CN105190968A - Binder for use in electrochemical device electrodes, particle composite for use in electrochemical device electrodes, electrochemical device electrode, electrochemical device, and electrochemical device electrode manufacturing method - Google Patents
Binder for use in electrochemical device electrodes, particle composite for use in electrochemical device electrodes, electrochemical device electrode, electrochemical device, and electrochemical device electrode manufacturing method Download PDFInfo
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- CN105190968A CN105190968A CN201480026238.XA CN201480026238A CN105190968A CN 105190968 A CN105190968 A CN 105190968A CN 201480026238 A CN201480026238 A CN 201480026238A CN 105190968 A CN105190968 A CN 105190968A
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- electrode
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- shaped polymer
- adhesive
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- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical class COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AUCNMQYOQYTGPE-UHFFFAOYSA-N n-(hydroxymethyl)-n-methylprop-2-enamide Chemical compound OCN(C)C(=O)C=C AUCNMQYOQYTGPE-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- LYJZNXAVZMEXDH-UHFFFAOYSA-N octadecan-8-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCC LYJZNXAVZMEXDH-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The purpose of the present invention is to provide a binder for use in electrochemical device electrodes which, by virtue not producing a slurry during electrode layer formation, has excellent productivity of electrodes and which, by virtue of not requiring a water-soluble polymer component as a dispersant, enables lower resistance and has excellent flexibility and accuracy of thickness of the obtained electrode; and also to provide an electrode composite using said binder, an electrode, an electrochemical device, and an electrochemical device manufacturing method. The present invention relates to a binder for use in electrochemical device electrodes which comprises a polymer with a glass transition temperature of 35-80DEG C and a D50 average particle diameter of 80-1000nm based on volume of the primary particles, has a volatile component at 120DEG C of less than 1 wt%, and consists of powder-form composite particles.
Description
Technical field
The present invention relates to the manufacture method of electro-chemical element electrode adhesive, electro-chemical element electrode particle complex, electro-chemical element electrode, electrochemical element and electro-chemical element electrode.
Background technology
The electrochemical elements such as lithium rechargeable battery, double electric layer capacitor and lithium-ion capacitor have small-sized, lightweight, energy density are high and the characteristic that can be repeatedly charged and discharged, and effectively utilize such characteristic, and its demand is expanded rapidly.Lithium rechargeable battery is because energy density is comparatively large, because being used to the mobile field such as mobile phone, subnotebook PC.On the other hand, double electric layer capacitor, because can promptly discharge and recharge, be therefore used as the slack storage Miniature Power Unit of PC etc., in addition, also expects the application of double electric layer capacitor as the accessory power supply of electric automobile etc.Further, with regard to effectively make use of the lithium-ion capacitor of the advantage of lithium rechargeable battery and double electric layer capacitor, because its energy density, output density are all high than double electric layer capacitor, therefore expanded be applicable to double electric layer capacitor the purposes that is suitable for and the research of failing the purposes meeting specification with the performance of double electric layer capacitor.Among these, particularly for lithium rechargeable battery, in recent years, not only to its application in the vehicle-mounted purposes such as mixed power electric car, electric automobile, even all inquire into for its application in electric power storage purposes.
In the another aspect raised the expectation of these electrochemical elements, for these electrochemical elements, with expansion and the development of its purposes, low resistance, high capacity, mechanical property, productive raising etc. are also required further to improve.In such a case, for electrode for electrochemical device, also require the manufacture method that productivity is higher.
Electrode for electrochemical device normally laminate electrode active material layer on the current collector, described electrode active material layer is by by electrode active material and as required and the conductive agent adopted utilizes adhesive to carry out boning being formed.In electrode for electrochemical device, have and utilize by by the coating electrode slurry coating containing electrode active material, adhesive, conductive agent etc. on the current collector and utilize heat etc. and remove the method for desolventizing and the coating electrode that manufactures.Such as, in patent documentation 1, describe use polymer-extruded film-like and the polymer particle carrying out pulverizing and obtain as adhesive, mix this adhesive, electrode active material, conductive agent and solvent obtain coating electrode slurry and coating on the current collector thus obtain the scheme of coating electrode.It should be noted that, the polymer particle used in patent documentation 1 is adhesive, the i.e. dry adhesives of drying.
But, with regard to these methods, owing to needing, for dry polymer film, the energy removing desolventizing from coating electrode slurry, therefore to exist and cause cost to raise, be difficult to improve productive situation.
So, propose and do not use coating electrode slurry to manufacture the method for electrode.Such as, in patent documentation 2, use by by dry adhesives or be scattered in adhesive in solvent, electrode active material, the conductive agent that comprises material with carbon element mix and the powder mixture carrying out drying and obtain and define electrode active material layer.In addition, in patent documentation 3, use and carbon dust and adhesive are mixed by wet type, then carry out drying/pulverizing and the mixed-powder obtained defines tunicle in the negative terminal surface of lithium primary battery.
In addition, proposed and not only do not used coating electrode slurry but also adhesive dispersion do not obtained electrode material in a solvent and form the method for electrode active material layer.Such as, in patent documentation 4, use mixed powder and define electrode active material layer, this mixed powder is the suspension polymerization that electrode active material and utilizing carried out under the existence of conductive agent and carries out being obtained by mixing with the binder particles that conductive agent there occurs compound.
In addition, in patent documentation 5, be used as Kynoar (PVDF) powder of dry adhesives as adhesive, make the mixed-powder that electrode active material, adhesive and conductive agent are obtained by mixing be attached to collector body surface by electrostatic coating, then, temperature more than the softening point of adhesive makes these compositions fusible, defines electrode active material layer on the current collector thus.
Prior art document
Patent documentation
Patent documentation 1: No. 2007/122947th, International Publication
Patent documentation 2: Japan Patent No. 4687458 publications
Patent documentation 3: Japanese Unexamined Patent Publication 2010-86738 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2011-14409 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2001-351616 publication
Summary of the invention
The problem that invention will solve
But, when dry adhesives being used as adhesive and the electrode material that dry adhesives and electrode active material are obtained by mixing is formed electrode active material layer by dry type by use, if use the adhesive recorded in patent documentation 1, then can cause obtaining the electrode with abundant flexibility because the glass transition temperature of adhesive is too high.In addition, if use the adhesive recorded in patent documentation 2 or 5, be then difficult to form homogeneous electrode active material layer because the glass transition temperature of adhesive is too low.In addition, in patent documentation 3 and 4, use dry adhesives is not recorded.
In addition, if use the adhesive used in patent documentation 5, then the particle diameter due to adhesive is large, and the bonding point therefore between connecting electrode active material is few, is difficult to the electrode obtaining having abundant intensity.
The object of the present invention is to provide the productivity owing to not making slurry therefore electrode when forming electrode layer excellent, owing to not needing water soluble polymer composition therefore, it is possible to realize low resistance as dispersant, and the electro-chemical element electrode adhesive of the thickness and precision of the electrode obtained and flexibility excellence, employ the electro-chemical element electrode particle complex of this electro-chemical element electrode adhesive, employ electro-chemical element electrode and the electrochemical element of this electro-chemical element electrode particle complex.Further, the object of the present invention is to provide the manufacture method of the electro-chemical element electrode of productivity excellence, thickness and precision and flexibility excellence.
The method of dealing with problems
The present inventor conducts in-depth research to solve the problem, and found that, by glass transition temperature and average grain diameter being controlled, in given scope, can reach above-mentioned purpose, thus complete the present invention.
That is, according to the present invention, can provide:
(1) a kind of electro-chemical element electrode adhesive, its by glass transition temperature be 35 ~ 80 DEG C, the volume reference D50 average grain diameter of primary particle is that the polymer of 80 ~ 1000nm is formed, the volatile ingredient of this adhesive 120 DEG C time is less than 1 % by weight, and this adhesive is Powdered Composite particle;
(2) the electro-chemical element electrode adhesive Gen Ju (1), it carries out drying by the aqueous dispersion of the particle shaped polymer by being dispersed with described polymer and obtains under the condition of the minimum masking temperature lower than described particle shaped polymer;
(3) according to (1) or the electro-chemical element electrode adhesive described in (2), it comprises at least one monomeric unit be selected from lower group: conjugated diene monomeric unit, acrylate monomeric units, methacrylate monomers unit, aromatic vinyl compound monomer unit, olefinically unsaturated nitriles monomeric unit, ethylenically unsaturated carboxylic acids monomeric unit, olefinic unsaturated acyl amine monomer units, multifunctional olefinic type monomers unit;
(4) an electro-chemical element electrode particle complex, it is obtained by mixing by the electro-chemical element electrode adhesive according to any one of electrode active material and (1) ~ (3) is carried out dry type;
(5) the electro-chemical element electrode particle complex Gen Ju (4), wherein, the ratio (Da/Db) of the volume reference D50 average grain diameter (Da) of this electro-chemical element electrode particle complex and the volume reference D50 average grain diameter (Db) of described electrode active material is 0.5 ~ 2;
(6) electro-chemical element electrode, it is that lamination comprises the electrode active material layer of the electro-chemical element electrode particle complex described in (5) on the current collector;
(7) electro-chemical element electrode Gen Ju (6), wherein, described electrode active material layer obtains by the electrode material comprising described electro-chemical element electrode particle complex is carried out extrusion forming on described collector body;
(8) electrochemical element, it possesses (6) or the electro-chemical element electrode described in (7);
(9) manufacture method for electro-chemical element electrode, it comprises: the aqueous dispersion being dispersed with the spherical particle shaped polymer that glass transition temperature is 35 ~ 80 DEG C, the volume reference average grain diameter D50 of primary particle is 80 ~ 1000nm is carried out the drying process that drying obtains Powdered Composite particle under the condition of the minimum masking temperature lower than described particle shaped polymer; Described Powdered Composite particle and electrode active material are carried out the mixed processes that dry type is obtained by mixing particle complex; And use described particle complex to manufacture the electrode manufacturing process of electrode.
