CN101578676A - Binder for capacitor electrode - Google Patents
Binder for capacitor electrode Download PDFInfo
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- CN101578676A CN101578676A CNA2007800479777A CN200780047977A CN101578676A CN 101578676 A CN101578676 A CN 101578676A CN A2007800479777 A CNA2007800479777 A CN A2007800479777A CN 200780047977 A CN200780047977 A CN 200780047977A CN 101578676 A CN101578676 A CN 101578676A
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- Prior art keywords
- electrode
- aromatic polyamides
- electrode sheet
- binding agent
- sheet
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- 239000011230 binding agent Substances 0.000 title claims abstract description 37
- 239000003990 capacitor Substances 0.000 title claims abstract description 30
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 42
- 239000004760 aramid Substances 0.000 claims abstract description 41
- 239000007772 electrode material Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000003860 storage Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011883 electrode binding agent Substances 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
-
- 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
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Disclosed is a binder for capacitor electrodes, which has a high binding characteristic with a powder electrode material and a high adhesive characteristic to a collector electrode. The binder also has excellent conductivity and wettability to an electrolytic solution, in a status where the powder electrode material is bound, i.e., in a status of an electrode sheet, and a high heat resistance. The binder is electrochemically stable and is composed of an aramid granulated by heating.
Description
Technical field
The present invention relates to be used to constitute the binding agent for electrode of the electrode etc. of electric storage means such as capacitor, lithium storage battery.
Background technology
Electronic equipment is noticeable aspect miniaturization and, high performance, and this is signifying the latest developments of portable communication device or high-speed data treatment facility etc.Especially, need small-sized, light weight, high performance capacitors, battery badly, and seek extensive use, the fast development of exploitation parts with the anti-long preservation of high power capacity.In order to respond these demands, the necessity that the technology relevant with the binding agent of bonding electrode active material in electrode sheet and quality are developed improves constantly.
Especially, in the binding agent for electrode in electric storage means such as the capacitor that requires high withstand voltage, big electric capacity, big output, battery, in desired various characteristics, recognize that following five feature projects are even more important to binding agent:
1) high powder electrode material caking property and with the high adherence of collector electrode,
2) under the state of powder electrode material that bondd, promptly the conductivity under the state at electrode sheet is good,
3) under the state of powder electrode material that bondd, promptly the wetability to electrolyte is good under the state at electrode sheet,
4) thermal endurance height,
5) electrochemical stability.
In the past, be extensive use of PVdF (Kynoar), PTFE (polytetrafluoroethylene), SBR (butadiene-styrene rubber) latex etc. are as binding agent, but in recent years, capacitor for used for electric vehicle, desired high withstand voltageization such as battery, high capacity or big outputization, and as a kind of means that are used to realize these requirements and by present inventors at first propose by collector electrode, the high temperature drying of the electrode group of electrode and dividing plate composition (being willing to the 2006-073898 specification with reference to Japanese patent application laid), these binding agents not necessarily can fully satisfy these requirements.In addition, PTFE (polytetrafluoroethylene) is difficult to make the thin electrodes sheet material in actual applications, is difficult to be applicable to the big output capacitor, the battery that need thin electrodes sometimes.
In addition, in TOHKEMY 2001-345103 communique, disclose: for the accumulator negative electrode active substance of high charge-discharge efficient is provided, for example use aromatic polyamides (aromatic polyamides) as storage battery with the negative electrode active material binding agent of holding concurrently, described storage battery obtains as the part negative electrode active material with the hold concurrently organic polymer of the carbonyl of binding agent by will having electro-chemical activity on main chain or side chain of negative electrode active material.Yet, because therefore powder electrode material caking property and realize jointly with the low electric conductivity that the adhesiveness of collector electrode is difficult to coexist on the electrode sheet can not get required battery behavior sometimes.
Summary of the invention
Summary of the invention
Main purpose of the present invention is to provide binder for capacitor electrode, its show high powder electrode material caking property and with the high adherence of collector electrode, and under the state of bond powders electrode material, i.e. conductivity under the state at electrode sheet and to the wetability excellence of electrolyte, the thermal endurance height, electrochemical stability.
