particle complex.
CN201480026238.XA 2013-05-29 2014-05-23 The manufacturing method of electro-chemical element electrode adhesive, electro-chemical element electrode particle complex, electro-chemical element electrode, electrochemical element and electro-chemical element electrode Active CN105190968B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2013-112800 2013-05-29
JP2013112800 2013-05-29
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