The effect of invention
According to the present invention, can provide the productivity owing to not making slurry therefore electrode when forming electrode layer excellent, owing to not needing water soluble polymer as dispersant therefore, it is possible to realize low resistance and the electro-chemical element electrode adhesive of the thickness and precision of the electrode obtained and flexibility excellence, the electro-chemical element electrode particle complex employing this electro-chemical element electrode adhesive, the electro-chemical element electrode employing this electro-chemical element electrode particle complex and electrochemical element.Further, according to the present invention, the manufacture method of the electro-chemical element electrode of productivity excellence, thickness and precision and flexibility excellence can be provided.
Embodiment
Below, be described for electro-chemical element electrode adhesive of the present invention.The feature of electro-chemical element electrode adhesive of the present invention (being also denoted as below " electrode binding agent ") is, it comprises, and glass transition temperature is 35 ~ 80 DEG C, the volume reference D50 average grain diameter of primary particle is the polymer of 80 ~ 1000nm, and the volatile ingredient of this adhesive 120 DEG C time is less than 1 % by weight, this adhesive is Powdered Composite particle.
It should be noted that, in this manual, described " positive active material " refers to the electrode active material of positive pole, and described " negative electrode active material " refers to the electrode active material of negative pole.In addition, described " positive electrode active material layer " refers to the electrode active material layer being arranged at positive pole, and described " negative electrode active material layer " refers to the electrode active material layer being arranged at negative pole.
(electro-chemical element electrode adhesive)
The glass transition temperature (Tg) of electrode binding agent of the present invention is 35 ~ 80 DEG C, is preferably 40 ~ 75 DEG C, is more preferably 40 ~ 70 DEG C, more preferably 40 ~ 60 DEG C, is particularly preferably 45 ~ 55 DEG C.If the glass transition temperature of electrode binding agent is in this scope, then softness can be obtained and the electrode of abundant intensity.In addition, if the glass transition temperature of electrode binding agent is too high, then the electrode being difficult to obtain and there is sufficient flexibility can be become.In addition, if the glass transition temperature of electrode binding agent is too low, then the mobility due to particle complex described later is insufficient, and the thickness and precision of the electrode obtained therefore can be caused to be deteriorated.That is, electrode can be caused uneven thickness to occur.
The volume reference D50 average grain diameter (hereinafter also referred to " primary particle diameter ") of the primary particle of electrode binding agent of the present invention is 80 ~ 1000nm, is preferably 80 ~ 800nm, is more preferably 100 ~ 500nm, more preferably 130 ~ 400nm.If the primary particle diameter of electrode binding agent is in this scope, then can keep the adhesive strength between collector body and electrode active material fully.In addition, if the primary particle diameter of electrode binding agent is excessive, then because cementability reduces, therefore dry linting can be there is when the flexibility test carrying out electrode described later.In addition, if the primary particle diameter of electrode binding agent is too small, then cementability can be caused to reduce because electrode binding agent is difficult to dispersion.
It should be noted that, electrode binding agent can be obtained by the aqueous dispersion of the particle utilizing polymerization as described below to obtain shaped polymer is carried out drying, but the primary particle diameter of particle shaped polymer in this aqueous dispersion is above-mentioned scope.In addition, the shape of particle shaped polymer is preferably spherical.
Particle shaped polymer is spherical referring to, minor axis diameter is set to Ls, major diameter be set to Ll and make La=(Ls+Ll)/2, when the value of (1-(Ll-Ls)/La) × 100 is set to sphericity (%), sphericity is more than 80%.
Here, minor axis diameter Ls and major diameter Ll be photo by observing transmission-type or scanning electron microscope and such as 10 ~ 30 of measuring etc. to the major diameter of the polymer particle of determined number (Ll) and the respective mean value of minor axis diameter (Ls).In addition, La is the value obtained by calculating La=(Ls+Ll)/2.
In addition, the volatile ingredient of electrode binding agent of the present invention 120 DEG C time is less than 1 % by weight.If the volatile ingredient of electrode binding agent 120 DEG C time is in this scope, then electrode binding agent can disperse, obtain having the electrode of abundant intensity equably.In addition, the mobility due to particle complex described later also becomes good, therefore can obtain the good electrode of thickness and precision.In addition, if the volatile ingredient of electrode binding agent 120 DEG C time is too much, then due to when manufacturing particle complex electrode binding agent do not disperse, therefore the electrode with abundant intensity cannot be obtained, in addition, because the mobility of particle complex is insufficient, the thickness and precision of the electrode therefore obtained is deteriorated.
In addition, the form of the Powdered i.e. Powdered Composite particle of the shape (agglomerate of ball) that is combined into spherical or multiple ball of electrode binding agent of the present invention exists.The primary particle of above-mentioned electrode binding agent also with independently particulate forms existence separately, but normally can be combined by molecular separating force etc. when keeping its shape by multiple primary particle and forms a particle.In addition, with regard to the particle formed by multiple primary particle, primary particle is caused to exist with the form of respective independently particle sometimes because of External Force Acting.By making the shape of electrode binding agent be the shape that spherical or multiple ball is combined into, the mobility of particle complex can be guaranteed.
Electrode binding agent of the present invention preferably comprises at least one monomeric unit be selected from conjugated diene monomeric unit, (methyl) acrylate monomeric units, aromatic vinyl compound monomer unit, olefinically unsaturated nitriles monomeric unit, ethylenically unsaturated carboxylic acids monomeric unit, olefinic unsaturated acyl amine monomer units, multifunctional olefinic type monomers unit.It should be noted that, in this manual, described " (methyl) acrylic acid " expression " acrylic acid " and " methacrylic acid ".
As the conjugate diene monomer forming conjugated diene monomeric unit, can enumerate: 1,3-butadiene, isoprene, 2,3-dimethyl-carbon number such as 1,3-butadiene, 1,3-pentadiene is the conjugated diene of more than 4.In these, preferred 1,3-butadiene.
As (methyl) acrylate monomer forming (methyl) acrylate monomeric units, can enumerate: the alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, amyl acrylate, Hexyl 2-propenoate, heptylacrylate, 2-ethyl hexyl acrylate, 2-EHA, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate, n-myristyl base ester, stearyl acrylate ester, methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, Tert-butyl Methacrylate, pentylmethacrylate, hexyl methacrylate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, 2-Ethylhexyl Methacrylate, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid n-tetradecane base ester, the alkyl methacrylates etc. such as stearyl methacrylate.Wherein, due to the flexibility of electrode can be improved, the stripping of electrode can be suppressed when making winding battery, and the characteristic (cycle characteristics etc.) employing the secondary cell of this electrode is excellent, the carbon number of the alkyl be therefore preferably combined with non-carbonyl oxygen atom is alkyl acrylate or the alkyl methacrylate of more than 4, and the carbon number of the alkyl be more preferably combined with non-carbonyl oxygen atom is more than 6 and the alkyl acrylate of less than 20 or alkyl methacrylate.
As the aromatic vinyl compound monomer forming aromatic vinyl compound monomer unit, can enumerate: styrene, AMS, vinyltoluene etc.
As the monomer forming α, β-olefinically unsaturated nitriles monomeric unit, as long as have the α of itrile group, β-alefinically unsaturated compounds does not then limit, and can enumerate: acrylonitrile; The alpha-halogen acrylonitrile such as α-chloro-acrylonitrile, α-bromopropene nitrile; The alpha-alkyl acrylonitrile such as methacrylonitrile; Etc., preferred acrylonitrile and methacrylonitrile.As α, β-olefinically unsaturated nitriles monomer, also the multiple combination in these can be used.
As the ethylenically unsaturated carboxylic acids monomer forming ethylenically unsaturated carboxylic acids monomeric unit, can enumerate: acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid etc.
As the olefinic unsaturated acyl amine monomers forming olefinic unsaturated acyl amine monomer units, can enumerate: (methyl) acrylamide, N-methylol (methyl) acrylamide, N, N'-dihydroxymethyl (methyl) acrylamide etc.
As the multifunctional ethylenically unsaturated monomer with more than 2 alkene double bonds forming multifunctional ethylenically unsaturated monomer unit, can enumerate: the divinyl compounds such as divinylbenzene; Two (methyl) esters of acrylic acids such as ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate; The trimethyl acrylic ester classes such as trimethylolpropane tris (methyl) acrylate; Etc..
For making the method for each monomer polymerization not limit processed especially, but such as preferably make with the following method: use the emulsifying agents such as neopelex obtain the latex (aqueous dispersion) of particle shaped polymer emulsion polymerization, use the dispersants such as polyvinyl alcohol to obtain the suspension polymerization (also comprising micro-suspension polymerization) etc. of the aqueous dispersion of particle shaped polymer.In these methods, because polymerization reactor control is easy, therefore more preferably emulsion polymerization.
In addition, electrode binding agent of the present invention can obtain by making the polymer that obtained by each monomer polymerization dry.That is, by making polymer dry, the electrode binding agent (powdery adhesive) as pulverous Composite particle can be obtained.With regard to drying means, as long as can not make the primary particle of particle shaped polymer to each other exceedingly bonding, drying can be carried out with the state of disperseing again, be not particularly limited, but can enumerate such as: make the spray-dired method of the aqueous dispersion of particle shaped polymer, utilize Rotary Evaporators to carry out dry method etc.In addition, after more preferably utilizing spraying dry, Rotary Evaporators to carry out drying, drying is carried out under vacuum.
As baking temperature, always can not cause the primary particle of particle shaped polymer to each other exceedingly bonding, can set out with the dewatered viewpoint of the state of disperseing again, preferably lower than the temperature of the minimum masking temperature of particle shaped polymer.If baking temperature is too high, be then difficult to disperse again due to the generation membranization of particle shaped polymer can be caused.
In addition, from the view point of can make that particle shaped polymer is dry with the state of disperseing again, mobility that particle complex described later can be taken into account and electrode formed after the flexibility of electrode, the minimum masking temperature of particle shaped polymer is preferably 35 ~ 100 DEG C.If the minimum masking temperature of particle shaped polymer is too high, then the flexibility of the electrode obtained can be caused to decline.In addition, if the minimum masking temperature of particle shaped polymer is too low, be then difficult to make it dry when not causing the primary particle of particle shaped polymer excessively bonding.That is, be difficult to make particle shaped polymer dry with the state that can disperse again.