Another object of the present invention is to provide electric storage means such as the capacitor that used above-mentioned binding agent, battery.
The present inventor furthers investigate to achieve these goals, found that to adopt by heat treated and the aromatic polyamides of granulation is extremely effective as binder for capacitor electrode, thereby finishes the present invention.
Therefore, the invention provides the binder for capacitor electrode of forming by the aromatic polyamides of granulation by heat treated.
In addition, the invention provides electrode sheet, it is prepared as follows: powder electrode material and binding agent and solvent are prepared slurry, this slurry is coated on the collector electrode and prepared, wherein, use aromatic polyamides as binding agent, and after coating, obtain described electrode sheet by heat treated.
The present invention also provides the electric storage means that has used above-mentioned electrode sheet, particularly capacitor and battery.
Binding agent of the present invention is the aromatic polyamides of thermal endurance height, electrochemical stability; because binding agent shrinks in the process that causes granulation by heat treated; thereby shrinkage stress works between the powder electrode material; and the part that covers the powder electrode material surface diminishes owing to shrinking; therefore the contact area between the powder electrode material increases, and the conductivity under the state of electrode sheet significantly improves.In addition, because aromatic polyamides contains amide groups in strand, therefore to contain the wetability of carbonate electrolyte of carboxyl good for binding agent of the present invention and molecule, and, owing to can adopt rubbing method to prepare electrode sheet, therefore described binding agent can prepare the thin electrodes sheet material, is applicable to the big output capacitor that needs thin electrodes, battery etc.
Brief description of drawings
Fig. 1 is the surperficial microphotograph (multiplication factor 3500) of collector electrode filming before heating (active carbon/aromatic polyamides=90% weight/10% weight) that has been coated with the mixed slurry of powder electrode material, aromatic polyamides and solvent.
Fig. 2 is the microphotograph (multiplication factor 3500) of the film coated surface of collector electrode shown in Figure 1 after heating (350 ℃).
Fig. 3 is the surperficial microphotograph (multiplication factor 3500) of collector electrode filming before heating (active carbon/aromatic polyamides=70% weight/30% weight) that has been coated with the mixed slurry of powder electrode material, aromatic polyamides and solvent.
Fig. 4 is the microphotograph (multiplication factor 3500) of the film coated surface of collector electrode shown in Figure 1 after heating (350 ℃).
Detailed Description Of The Invention
Below the present invention will be described in more detail.
The powder electrode material:
Powder electrode material among the present invention is to comprise electrode active material and as required interpolation The material of mixture of conductive agent, other auxiliary agent.
Electrode active material:
Employed electrode active material is so long as capacitor and/or battery in the present invention Electrode, just have no particular limits, particularly, in the situation of capacitor, can be listed as Enumerate: for example, using the electric power storage electric double layer of Helmholtz at the electric double layer of finding in 1879 The active carbon that uses in the capacitor etc., foamy carbon, CNT, poly-acene, nanometer door carbon Deng carbon class material; Can utilize the false capacity of following redox reaction metal oxide, lead Electrical polymer, organic free radical etc., and can use battery electrode as single-sided electrode. This Outward, in the situation of battery, particularly lithium-ions battery, for example can use cobalt acid lithium, The works such as metal oxide of the lithiums such as lithium chromate, lithium vanadate, lithium chromate, lithium nickelate, LiMn2O4 Be positive pole, and can use carbonaceous material, lithium metal etc. as negative pole, described carbonaceous material example As be carbide, the petroleum coke of native graphite, Delanium, resin carbon, natural materials Charcoal, coal coke, pitch coke, carbonaceous mesophase spherules etc.
Conductive agent:
As long as employed conductive agent has the merit that improves the electrode sheet electrical conductivity in the present invention Can, just have no particular limits, can list: for example, acetylene black, Ketjen black (ケ Star チ エ Application Block ラ Star Network) etc. carbon blacks etc. are as the conductive agent that is fit to.