At this, minimum masking temperature is the minimum temperature of the film that can form above-mentioned particle shaped polymer.Minimum masking temperature such as can measure based on JISK6828-2 (2003), ISO2115.Specifically, on the flat board such as iron plate with proper temperature gradient coated particle shaped polymer aqueous dispersions and carry out drying, make it reach the thickness of about 100 μm, and measure the critical temperature that there occurs between the part of membranization and the part that membranization does not occur.Here, because the part that there occurs membranization becomes transparent, and the part that membranization does not occur is gonorrhoea, the boundary of the part that therefore can confirm to there occurs membranization by estimating and the part that membranization does not occur.In addition, due to when to the aqueous dispersion of coated particle shaped polymer and dried flat board wipe rub, can there is dry linting in the part that membranization does not occur, therefore, also can confirm to there occurs the part of membranization according to the presence or absence of dry linting and the boundary of part of membranization not occur.
(electro-chemical element electrode particle complex)
Electro-chemical element electrode particle complex of the present invention (hereinafter also referred to " particle complex ") comprises above-mentioned electrode binding agent and electrode active material.Particle complex also can comprise conductive agent as required.Here, in particle complex, electrode binding agent and electrode active material also can exist with the form of respective independently particle respectively, but normally form a particle in the multiple electrode binding agent of the surface attachment of electrode active material.And then the respective independent particle of electrode binding agent and electrode active material and above-mentioned particle, form offspring to keep in fact the state of shape by multiple combination.In addition, with regard to this offspring, when being subject to external force, its primary particle exists with the form of respective independently particle sometimes.
(electrode active material)
Positive active material when being lithium rechargeable battery as electrochemical element of the present invention, can use and can adulterate and the active material of dedoping lithium ion, it is roughly divided into the active material be made up of inorganic compound and the active material be made up of organic compound.
As the positive active material be made up of inorganic compound, can enumerate: the lithium-contained composite metal oxide etc. that transition metal oxide, transient metal sulfide, lithium and transition metal are formed.As above-mentioned transition metal, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc. can be used.
As transition metal oxide, can enumerate: MnO, MnO
2, V
2o
5, V
6o
13, TiO
2, Cu
2v
2o
3, noncrystalline V
2o-P
2o
5, MoO
3, V
2o
5, V
6o
13deng, wherein, from the view point of cyclical stability and capacity, preferred MnO, V
2o
5, V
6o
13, TiO
2.As transient metal sulfide, can enumerate: TiS
2, TiS
3, noncrystalline MoS
2, FeS etc.As lithium-contained composite metal oxide, can enumerate: the lithium-contained composite metal oxide with layer structure, the lithium-contained composite metal oxide with spinel structure, there is the lithium-contained composite metal oxide etc. of olivine-type structure.
As the lithium-contained composite metal oxide with layer structure, can enumerate: containing the cobalt/cobalt oxide (LiCoO of lithium
2), containing the nickel oxide (LiNiO of lithium
2), the lithium composite xoide of Co-Ni-Mn, the lithium composite xoide of Ni-Mn-Al, the lithium composite xoide etc. of Ni-Co-Al.As the lithium-contained composite metal oxide with spinel structure, can enumerate: LiMn2O4 (LiMn
2o
4), by the Li [Mn of a part of Mn with other transition metal substitution
3/2m
1/2] O
4(at this, M is Cr, Fe, Co, Ni, Cu etc.) etc.As the lithium-contained composite metal oxide with olivine-type structure, can enumerate: Li
xmPO
4olivine-type lithium phosphate compound shown in (in formula, M represents at least a kind of being selected from Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and Mo, 0≤X≤2).
As organic compound, such as polyacetylene, poly-to electroconductive polymers such as benzene also can be used.For the ferrous oxide of conductivity deficiency, by making carbon source material exist when carrying out reduction and firing, thus the positive active material use covered by material with carbon element can be made into.In addition, the material these compounds being carried out to Partial Elements displacement can also be used.Positive active material also can be above-mentioned inorganic compound and the mixture of organic compound.
Positive active material when being lithium-ion capacitor as electrochemical element, as long as can the material of reversibly load lithium ion and the such anion of such as tetrafluoroborate.Specifically, preferably can use the allotrope of carbon, can be widely used in double electric layer capacitor by the electrode active material used.As the concrete example of the allotrope of carbon, can enumerate: active carbon, polyacene (PAS), carbon whisker, carbon nano-tube and graphite etc.
Negative electrode active material when being lithium rechargeable battery as electrochemical element of the present invention, such as, can enumerate: the carbonaceous materials such as amorphous carbon, graphite, native graphite, carbonaceous mesophase spherules, pitch-based carbon fiber; The electroconductive polymers such as polyacene; Metal or their alloys such as silicon, tin, zinc, manganese, iron, nickel; The oxide of above-mentioned metal or alloy or sulfate; Lithium metal; The lithium alloys such as Li-Al, Li-Bi-Cd, Li-Sn-Cd; Lithium transition-metal nitride; Silicon etc.In addition, as negative electrode active material, the surface that also can be used in the particle of this negative electrode active material attached to the material of conductive agent by such as mechanically modifying method.In addition, negative electrode active material can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
In addition, as the negative electrode active material preferably used when electrochemical element is lithium-ion capacitor, the negative electrode active material formed by above-mentioned carbon can be enumerated.
Usually, for the particle diameter of the particle of electrode active material, balance between other inscape of electrochemical element can be considered and suitably select.Wherein, from the view point of battery behaviors such as raising initial efficiency, part throttle characteristics, cycle characteristicss, the particle volume benchmark D50 average grain diameter of electrode active material is preferably 1 ~ 50 μm, is more preferably 15 ~ 30 μm.
Can improve the flexibility of electrode and the close-burning viewpoint between collector body and electrode active material layer from the capacity that can improve lithium rechargeable battery, in electrode active material layer, the content of electrode active material is preferably 90 ~ 99.9 % by weight, is more preferably 95 ~ 99 % by weight.
(conductive agent)
In addition, as the conductive agent used as required in the present invention, preferred use furnace black, acetylene black (following, also referred to as " AB ") and the conductive carbon such as Ketjen black (registered trade mark of AkzoNobelChemicalsBesurotenFennotesshutup company), carbon nano-tube, carbon nanohorn, Graphene.In these, more preferably acetylene black.The average grain diameter of conductive agent is not particularly limited, but play sufficient conductivity from the view point of with less use amount, preferably little than the average grain diameter of electrode active material, be preferably 0.001 ~ 10 μm, be more preferably 0.005 ~ 5 μm, more preferably 0.01 ~ 1 μm.
When adding conductive agent, the use amount of conductive agent is preferably 1 ~ 10 weight portion relative to electrode active material 100 weight portion, is more preferably 1 ~ 5 weight portion.
(manufacture method of particle complex)
Particle complex is by carrying out dry type mixing by electrode binding agent, electrode active material and the conductive agent that uses as required and obtain.Here alleged " dry type mixing " refers to, mixer is used to mix electrode binding agent, electrode active material and the conductive agent that uses as required, specifically, the solid component concentration referred to when making mixing be more than 99 % by weight mode mix.As concrete mixed method, can enumerate: carry out container paddling process that mix, that use shaker mixer (RockingMixer), rotary drum mixer etc. by container self-oscillation, rotation or vibration; Be used in the mixer relative to level in container or vertical rotating shaft being provided with blade, rotating disk or screw rod etc. for stirring, namely the mechanical type of Fast Rotating Cylinder, V-Mixer, ribbon stirrer, pyramid type screw mixer, high velocity stream ejector half mixer, rotary disk type mixer and high speed rotational blade mixer etc. stirs; Utilize based on Compressed Gas gyration airflow, in fluid bed to the airflow stirring etc. that powder mixes.In addition, the mixer these mechanisms be used alone or in combination can also be used.In addition, also can, after carrying out dry type mixing, mortar etc. be utilized to carry out being crushed to the degree of breaking cohesion.By carrying out dry type mixing, the dispersion of electro-chemical element electrode particle complex is kept well, and then each physical property such as coating accuracy is improved.
The ratio (Da/Db) of the volume reference D50 average grain diameter (Da) of particle complex of the present invention and the volume reference D50 average grain diameter (Db) of electrode active material is preferably 0.5 ~ 2, is more preferably 0.8 ~ 2.That is, preferred multiple electrode active material is without Composite.
(electro-chemical element electrode)
Electro-chemical element electrode of the present invention is by the electrode active material layer lamination electrode on the current collector containing above-mentioned particle complex.As the material of collector body, such as, metal, carbon, electroconductive polymer etc. can be used, preferably use metal.As metal, usually use copper, aluminium, platinum, nickel, tantalum, titanium, stainless steel, other alloys etc.Among these, from the aspect of conductivity, proof voltage, preferably use copper, aluminum or aluminum alloy.In addition, when requiring high withstand voltage, highly purified aluminium disclosed in Japanese Unexamined Patent Publication 2001-176757 publication etc. can be preferably used in.Collector body is film or sheet, and its thickness suitably can be selected according to application target, is preferably 1 ~ 200 μm, is more preferably 5 ~ 100 μm, more preferably 10 ~ 50 μm.
During by electrode active material layer lamination on the current collector, particle complex can be shaped to sheet, then lamination on the current collector, but the method for preferred direct weighting shaped particle complex on the current collector.As the method for carrying out extrusion forming, can enumerate such as: use the roll-type pressing shaping device possessing pair of rolls, while transmitting collector body with roller, utilize the feedwaies such as screw feeder that particle complex is supplied to roll-type pressing shaping device, thus the roller extrusion forming method of shaped electrode active material layer on the current collector; Particle complex is scattered on the current collector, utilizes scraper etc. that particle complex is shakeout to adjust thickness, then utilize pressue device to carry out shaping method; Particle complex is filled in a mold, and mould is pressurizeed and shaping method etc.This wherein, preferred roller extrusion forming method.Particularly, because particle complex of the present invention has high fluidity, therefore, it is possible to utilizing constant feeder to carry out to supply, utilize scraper etc. make powder layer homogeneous after undertaken shaping by roller extrusion forming, can productivity be improved thus.
With regard to roll temperature during with regard to carrying out roller extrusion forming, from making the sufficient viewpoint of the adaptation between electrode active material layer and collector body, being preferably 25 ~ 200 DEG C, being more preferably 50 ~ 150 DEG C, more preferably 80 ~ 120 DEG C.In addition, as the compacting line pressure between roller during roller extrusion forming, from the view point of the homogeneity of thickness that can improve electrode active material layer, be preferably 10 ~ 1000kN/m, be more preferably 200 ~ 900kN/m, more preferably 300 ~ 600kN/m.In addition, shaping speed during roller extrusion forming is preferably 0.1 ~ 20m/ minute, is more preferably 4 ~ 10m/ minute.
In addition, in order to make the thickness of shaping electro-chemical element electrode not have deviation, the density of electrode active material layer is improved, thus pursuing high capacity, rear pressurization can be carried out further as required.The pressurization operation that the method for rear pressurization preferably utilizes roller to carry out.In roller pressurization operation, by 2 columned rollers spaced and parallel to be arranged above and below with narrow, make to rotate in the opposite direction separately, and holding electrode betwixt, pressurize thus.Now, as required, also can carry out heating or cool equitemperature adjustment by pair roller.
(electrochemical element)
The electro-chemical element electrode obtained as mentioned above is used at least one in positive pole and negative pole by electrochemical element of the present invention, and possesses dividing plate and electrolyte further.As electrochemical element, such as lithium rechargeable battery, lithium-ion capacitor etc. can be enumerated.
(dividing plate)
As dividing plate, can use and comprise the vistanex such as polyethylene, polypropylene, the microporous barrier of aromatic polyamide resin or nonwoven fabrics; Comprise the porous resin coating etc. of inorganic ceramic powder.As concrete example, can enumerate: the micro-porous film formed by TPO (polyethylene, polypropylene, polybutene, polyvinyl chloride) and the resin such as their mixture or copolymer; The micro-porous film formed by resins such as PETG, polycyclic alkene, polyether sulfone, polyamide, polyimides, polyimide amide, Nomex, polycyclic alkene, nylon, polytetrafluoroethylene; The material of the fiber of braiding TPO or its nonwoven fabrics; The aggregation etc. of insulating properties material particle.Among these, due to can the thickness of thinning dividing plate entirety, increase the active material ratio in lithium rechargeable battery, thus improve the capacity of per unit volume, the therefore preferred micro-porous film formed by the resin of TPO.
With regard to the thickness of dividing plate, from the view point of the viewpoint of the internal resistance caused by dividing plate in lithium rechargeable battery and the workability excellence when manufacturing lithium rechargeable battery can be reduced, being preferably 0.5 ~ 40 μm, being more preferably 1 ~ 30 μm, more preferably 1 ~ 25 μm.
(electrolyte)
As the electrolyte of lithium rechargeable battery, such as, can be used in nonaqueous solvents the nonaqueous electrolytic solution dissolving supporting electrolyte.As supporting electrolyte, preferably adopt lithium salts.As lithium salts, can enumerate such as: LiPF
6, LiAsF
6, LiBF
4, LiSbF
6, LiAlCl
4, LiClO
4, CF
3sO
3li, C
4f
9sO
3li, CF
3cOOLi, (CF
3cO)
2nLi, (CF
3sO
2)
2nLi, (C
2f
5sO
2) NLi etc.Wherein, preferably easily dissolve in a solvent and show the LiPF of high degree of dissociation
6, LiClO
4, CF
3sO
3li.These can be used alone a kind, also can use two or more with arbitrary ratio combination.Then lithium ion conductivity is higher to use the supporting electrolyte that degree of dissociation is higher, therefore, can regulate lithium ion conductivity according to the kind of supporting electrolyte.
With regard to the concentration of the supporting electrolyte in electrolyte, preferably according to the kind of supporting electrolyte, use with the concentration of 0.5 ~ 2.5mol/L.The concentration of supporting electrolyte too low or too high all exist cause ionic conductance degree to reduce possibility.
As nonaqueous solvents, as long as be that the solvent that can dissolve supporting electrolyte is just not particularly limited.As the example of nonaqueous solvents, can enumerate: the carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (MEC); The ester such as gamma-butyrolacton, methyl formate class; The ethers such as 1,2-dimethoxy-ethane, oxolane; The sulfur-containing compound such as sulfolane, methyl-sulfoxide class; Also the ionic liquid etc. of supporting electrolyte is used as.Wherein, the potential range high, stable due to dielectric constant is wide, therefore preferred carbonates.Nonaqueous solvents can be used alone a kind, also can combinationally use two or more with arbitrary proportion.Usually, the lower then lithium ion conductivity of viscosity of nonaqueous solvents is higher, the solubility of the higher then supporting electrolyte of dielectric constant is higher, but both are in the relation of compromise (tradeoff), therefore can regulate lithium ion conductivity according to the kind of solvent, mixing ratio and use.In addition, nonaqueous solvents can combinationally use or the overall solvent using all or part of hydrogen to replaced by fluorine.
In addition, also additive can be contained in electrolyte.As additive, such as, can enumerate: the carbonats compounds such as vinylene carbonate (VC); The sulfur-containing compounds such as glycol sulfite (ES); The fluorochemicals such as fluoroethylene carbonate (FEC).Additive can be used alone a kind, also can use two or more with arbitrary ratio combine.
It should be noted that, as the electrolyte of lithium-ion capacitor, the electrolyte same with the above-mentioned electrolyte that can be used for lithium rechargeable battery can be used.
(manufacture method of electrochemical element)
As the concrete manufacture method of the electrochemical element such as lithium rechargeable battery, lithium-ion capacitor, such as method can be listed below: across the superimposed positive pole of dividing plate and negative pole, and put into battery case after it is curling according to cell shapes, bending etc., inject electrolyte to battery case and seal.Further, also expansion alloy can be put into as required; The overcurrent such as fuse, PTC element prevent element; Lead plate etc., thus prevent the pressure of inside battery from raising, cross discharge and recharge.The shape of lithium rechargeable battery can be the arbitrary shape in Coin shape, coin shape, flap-type, cylinder type, square, platypelloid type etc.With regard to the material of battery case, as long as moisture can be hindered to invade the material of inside battery, be not particularly limited in the laminated material etc. of metal, aluminium etc.
Electro-chemical element electrode adhesive according to the present embodiment, the productivity of electrode is excellent, and thickness and precision and the flexibility of the electrode obtained are good.In addition, because electro-chemical element electrode of the present invention does not use the dispersants such as carboxymethyl cellulose, therefore, it is possible to reduce the resistance of the electrochemical element obtained.
In addition, by making the glass transition temperature of electrode binding agent in given scope, even the particle complex obtained is small particle diameter also can guarantee mobility, therefore, it is possible to guarantee the thickness and precision of electrode.Further, by making the glass transition temperature of electro-chemical element electrode adhesive in given scope, intensity and the flexibility of the electrode obtained can be guaranteed.
In addition, owing to not using slurry when obtaining particle complex, the energy spent by manufacture therefore can be reduced.Further, because continued operation is easy, therefore rate of finished products can be improved.
Embodiment
Below, the present invention is described particularly, but the present invention is not limited to embodiment shown below in conjunction with the embodiments, at random can changes in the scope of scope being no more than main idea of the present invention and equalization thereof and implement.It should be noted that, in the following description, " % " and " part " of expression amount unless otherwise specified, is then weight basis.
In embodiment and comparative example, the mensuration of the volume reference D50 average grain diameter (Db) of the mensuration of glass transition temperature (Tg) of electrode binding agent (negative pole adhesive or positive pole adhesive), the mensuration of the volume reference D50 average grain diameter (primary particle diameter) of primary particle, the volume reference D50 average grain diameter (Da) of particle complex and electrode active material, 120 DEG C of volatile ingredients mensuration of electrode binding agent, the mensuration of minimum masking temperature of electrode binding agent and the measuring shape of electrode binding agent are carried out respectively as follows.
< glass transition temperature >
The glass transition temperature (Tg) of electrode binding agent uses differential scanning calorimeter (Nanotechnology Inc. DSC6220SII), measures based on JISK7121:1987.
The mensuration > of < primary particle diameter
The electrode binding agent (negative pole adhesive 1 ~ 12, positive pole adhesive 1 ~ 13) of embodiment and comparative example manufacture is added respectively in 1% aqueous solution of sodium n-alkylbenzenesulfonate, ultrasonic wave is utilized to carry out decentralized, then the accumulation domain size distribution obtained based on utilizing CoulterCounterLS230 (Coulter Inc. particle size determination device) measures, and will be equivalent to the volume reference D50 average grain diameter (primary particle diameter) of particle diameter as electrode binding agent of its 50% accumulated value.
The mensuration > of <Da and Db
Based on utilizing laser diffraction/diffuse transmission type particle size distribution device (MicrotracMT3200II; Day machine dress) the volume reference D50 average grain diameter (Db) of electrode active material that uses in the volume reference D50 average grain diameter (Da) of particle complex that manufactures in the accumulation particle size distribution measuring of dry type that obtains embodiment and comparative example and embodiment and comparative example, obtain than (Da/Db).
The mensuration > of <120 DEG C of volatile ingredient
Powdered negative pole adhesive 1 ~ 12, Powdered positive pole adhesive 1 ~ 13 that embodiment and comparative example manufacture is put into respectively in the baking oven being set as 120 DEG C, every mensuration of carrying out binder wt for 10 minutes, stopped measuring in the moment that weight change reaches lower than 0.1%.Using now from initial stage weight play measure stop time till weight rate (ratio of minimizing) as 120 DEG C of volatile ingredients.
The minimum masking temperature > of <
Use minimum masking temperature measuring apparatus (MFFTB90; RHOPOINT Inc.), test according to ISO2115.
< measuring shape >
Utilize SEM to observe powdered electrode adhesive, 30, the particle observed in random taking-up image, obtains the average minor axis diameter of each particle, average major axis diameter, and calculates average spherical degree.By now average spherical degree be more than 80% situation be considered as spherical, average spherical degree and be considered as non-spherical lower than the particle of 80%.