Aromatic polyamides:
In the employed in the present invention aromatic polyamides, comprise the wire macromolecular compound that amido link and aromatic rings more than 60% directly combine, particularly, can list: for example, poly and copolymer thereof, PPTA and copolymer thereof, (poly P phenylene diamine terephthalamide)-(paraphenylene terephthalamide-3,4 '-oxygen connects two phenylenediamines) copolymer (Port リ (パ ラ Off エ ニ レ Application)-コ Port リ (3,4-ジ Off エ ニ Le エ one テ Le) テ レ Off one Le ア ミ De) etc.Though these aromatic polyamides can carry out industry manufacturing by known interfacial polymerization own, solution polymerization process etc. by for example adopting m-phthaloyl chloride and m-phenylene diamine (MPD), and can be used as the commercially available product acquisition, are not limited to this.In these aromatic polyamides,, especially preferably adopt poly from possessing the aspect of characteristics such as good processing and forming, Thermoadhesive, anti-flammability, thermal endurance.
The aromatic polyamides of granulation by heat treated:
The aromatic polyamides of granulation can obtain by the following method by heat treated: for example, powder electrode material, aromatic polyamides and solvent are prepared slurry, this slurry is coated on the collector electrode, then heating.Be as shown in Figure 1 tree-shaped before the aromatic polyamides of filming heats after coating, but if with it in for example 350 ℃ of heating 2 hours down, then become shown in Figure 2 granular.Aromatic polyamides shrinks in becoming granular process; shrinkage stress works between the powder electrode material; and the part that covers the powder electrode material surface diminishes owing to shrinking; therefore the contact area between the powder electrode material increases; owing to making resistance value, the high conductionization of the characteristic of electric storage means, particularly electrode sheet reduces; have high cohesive force through the aromatic polyamides of granulation in this wise in addition, even therefore in electrolyte behind the dipping, capacitor still can keep low resistance.
In the present invention, so long as become granular by heating, the use amount of aromatic polyamides binding agent just has no particular limits, but total amount based on aromatic polyamides and powder electrode material, the use amount of aromatic polyamides binding agent is generally 3% weight-15% weight, preferred especially 5% weight-13% weight.The use amount of aromatic polyamides binding agent exceeds above-mentioned scope when too much, in general is difficult to granulation, and as shown in Figure 3 and Figure 4, even heating is after 2 hours down at 350 ℃, binding agent still can cover the powder electrode material, and the function of electric storage means significantly reduces.
As long as above-mentioned heat treated condition can realize the electric storage means characteristic of expecting, just have no particular limits, but for the cohesive force that makes aromatic polyamides is the highest consideration, so heat treated is particularly suitable for carrying out under near the temperature the crystallized temperature of aromatic polyamides.For example, using under the situation of poly as aromatic polyamides, then may thermal decomposition if surpass 370 ℃, therefore heat treated is preferably carried out under the temperature below 370 ℃, from the viewpoint of crystallized temperature, particularly preferably in carrying out under the temperature in 330 ℃ of-365 ℃ of scopes.In addition, the opportunity of heat treated is so long as just be not particularly limited after coating, but the characteristic that does not hinder electric storage means for the foaming that bumping caused that makes solvent is preferably temporarily being carried out drying with except that desolvating under near the lower temperature the solvent boiling point after the coating, and then carry out heat treated.Can list as heating means: for example, between pair of plates or the method for carrying out hot pressing between metallic roll with HTHP.The condition of hot pressing can example illustrate: for example, under the situation of using metallic roll, it is in the scope of 50kg/cm-400kg/cm with line pressure that temperature is 275 ℃-365 ℃, but is not limited to these, also can not carry out pressurized operation and only heat.But laminated multilayer electrode sheet during hot pressing, and can repeatedly repeat above-mentioned hot pressing processing according to random order.In addition, assembling collector electrode, electrode and dividing plate can carry out heat treated then as electrode unit.