In addition, in embodiment and comparative example, electrode precision, the flexibility of electrode and the evaluation of speed characteristic has been carried out as follows respectively.
< electrode precision >
The upper 10cm in upper 10cm, MD direction (longitudinal direction), TD direction (transverse direction) for the electrode active material layer made in embodiment and comparative example, determine to get equably on TD direction 3 points, in the MD direction get equably 3, the thickness of 9 altogether.The mean value of this thickness is set to A, when distance average thickness is farthest set to B, utilizes following formula to calculate thickness of electrode deviation.
Thickness of electrode deviation precision (%)=(| A-B|) × 100/A
It can be used as electrode precision, utilize following benchmark to evaluate.Result is as shown in table 1 and table 2.This value less expression mouldability is more excellent.
A: lower than 4%
More than B:4% and lower than 9%
More than C:9% and lower than 15%
More than D:15%
E: porose on electrode
The flexibility > of < electrode
The electro-chemical element electrode made in embodiment and comparative example is cut into 1cm × 8cm, is wound in the metal bar of diameter 3mm, 4mm, 5mm respectively, the crackle produced is evaluated as follows.Result is as shown in table 1 and table 2.Crackle fewer expression flexibility is more excellent, namely represents that pole strength is more excellent.
A: do not have crackle on the metal bar of diameter 3mm
B: do not have crackle on the metal bar of diameter 4mm, but crackle is there is on the metal bar of diameter 3mm
C: there is crackle on the metal bar of diameter 5mm
< speed characteristic >
For the lithium rechargeable battery of the laminated units type made in embodiment and comparative example, after injecting electrolytic solution, leave standstill 5 hours, in 25 DEG C of atmospheres, charge to cell voltage by the constant flow method of 0.2C is 3.65V, then 60 DEG C are warming up to, carry out 12 hours maturation process, in 25 DEG C of atmospheres, be discharged to cell voltage by the constant flow method of 0.2C is 3.00V.
Then, in 25 DEG C of atmospheres, carried out charging with 4.2V, 0.2C speed, discharged with 0.2C and 2.0C speed.Now, discharge capacity during each discharge rate is defined as C
0.2(discharge capacity during 0.2C), C
2.0(discharge capacity during 2.0C), obtains with Δ C=C
2.0/ C
0.2time the Capacitance Shift Rate that represents of discharge capacity × 100 (%), and to evaluate according to following benchmark.Result is as shown in table 1 and table 2.The value of this Capacitance Shift Rate Δ C is higher, represents that discharging-rate performance (speed characteristic) is more excellent.
A: Δ C is more than 83%
B: Δ C is more than 82% and lower than 83%
C: Δ C is more than 80% and lower than 82%
D: Δ C is lower than 80%
< embodiment 1>
(the negative pole manufacture of particle shaped polymer 1)
Styrene (hereinafter also referred to as " ST ") 78 parts is added in the 5MPa pressure vessel of band mixer, 1, 3-butadiene (hereinafter also referred to as " BD ") 19 parts, itaconic acid (hereinafter also referred to as " IA ") 3 parts, as alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1 of emulsifying agent, DowChemical Inc.) work as gauge 0.4 part with solid constituent, ion exchange water 150 parts, as the tertiary lauryl mercaptan (hereinafter also referred to as " TDM ") 0.3 part of chain-transferring agent and the potassium peroxydisulfate 0.5 part as polymerization initiator, after stirring fully, heat to 75 DEG C with initiated polymerization.The moment reaching 96% at polymerisation conversion cools, and stops reaction, obtains negative pole particle shaped polymer 1 (Styrene-Butadiene; Hereinafter also referred to as " SBR ") aqueous dispersion.The minimum masking temperature of negative pole particle shaped polymer 1 is 55 DEG C, glass transition temperature (Tg) is 50 DEG C, primary particle diameter is 132nm.
(drying of particle shaped polymer and fragmentation)
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 1, to remove moisture in 40 DEG C, then utilize vacuum drier 40 DEG C, make it dry under the condition of 0.6kPa.Then, utilize the negative pole particle shaped polymer 1 of the broken drying of mortar, obtain pulverous negative pole adhesive 1.120 DEG C of volatile ingredients of pulverous negative pole adhesive 1 are 0.1%.
(manufacture of particle complex)
Using the Delanium (average grain diameter: 24.5 μm, graphite layers is apart from (interval, face (d value) in (002) face based on X-ray diffraction method measures): 0.354nm) 98.8 parts and above-mentioned negative pole adhesive are with solid constituent conversion gauge 1.2 parts as negative electrode active material, Henschel mixer (Mitsui three pond Inc.) is used to mix 10 minutes, make negative pole adhesive attachment in negative electrode active material, obtain particle complex.
(manufacture of negative pole)
Constant feeder (Nikka Inc. " NikkasprayK-V ") is used particle complex obtained above to be supplied to the compacting roller (roll temperature 100 DEG C, compacting line pressure 500kN/m) of roll squeezer (HIRANOGIKENKOGYO Inc. " shears asperities hot-rolling ").The Copper Foil of inserting thickness 20 μm between compacting roller, makes to be attached to Copper Foil from the above-mentioned particle complex of constant feeder supply, carries out extrusion forming, obtain the negative pole with negative electrode active material with shaping speed 1.5m/ minute.
(manufacture of positive pole slurry and positive pole)
To the LiCoO as positive active material
2kynoar (the PVDF as positive pole adhesive is added in 92 parts; KurehaChemical Inc. " KF-1100 ") and make solid constituent amount reach 2 parts, then, add acetylene black (Denki Kagaku Kogyo kabushiki's system " HS-100 ") 6 parts, 1-METHYLPYRROLIDONE 20 parts, utilize planetary-type mixer to mix, obtain positive pole slurry.This positive pole slurry is coated the aluminium foil of thickness 18 μm, after 30 minutes, carry out roll-in in 120 DEG C of dryings, obtain the positive pole of thickness 60 μm.
(preparation of dividing plate)
The polypropylene dividing plate of individual layer (wide 65mm, long 500mm, thick 25 μm, utilize dry process manufacture, the porosity 55%) is punched to 5 × 5cm
2square.
(manufacture of lithium rechargeable battery)
As the external packing of battery, prepare aluminium housing material.Positive pole obtained above is punched to 4 × 4cm
2square, configure in the mode making the surface on current collection side contact with aluminium housing material.In addition, the face of the positive electrode active material layer of positive pole obtained above is configured with foursquare dividing plate obtained above.Then, negative pole obtained above is cut into 4.2 × 4.2cm
2square, be configured on dividing plate towards the mode of dividing plate to make the surface of negative electrode active material layer side.Further, be filled with containing 2.0% vinylene carbonate, concentration is the LiPF of 1.0M
6solution.This LiPF
6the solvent of solution is the mixed solvent (EC/EMC=3/7 (volume ratio)) of ethylene carbonate (EC) and methyl ethyl carbonate (EMC).And then, in order to by the opening of aluminium packaging material seal, in 150 DEG C carry out sealing and by aluminium external packing seal, manufactured the lithium rechargeable battery (laminated-type battery) of laminated-type.
< embodiment 2>
(the negative pole manufacture of particle shaped polymer 2)
Styrene 74.5 parts, 1 is added in the 5MPa pressure vessel of band mixer, 3-butadiene 22.5 parts, itaconic acid 3 parts, as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of emulsifying agent using solid constituent when gauge 0.4 part, ion exchange water 150 parts, the tertiary lauryl mercaptan 0.3 part as chain-transferring agent and the potassium peroxydisulfate 0.5 part as polymerization initiator, after stirring fully, heat to 75 DEG C with initiated polymerization.The moment reaching 96% at polymerisation conversion cools, and stops reaction, obtains the aqueous dispersion of negative pole particle shaped polymer 2.The minimum masking temperature of particle shaped polymer 2 is 40 DEG C, and glass transition temperature (Tg) is 40 DEG C, and primary particle diameter is 135nm.
(drying of particle shaped polymer and fragmentation)
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 2, to remove moisture in 25 DEG C, then utilize vacuum drier 25 DEG C, make it dry under the condition of 0.6kPa.Then, utilize the negative pole particle shaped polymer 2 of the broken drying of mortar, obtain pulverous negative pole adhesive 2.120 DEG C of volatile ingredients of pulverous negative pole adhesive 2 are 0.1%.
Except employing above-mentioned negative pole adhesive 2, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< embodiment 3>
(the negative pole manufacture of particle shaped polymer 3)
Styrene 85 parts, 1 is added in the 5MPa pressure vessel of band mixer, 3-butadiene 12 parts, itaconic acid 3 parts, as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of emulsifying agent using solid constituent when gauge 0.4 part, ion exchange water 150 parts, the tertiary lauryl mercaptan 0.3 part as chain-transferring agent and the potassium peroxydisulfate 0.5 part as polymerization initiator, after stirring fully, heat to 75 DEG C with initiated polymerization.The moment reaching 96% at polymerisation conversion cools, and stops reaction, obtains the aqueous dispersion of negative pole particle shaped polymer 3.The minimum masking temperature of negative pole particle shaped polymer 3 is 88 DEG C, and glass transition temperature (Tg) is 70 DEG C, and primary particle diameter is 134nm.
(drying of particle shaped polymer and fragmentation)
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 3, to remove moisture in 60 DEG C, then utilize vacuum drier 60 DEG C, make it dry under the condition of 0.6kPa.Then, utilize the negative pole particle shaped polymer 3 of the broken drying of mortar, obtain pulverous negative pole adhesive 3.120 DEG C of volatile ingredients of pulverous negative pole adhesive 3 are 0.1%.
Except employing above-mentioned negative pole adhesive 3, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< embodiment 4>
(the negative pole manufacture of particle shaped polymer 4)
Styrene 78 parts, 1 is added in the 5MPa pressure vessel of band mixer, 3-butadiene 19 parts, itaconic acid 3 parts, as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of emulsifying agent using solid constituent when gauge 2.0 parts, ion exchange water 150 parts, the tertiary lauryl mercaptan 0.3 part as chain-transferring agent and the potassium peroxydisulfate 0.5 part as polymerization initiator, after stirring fully, heat to 75 DEG C with initiated polymerization.The moment reaching 96% at polymerisation conversion cools, and stops reaction, obtains the aqueous dispersion of negative pole particle shaped polymer 4.The minimum masking temperature of negative pole particle shaped polymer 4 is 53 DEG C, and glass transition temperature (Tg) is 50 DEG C, and primary particle diameter is 80nm.
(drying of particle shaped polymer and fragmentation)
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 4, to remove moisture in 40 DEG C, then utilize vacuum drier 40 DEG C, make it dry under the condition of 0.6kPa.Then, utilize the negative pole particle shaped polymer 4 of the broken drying of mortar, obtain pulverous negative pole adhesive 4.120 DEG C of volatile ingredients of pulverous negative pole adhesive 4 are 0.4%.
Except employing above-mentioned negative pole adhesive 4, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< embodiment 5>
(the negative pole manufacture of particle shaped polymer 5)
In the 5MPa pressure vessel of band mixer, add ion exchange water 210 parts, be heated to 75 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, styrene 78 parts, 1 is added to from the 5MPa pressure vessel of above-mentioned different other band mixer, 3-butadiene 19 parts, itaconic acid 3 parts, as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of emulsifying agent using solid constituent when gauge 0.4 part, as the tertiary lauryl mercaptan 0.3 part of chain-transferring agent and ion exchange water 26 parts, stirring and emulsifying is carried out to it, thus has prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 3.5 hours with constant speed, this monomer mixed solution is added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain the aqueous dispersion of negative pole particle shaped polymer 5.The minimum masking temperature of negative pole particle shaped polymer 5 is 56 DEG C, and glass transition temperature (Tg) is 50 DEG C, and primary particle diameter is 304nm.
(drying of particle shaped polymer and fragmentation)
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 5, to remove moisture in 40 DEG C, then utilize vacuum drier 40 DEG C, make it dry under the condition of 0.6kPa.Then, utilize the negative pole particle shaped polymer 5 of the broken drying of mortar, obtain pulverous negative pole adhesive 5.120 DEG C of volatile ingredients of pulverous negative pole adhesive 5 are 0.1%.
Except employing above-mentioned negative pole adhesive 5, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< embodiment 6>
(the negative pole manufacture of particle shaped polymer 6)
In the 5MPa pressure vessel of band mixer, add ion exchange water 210 parts, be heated to 75 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, styrene 78 parts, 1 is added to from the 5MPa pressure vessel of above-mentioned different other band mixer, 3-butadiene 19 parts, itaconic acid 3 parts, as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of emulsifying agent using solid constituent when gauge 0.2 part, as the tertiary lauryl mercaptan 0.3 part of chain-transferring agent and ion exchange water 26 parts, stirring and emulsifying is carried out to it, thus has prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 3.5 hours with constant speed, be added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain the aqueous dispersion of negative pole particle shaped polymer 6.The minimum masking temperature of negative pole particle shaped polymer 6 is 56 DEG C, and glass transition temperature (Tg) is 50 DEG C, and primary particle diameter is 625nm.
(drying of particle shaped polymer and fragmentation)
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 6, to remove moisture in 40 DEG C, then utilize vacuum drier 40 DEG C, make it dry under the condition of 0.6kPa.Then, utilize the negative pole particle shaped polymer 6 of the broken drying of mortar, obtain pulverous negative pole adhesive 6.120 DEG C of volatile ingredients of pulverous negative pole adhesive 6 are 0.1%.
Except employing above-mentioned negative pole adhesive 6, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< embodiment 7>
Rotary Evaporators is utilized from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 1, to remove moisture in 40 DEG C, then, except do not utilize vacuum drier 40 DEG C, make except its drying under the condition of 0.6kPa, carry out drying and the fragmentation of particle shaped polymer similarly to Example 1, obtain pulverous negative pole adhesive 7.120 DEG C of volatile ingredients of pulverous negative pole adhesive 7 are 0.8%.
Except employing above-mentioned negative pole adhesive 7, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< comparative example 1>
(the negative pole manufacture of particle shaped polymer 7)
Styrene 70 parts, 1 is added in the 5MPa pressure vessel of band mixer, 3-butadiene 27 parts, itaconic acid 3 parts, as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of emulsifying agent using solid constituent when gauge 0.4 part, ion exchange water 150 parts, the tertiary lauryl mercaptan 0.3 part as chain-transferring agent and the potassium peroxydisulfate 0.5 part as polymerization initiator, after stirring fully, heat to 75 DEG C with initiated polymerization.The moment reaching 96% at polymerisation conversion cools, and stops reaction, obtains the aqueous dispersion of negative pole particle shaped polymer 7.The minimum masking temperature of negative pole particle shaped polymer 7 is 27 DEG C, and glass transition temperature (Tg) is 30 DEG C, and primary particle diameter is 130nm.
(drying of particle shaped polymer and fragmentation)
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 7, to remove moisture in 20 DEG C, then utilize vacuum drier 20 DEG C, make it dry under the condition of 0.6kPa.Then, utilize the negative pole particle shaped polymer 7 of the broken drying of mortar, obtain pulverous negative pole adhesive 8 that coherency is slightly high.120 DEG C of volatile ingredients of pulverous negative pole adhesive 8 are 0.1%.
Except employing above-mentioned negative pole adhesive 8, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< comparative example 2>
(the negative pole manufacture of particle shaped polymer 8)
Styrene 94 parts, 1 is added in the 5MPa pressure vessel of band mixer, 3-butadiene 3 parts, itaconic acid 3 parts, as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of emulsifying agent using solid constituent when gauge 0.4 part, ion exchange water 150 parts and the potassium peroxydisulfate 0.5 part as polymerization initiator, after stirring fully, heat to 75 DEG C with initiated polymerization.The moment reaching 96% at polymerisation conversion cools, and stops reaction, obtains the aqueous dispersion of negative pole particle shaped polymer 8.The minimum masking temperature of negative pole particle shaped polymer 8 is 120 DEG C, and glass transition temperature (Tg) is 100 DEG C, and primary particle diameter is 135nm.
(drying of particle shaped polymer and fragmentation)
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 8, to remove moisture in 80 DEG C, then utilize vacuum drier 80 DEG C, make it dry under the condition of 0.6kPa.Then, utilize the negative pole particle shaped polymer 8 of the broken drying of mortar, obtain pulverous negative pole adhesive 9.
Except employing above-mentioned negative pole adhesive 9, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< comparative example 3>
(the negative pole manufacture of particle shaped polymer 9)
Relative to the aqueous dispersion of negative pole with particle shaped polymer 1, to be that the weight ratio of 100 parts adds toluene relative to polymer weight 10 parts, utilize emulsion dispersion device (MilderMDN303V; Pacific Ocean Ji Gong Inc.) carry out emulsification with 15000rpm.Then, use Rotary Evaporators to remove desolventizing from this emulsion, obtain the aqueous dispersion of negative pole particle shaped polymer 9.The minimum masking temperature of negative pole particle shaped polymer 9 is 53 DEG C, and glass transition temperature (Tg) is 50 DEG C, and primary particle diameter is 3020nm.
(drying of particle shaped polymer and fragmentation)
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 9, to remove moisture in 40 DEG C, then utilize vacuum drier 40 DEG C, make it dry under the condition of 0.6kPa.Then, utilize the negative pole particle shaped polymer 9 of the broken drying of mortar, obtain pulverous negative pole adhesive 10.120 DEG C of volatile ingredients of pulverous negative pole adhesive 10 are 0.1%.
Except employing above-mentioned negative pole adhesive 10, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< comparative example 4>
Utilize Rotary Evaporators in time removing moisture for 40 DEG C from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 1, stop the removing of moisture in midway, obtain pulverous negative pole adhesive 11.120 DEG C of volatile ingredients of pulverous negative pole adhesive 11 are 2%.
Except employing above-mentioned negative pole adhesive 11, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< comparative example 5>
Utilize Rotary Evaporators from the aqueous dispersion of above-mentioned negative pole particle shaped polymer 1, to remove moisture in 60 DEG C, then utilize vacuum drier 60 DEG C, make it dry under the condition of 0.6kPa.Then, the negative pole particle shaped polymer 1 utilizing mortar to pulverize through membranization, then utilizes jet mill to carry out pulverizing until average grain diameter reaches about 5000nm further, obtains pulverous negative pole adhesive 12.120 DEG C of volatile ingredients of pulverous negative pole adhesive 12 are 0.1%.
Except employing above-mentioned negative pole adhesive 12, the manufacture of negative pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 1.
< embodiment 8>
(the positive pole manufacture of particle shaped polymer 1)
To in the reactor being provided with mechanical agitator and condenser, in nitrogen atmosphere, charging ion exchange water 210 parts, is heated to 70 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, to be provided with mechanical agitator from above-mentioned different other container, in nitrogen atmosphere, add butyl acrylate (hereinafter also referred to as " BA ") 20 parts, EMA (hereinafter also referred to as " EMA ") 77.5 parts, methacrylic acid (hereinafter also referred to as " MAA ") 2.4 parts, allyl methacrylate (hereinafter also referred to as " AMA ") 0.1 part, as alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1 of the concentration 30% of emulsifying agent, DOWChemical Inc.) work as gauge 1.0 parts with solid constituent, and ion exchange water 22.7 parts, stirring and emulsifying is carried out to it, thus prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, this monomer mixed solution is added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain positive pole particle shaped polymer 1 (acrylic polymer; Hereinafter also referred to as " acrylic compounds ") aqueous dispersion.In addition, the minimum masking temperature of positive pole particle shaped polymer 1 is 45 DEG C, and glass transition temperature (Tg) is 40 DEG C, and primary particle diameter is 310nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 1, and utilize vacuum drier 30 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 1.120 DEG C of volatile ingredients of pulverous positive pole adhesive 1 are 0.1%.
(manufacture of particle complex)
For the NMC (111) 92.5 parts as positive active material, the acetylene black 6 parts as conductive agent and above-mentioned positive pole adhesive with solid constituent conversion gauge 1.5 parts, Henschel mixer (Mitsui three pond Inc.) is used to mix 10 minutes, make positive pole adhesive attachment in positive active material, obtain particle complex.