As electrode unit, so long as collector electrode, electrode and dividing plate are assembled, just be not particularly limited, module units in the following way: for example, order stack according to collector electrode/electrode/dividing plate/electrode/collector electrode, perhaps, perhaps repeat these stacks, or the layered product that will superpose is in this wise reeled further according to the order stack of electrode/collector electrode/electrode/dividing plate/electrode/collector electrode/electrode/dividing plate.At this moment, can be in advance with adhesive etc. with bonding between each parts.
Solvent:
Employed in the present invention solvent is so long as the solvent of solubilized aromatic polyamides, just have no particular limits, wherein, especially preferably as the N of good solvent, N-dimethylacetylamide (DMAC), N-N-methyl-2-2-pyrrolidone N-(NMP) any or their mixture.
Collector electrode:
The collector electrode of Shi Yonging is made of the raw material of conductivity in the present invention, so long as to the stable raw material of electrode, solvent and electrolyte, just have no particular limits, can list sheet metals such as aluminium sheet, platinum thin plate, copper sheet.
Electrode sheet:
Electrode sheet among the present invention can be prepared as follows: for example, preparation has mixed the slurry of powder electrode material, aromatic polyamides binding agent and solvent, and this slurry is coated on the collector electrode, carries out heat treated then.Particularly, for example can be prepared as follows:
1) pulp preparation operation:
Aromatic polyamides is dissolved in the solvent preparation aromatic polyamides solution.By this solution and powder electrode material mixing and stirring are prepared uniform sizing material.
2) thick sheet preparation section:
Adopt paste coater such as scraper that above-mentioned slurry is coated the single or double of collector electrode, pass continuous stove, it is solidified at fixed drying oven inner drying prepare thick sheet by for example making this collector electrode.The baking temperature of this moment but is not limited thereto preferably in the scope of solvent boiling point ± 5 ℃.
3) extrusion process:
By for example coming hot pressing sheets thus obtained with HTHP between pair of plates or between metallic roll, can improve density, the mechanical strength of sheet material.Electrode sheet after the extruding preferably satisfies the scope shown in the following formula (1).
0.25＜D×(1/D-We/De-Wc/Dc-Wb/Db)＜0.75··(1)
In the formula,
D is the density of removing the electrode sheet of collector electrode,
We is the weight fraction of electrode active material,
De is the true specific gravity of electrode active material,
Wc is the weight fraction of conductive agent,
Dc is the true specific gravity of conductive agent,
Wb is the weight fraction of binding agent,
Db is the true specific gravity of binding agent.
When D * (1/D-We/De-Wc/Dc-Wb/Db) is 0.75 when above, electrode sheet is densification fully not, is difficult to obtain the enough electric capacity as capacitor, battery.On the contrary, when D * (1/D-We/De-Wc/Dc-Wb/Db) is 0.25 when following, the excessive densification of electrode sheet is difficult to obtain the enough output as battery.
Embodiment
To list embodiment below to be described more specifically the present invention.In addition, these embodiment only are exemplary, content of the present invention are not done any qualification.
Reference example 1 (preparation of electrode sheet)
1) pulp preparation operation:
Poly (true specific gravity 1.38) is dissolved among the NMP preparation meta-aramid solution.
By with above-mentioned solution and active carbon (Network ラ レ ケ ミ カ Le society makes, RP-20) and Ketjen black mix and stir and prepare uniform sizing material.Evaporation is adjusted into active carbon with the blending ratio behind the NMP: Ketjen black: the weight ratio of poly=85: 5: 10.
2) electrode sheet preparation section:
The slurry that adopts scraper to obtain is as mentioned above coated the single face of aluminium foil collector electrode (giving conductivity phenolic resins in advance), carry out (100 ℃ of dryings, 20 minutes, normal pressure, air atmosphere), (temperature is 170 ℃, and pressure is below 1 holder for extruding then, drying, 10 hours), be the electrode sheet of 93 μ m to obtain thickness.
Reference example 2 (preparation of electrode unit)
According to the record of the embodiment of Japanese kokai publication hei 2005-307360 communique, (basic weight is 24.4g/m to the dividing plate that preparation is made up of meta-aramid and para-aramid
2, thickness is 46 μ m, density is 0.53g/cm
3), obtain to be clamped in 1 pair as the electrode unit between the above-mentioned electrode sheet of both positive and negative polarity.