(manufacture of positive pole)
Constant feeder (Nikka Inc. " NikkasprayK-V ") is used particle complex obtained above to be supplied to the compacting roller (roll temperature 100 DEG C, compacting line pressure 500kN/m) of roll squeezer (HIRANOGIKENKOGYO Inc. " shears asperities hot-rolling ").The aluminium foil of inserting thickness 20 μm between compacting roller, makes to be attached to aluminium foil from the above-mentioned particle complex of constant feeder supply, carries out extrusion forming, obtain the positive pole with positive active material with shaping speed 1.5m/ minute.
(manufacture of negative pole slurry and negative pole)
Using the Delanium (average grain diameter: 24.5 μm as negative electrode active material, graphite layers is apart from (interval, face (d value) based on (002) face that X-ray diffraction method measures): 0.354nm) 96 parts, styrene butadiene copolymers latex (BM-400B) is with solid constituent conversion gauge 3.0 parts, 1.5% aqueous solution (DN-800H:Daicel chemical industrial company system) of carboxymethyl cellulose measures 1.0 parts of mixing with solid constituent conversion, then adding ion exchange water makes solid component concentration reach 50%, carry out mixing dispersion, obtain negative pole slurry.This negative pole slurry is applied to the Copper Foil of thickness 18 μm, in 120 DEG C of dryings 30 minutes, then carries out roll-in, obtain the negative pole of thickness 50 μm.
(preparation of dividing plate)
The polypropylene dividing plate of individual layer (wide 65mm, long 500mm, thick 25 μm, utilize dry process manufacture, the porosity 55%) is punched to 5 × 5cm
2square.
(manufacture of lithium rechargeable battery)
As the external packing of battery, prepare aluminium housing material.Positive pole obtained above is punched to 4 × 4cm
2square, configure in the mode making the surface on current collection side contact with aluminium housing material.In addition, the face of the positive electrode active material layer of positive pole obtained above is configured with foursquare dividing plate obtained above.Then, negative pole obtained above is cut into 4.2 × 4.2cm
2square, be configured on dividing plate towards the mode of dividing plate to make the surface of negative electrode active material layer side.Further, be filled with containing 2.0% vinylene carbonate, concentration is the LiPF of 1.0M
6solution.This LiPF
6the solvent of solution is the mixed solvent (EC/EMC=3/7 (volume ratio)) of ethylene carbonate (EC) and methyl ethyl carbonate (EMC).And then, in order to by the opening of aluminium packaging material seal, in 150 DEG C carry out sealing and by aluminium external packing seal, manufactured the lithium rechargeable battery (laminated-type battery) of laminated-type.
< embodiment 9>
(the positive pole manufacture of particle shaped polymer 2)
To in the reactor being provided with mechanical agitator and condenser, in nitrogen atmosphere, charging ion exchange water 210 parts, is heated to 70 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, to be provided with mechanical agitator from above-mentioned different other container, in nitrogen atmosphere, add butyl acrylate 12 parts, EMA 85.5 parts, methacrylic acid 2.4 parts, allyl methacrylate 0.1 part, work as gauge 1.0 parts and ion exchange water 22.7 parts as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of the concentration 30% of emulsifying agent with solid constituent, stirring and emulsifying is carried out to it, thus has prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, this monomer mixed solution is added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain the aqueous dispersion of positive pole particle shaped polymer 2.In addition, the minimum masking temperature of positive pole particle shaped polymer 2 is 52 DEG C, and glass transition temperature (Tg) is 50 DEG C, and primary particle diameter is 319nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 2, and utilize vacuum drier 40 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 2.120 DEG C of volatile ingredients of pulverous positive pole adhesive 2 are 0.1%.
Except employing above-mentioned positive pole adhesive 2, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< embodiment 10>
(the positive pole manufacture of particle shaped polymer 3)
To in the reactor being provided with mechanical agitator and condenser, in nitrogen atmosphere, charging ion exchange water 210 parts, is heated to 70 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, to be provided with mechanical agitator from above-mentioned different other container, in nitrogen atmosphere, add butyl acrylate 6 parts, EMA 91.5 parts, methacrylic acid 2.4 parts, allyl methacrylate 0.1 part, work as gauge 1.0 parts and ion exchange water 22.7 parts as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of the concentration 30% of emulsifying agent with solid constituent, stirring and emulsifying is carried out to it, thus has prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, this monomer mixed solution is added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain the aqueous dispersion of positive pole particle shaped polymer 3.In addition, the minimum masking temperature of positive pole particle shaped polymer 3 is 65 DEG C, and glass transition temperature (Tg) is 60 DEG C, and primary particle diameter is 331nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 3, and utilize vacuum drier 40 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 3.120 DEG C of volatile ingredients of pulverous positive pole adhesive 3 are 0.1%.
Except employing above-mentioned positive pole adhesive 3, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< embodiment 11>
(the positive pole manufacture of particle shaped polymer 4)
To in the reactor being provided with mechanical agitator and condenser, in nitrogen atmosphere charging ion exchange water 210 parts, as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of the concentration 30% of emulsifying agent with solid constituent when gauge 0.5 part, be heated to 70 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, to be provided with mechanical agitator from above-mentioned different other container, in nitrogen atmosphere, add butyl acrylate 20 parts, EMA 77.5 parts, methacrylic acid 2.4 parts, allyl methacrylate 0.1 part, work as gauge 0.5 part and ion exchange water 22.7 parts as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of the concentration 30% of emulsifying agent with solid constituent, stirring and emulsifying is carried out to it, thus has prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, this monomer mixed solution is added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain the aqueous dispersion of positive pole particle shaped polymer 4.In addition, the minimum masking temperature of positive pole particle shaped polymer 4 is 43 DEG C, and glass transition temperature (Tg) is 40 DEG C, and primary particle diameter is 139nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 4, and utilize vacuum drier 30 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 4.120 DEG C of volatile ingredients of pulverous positive pole adhesive 4 are 0.1%.
Except employing above-mentioned positive pole adhesive 4, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< embodiment 12>
(the positive pole manufacture of particle shaped polymer 5)
To in the reactor being provided with mechanical agitator and condenser, in nitrogen atmosphere charging ion exchange water 210 parts, as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of the concentration 30% of emulsifying agent with solid constituent when gauge 0.8 part, be heated to 70 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, to be provided with mechanical agitator from above-mentioned different other container, in nitrogen atmosphere, add butyl acrylate 20 parts, EMA 77.5 parts, methacrylic acid 2.4 parts, allyl methacrylate 0.1 part, work as gauge 0.8 part and ion exchange water 22.7 parts as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of the concentration 30% of emulsifying agent with solid constituent, stirring and emulsifying is carried out to it, thus has prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, this monomer mixed solution is added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain the aqueous dispersion of positive pole particle shaped polymer 5.In addition, the minimum masking temperature of positive pole particle shaped polymer 5 is 43 DEG C, and glass transition temperature (Tg) is 40 DEG C, and primary particle diameter is 100nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 5, and utilize vacuum drier 30 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 5.120 DEG C of volatile ingredients of pulverous positive pole adhesive 5 are 0.1%.
Except employing above-mentioned positive pole adhesive 5, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< embodiment 13>
(the positive pole manufacture of particle shaped polymer 6)
To in the reactor being provided with mechanical agitator and condenser, in nitrogen atmosphere, charging ion exchange water 210 parts, is heated to 70 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, to be provided with mechanical agitator from above-mentioned different other container, in nitrogen atmosphere, add butyl acrylate 20 parts, EMA 77.5 parts, methacrylic acid 2.4 parts, allyl methacrylate 0.1 part, work as gauge 0.4 part and ion exchange water 22.7 parts as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of the concentration 30% of emulsifying agent with solid constituent, stirring and emulsifying is carried out to it, thus has prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, this monomer mixed solution is added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain the aqueous dispersion of positive pole particle shaped polymer 6.In addition, the minimum masking temperature of positive pole particle shaped polymer 6 is 48 DEG C, and glass transition temperature (Tg) is 40 DEG C, and primary particle diameter is 625nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 6, and utilize vacuum drier 30 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 6.120 DEG C of volatile ingredients of pulverous positive pole adhesive 6 are 0.1%.
Except employing above-mentioned positive pole adhesive 6, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< embodiment 14>
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 1, obtains particle.Then, except do not utilize vacuum drier 30 DEG C, make under the condition of 0.6kPa, except the particle drying that obtains, to carry out the drying of particle shaped polymer similarly to Example 8, obtain pulverous positive pole adhesive 7.120 DEG C of volatile ingredients of pulverous positive pole adhesive 7 are 0.8%.
Except employing above-mentioned positive pole adhesive 7, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< comparative example 6>
(the positive pole manufacture of particle shaped polymer 7)
To in the reactor being provided with mechanical agitator and condenser, in nitrogen atmosphere, charging ion exchange water 210 parts, is heated to 70 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, to be provided with mechanical agitator from above-mentioned different other container, in nitrogen atmosphere, add butyl acrylate 27.6 parts, EMA 70.0 parts, methacrylic acid 2.4 parts, allyl methacrylate 0.1 part, work as gauge 1.0 parts and ion exchange water 22.7 parts as the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) of the concentration 30% of emulsifying agent with solid constituent, stirring and emulsifying is carried out to it, thus has prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, this monomer mixed solution is added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain the aqueous dispersion of positive pole particle shaped polymer 7.In addition, the minimum masking temperature of positive pole particle shaped polymer 7 is 27 DEG C, and glass transition temperature (Tg) is 30 DEG C, and primary particle diameter is 307nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 7, and utilize vacuum drier 25 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 8.120 DEG C of volatile ingredients of pulverous positive pole adhesive 8 are 0.1%.
Except employing above-mentioned positive pole adhesive 8, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< comparative example 7>
(the positive pole manufacture of particle shaped polymer 8)
To in the reactor being provided with mechanical agitator and condenser, in nitrogen atmosphere, charging ion exchange water 210 parts, is heated to 70 DEG C while stirring, and 1.96% persulfate aqueous solution 25.5 parts is added into reactor.Then, to be provided with mechanical agitator from above-mentioned different other container, in nitrogen atmosphere, add EMA 22.5 parts, methyl methacrylate (hereinafter also referred to as " MMA ") 75.0 parts, methacrylic acid 2.4 parts, allyl methacrylate 0.1 part, as alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1 of the concentration 30% of emulsifying agent, DOWChemical Inc.) work as gauge 1.0 parts with solid constituent, and ion exchange water 22.7 parts, stirring and emulsifying is carried out to it, thus prepared monomer mixed solution.Then, under the state making this monomer mixed solution stirring and emulsifying, through 2.5 hours with constant speed, this monomer mixed solution is added into the reactor that charging has ion exchange water 210 parts and persulfate aqueous solution, make it react until polymerisation conversion reaches 95%, obtain the aqueous dispersion of positive pole particle shaped polymer 8.In addition, the minimum masking temperature of positive pole particle shaped polymer 8 is 115 DEG C, and glass transition temperature (Tg) is 100 DEG C, and primary particle diameter is 280nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 8, and utilize vacuum drier 80 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 9.120 DEG C of volatile ingredients of pulverous positive pole adhesive 9 are 0.1%.
Except employing above-mentioned positive pole adhesive 9, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< comparative example 8>
(the positive pole manufacture of particle shaped polymer 9)
To in the reactor being provided with mechanical agitator and condenser, the alkyl diphenyl ether disulfonate (DOWFAX (registered trade mark) 2A1, DOWChemical Inc.) adding ion exchange water 831 parts and the concentration 30% as emulsifying agent in nitrogen atmosphere works as gauge 10 parts with solid constituent, and add butyl acrylate 6 parts, EMA 91.5 parts, methacrylic acid 2.4 parts, allyl methacrylate 0.1 part, stirring and emulsifying is carried out to this monomer mixed solution.While carry out stirring limit to it to be heated to 60 DEG C, 1.96% persulfate aqueous solution 51 parts is added into reactor.Carry out reacting until polymerisation conversion reaches 98%, obtain the aqueous dispersion of positive pole particle shaped polymer 9.In addition, the minimum masking temperature of positive pole particle shaped polymer 9 is 42 DEG C, and glass transition temperature (Tg) is 60 DEG C, and primary particle diameter is 50nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 9, and utilize vacuum drier 40 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 10.120 DEG C of volatile ingredients of pulverous positive pole adhesive 10 are 0.1%.
Except employing above-mentioned positive pole adhesive 10, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< comparative example 9>
(the positive pole manufacture of particle shaped polymer 10)
Relative to the aqueous dispersion of positive pole with particle shaped polymer 1, to be that the weight ratio of 100 parts adds toluene relative to polymer weight 10 parts, utilize emulsion dispersion device (MilderMDN303V; Pacific Ocean Ji Gong Inc.) carry out emulsification with 15000rpm.Then, use Rotary Evaporators to remove desolventizing from this emulsion, obtain the aqueous dispersion of positive pole particle shaped polymer 10.The minimum masking temperature of positive pole particle shaped polymer 10 is 53 DEG C, and glass transition temperature (Tg) is 40 DEG C, and primary particle diameter is 3050nm.
(drying of particle shaped polymer)
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 9, and utilize vacuum drier 40 DEG C, under the condition of 0.6kPa, make the particle that obtains dry, obtain pulverous positive pole adhesive 11.120 DEG C of volatile ingredients of pulverous positive pole adhesive 11 are 0.1%.
Except employing above-mentioned positive pole adhesive 11, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< comparative example 10>
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 30 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 1, vacuumize is not carried out to gained particle, obtain pulverous positive pole adhesive 12.120 DEG C of volatile ingredients of pulverous positive pole adhesive 12 are 2%.
Except employing above-mentioned positive pole adhesive 12, the manufacture of positive pole and the manufacture of lithium rechargeable battery are carried out similarly to Example 8.
< comparative example 11>
In spray dryer (great river former chemical industry machine Inc.), use the sprayer (diameter 65mm) of rotating circular disk mode, setting speed is 25,000rpm, hot air temperature are 40 DEG C, spray drying granulation is carried out to the aqueous dispersion of above-mentioned positive pole particle shaped polymer 1, and utilize vacuum drier 70 DEG C, under the condition of 0.6kPa, make the particle that obtains dry.Then, the positive pole particle shaped polymer 1 utilizing mortar to pulverize through membranization, then utilizes jet mill to carry out pulverizing until average grain diameter reaches about 5000nm further, obtains pulverous positive pole adhesive 13.120 DEG C of volatile ingredients of pulverous positive pole adhesive 13 are 0.1%.
As shown in table 1 and table 2, use the electrode precision of the particle complex that comprises following electrode binding agent and the electrode that manufactures, flexibility good, and then, use the speed characteristic of the lithium rechargeable battery of this electrode good, described electrode binding agent by glass transition temperature be 35 ~ 80 DEG C, the volume reference D50 average grain diameter of primary particle is that the polymer of 80 ~ 1000nm is formed, its volatile ingredient 120 DEG C time is less than 1 % by weight, and this adhesive is Powdered Composite particle.
Claims (9)
1. an electro-chemical element electrode adhesive, its by glass transition temperature be 35 ~ 80 DEG C, the volume reference D50 average grain diameter of primary particle is that the polymer of 80 ~ 1000nm is formed,
The volatile ingredient of this adhesive 120 DEG C time is less than 1 % by weight,
This adhesive is Powdered Composite particle.
2. electro-chemical element electrode adhesive according to claim 1, it carries out drying by the aqueous dispersion of the particle shaped polymer by being dispersed with described polymer and obtains under the condition of the minimum masking temperature lower than described particle shaped polymer.
3. electro-chemical element electrode adhesive according to claim 1 and 2, it comprises at least one monomeric unit be selected from lower group: conjugated diene monomeric unit, acrylate monomeric units, methacrylate monomers unit, aromatic vinyl compound monomer unit, olefinically unsaturated nitriles monomeric unit, ethylenically unsaturated carboxylic acids monomeric unit, olefinic unsaturated acyl amine monomer units, multifunctional olefinic type monomers unit.
4. an electro-chemical element electrode particle complex, it is obtained by mixing by the electro-chemical element electrode adhesive according to any one of electrode active material and claims 1 to 3 is carried out dry type.
5. electro-chemical element electrode particle complex according to claim 4, wherein, the ratio (Da/Db) of the volume reference D50 average grain diameter (Da) of this electro-chemical element electrode particle complex and the volume reference D50 average grain diameter (Db) of described electrode active material is 0.5 ~ 2.
6. an electro-chemical element electrode, it is that lamination comprises the electrode active material layer of electro-chemical element electrode particle complex according to claim 5 on the current collector.
7. electro-chemical element electrode according to claim 6, wherein, described electrode active material layer obtains by the electrode material comprising described electro-chemical element electrode particle complex is carried out extrusion forming on described collector body.
8. an electrochemical element, it possesses the electro-chemical element electrode described in claim 6 or 7.
9. a manufacture method for electro-chemical element electrode, it comprises:
Drying process: the aqueous dispersion being dispersed with the spherical particle shaped polymer that glass transition temperature is 35 ~ 80 DEG C, the volume reference average grain diameter D50 of primary particle is 80 ~ 1000nm is carried out drying under the condition of the minimum masking temperature lower than described particle shaped polymer and obtains Powdered Composite particle;
Mixed processes: described Powdered Composite particle and electrode active material are carried out dry type and is obtained by mixing particle complex; And
Electrode manufacturing process: use described particle complex to manufacture electrode.
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| JP2013-112800 | 2013-05-29 | ||
| PCT/JP2014/063678 WO2014192652A1 (en) | 2013-05-29 | 2014-05-23 | Binder for use in electrochemical device electrodes, particle composite for use in electrochemical device electrodes, electrochemical device electrode, electrochemical device, and electrochemical device electrode manufacturing method |
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| JP (1) | JP6327249B2 (en) |
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| CN109314245A (en) * | 2016-06-29 | 2019-02-05 | 日本瑞翁株式会社 | Binder composition for non-aqueous secondary battery electrode, non-aqueous secondary battery slurry composition for electrode, non-aqueous secondary battery electrode and non-aqueous secondary battery |
| CN111108629A (en) * | 2017-09-28 | 2020-05-05 | 日本瑞翁株式会社 | Composition for functional layer of nonaqueous secondary battery, functional layer for nonaqueous secondary battery, and nonaqueous secondary battery |
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| JP2015069928A (en) * | 2013-09-30 | 2015-04-13 | 日本ペイントホールディングス株式会社 | Composite particle for electrode and method for producing composite particle for electrode |
| JP6511759B2 (en) * | 2014-09-30 | 2019-05-15 | 株式会社豊田中央研究所 | Composite particle for electrode and method for producing the same |
| WO2016152164A1 (en) * | 2015-03-24 | 2016-09-29 | 日本ゼオン株式会社 | Method for producing slurry composition for secondary battery positive electrode, positive electrode for secondary battery, and secondary battery |
| US11183693B2 (en) | 2016-07-29 | 2021-11-23 | Kao Corporation | Resin composition for power storage device electrode |
| JP6790877B2 (en) * | 2017-01-31 | 2020-11-25 | 株式会社Ｇｓユアサ | Non-aqueous electrolyte power storage element and its manufacturing method |
| JP2019133908A (en) * | 2018-01-26 | 2019-08-08 | 花王株式会社 | Lithium ion secondary battery positive electrode |
| WO2019146720A1 (en) * | 2018-01-26 | 2019-08-01 | 花王株式会社 | Lithium ion secondary battery positive electrode |
| WO2023182248A1 (en) * | 2022-03-24 | 2023-09-28 | 東亞合成株式会社 | Powdery binder for secondary battery positive electrode and use of same |
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| JPWO2014192652A1 (en) | 2017-02-23 |
| WO2014192652A1 (en) | 2014-12-04 |
| KR102232551B1 (en) | 2021-03-25 |
| KR20160013867A (en) | 2016-02-05 |
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| CN105190968B (en) | 2018-07-24 |
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