Embodiment 1
The electrode unit of preparation in the reference example 2 is being carried out heat treated (pressure is below 1 holder, 12 hours) under 350 ℃ the temperature, dry and insert aluminium lamination and press in the material external packing in dry atmosphere then.Make three sides of external packing become the state of sealing subsequently, inject 1.5MTEMABF
4/ PC (triethyl group ammonium methyl tetrafluoroborate is dissolved in solution in the propene carbonate) is as electrolyte, the decompression dipping, and remaining side decompression in the external packing sealed, prepare the capacitor that constitutes shown in the following table 1.
Comparative example 1
Except the heat treated temperature with the electrode unit of preparation in the reference example 2 is made as 150 ℃, prepare the capacitor of formation shown in the table 1 with method similarly to Example 1.For the dried active carbon electrode carries out heat treated in the case, the suffered heating-up temperature of the binding agent after the coating is 170 ℃, and is the highest in the electrode sheet preparation section.
Table 1: capacitor constitutes
＜evaluating characteristics 〉
Measure initial stage characteristic (initial stage characteristic), multiplying power property and the low-temperature characteristics of above-mentioned capacitor with following method.
1) initial stage charge-discharge characteristic
As the initial stage characteristic, carry out in the early stage discharging and recharging mensuration and impedance measuring and calculated resistance under the 1C multiplying power.Condition determination is as follows:
Initial capacity is measured (25 ℃)
Charging: CCCV 3.0mA (1C), 2.8V-2 hour (*)
Discharge: CC 3.0mA (1C), 0.01V (* *)
(*) CCCV: constant current constant voltage, (* *) CC: constant current
Impedance measuring (25 ℃)
Mensuration state: discharge end
Measure frequency: 20,000Hz-0.1Hz
Amplitude (Δ E): 10mV
2) low-temperature characteristics
Low-temperature characteristics during as-30 ℃ discharges and recharges mensuration and impedance measuring and calculated resistance under the 1C multiplying power.Condition determination is as follows:
Solid measure (30 ℃)
Charging: CCCV 3.0mA (1C), 2.8V-2 hour (*)
Discharge: CC 3.0mA (1C), 0.01V (* *)
(*) CCCV: constant current constant voltage, (* *) CC: constant current
Impedance measuring (30 ℃)
Mensuration state: discharge end
Measure frequency: 20,000Hz-0.1Hz
Amplitude (Δ E): 10mV
These results are as shown in table 2.
Table 2: capacitor specific characteristics
As shown in table 2, according to the present invention, the resistance of the capacitor of embodiment 1 is lower than the resistance of the capacitor of comparative example 1, and the result is good, confirms that capacitor plays one's part to the full.
Think that the reason of The above results is as follows: under 350 ℃ temperature, cause in the process of granulation by heating; because binding agent shrinks so shrinkage stress works between the powder electrode material; and the part that covers the powder electrode material surface diminishes owing to shrinking, so the contact area between the powder electrode material increases.
Claims (11)
1. binder for capacitor electrode, described binding agent is made up of the aromatic polyamides of the granulation by heat treated.
2. electrode sheet, the following manufacturing of described sheet material: powder electrode material, binding agent and solvent are prepared slurry, described slurry is coated collector electrode, wherein, described binding agent is an aromatic polyamides, obtains described sheet material by heat treated after coating.
3. the electrode sheet of claim 2, wherein, based on the total amount of aromatic polyamides and powder electrode material, slurry contains the aromatic polyamides of 3% weight-15% weight.
4. the electrode sheet of claim 2 wherein, carries out heat treated under near the temperature the crystallized temperature of aromatic polyamides.
5. the electrode sheet of the binding agent of claim 1 or claim 2, wherein, aromatic polyamides is a poly.
6. the electrode sheet of the binding agent of claim 5 or claim 5 wherein, carries out heat treated under the temperature in 330 ℃ of-365 ℃ of scopes.
7. the electrode sheet of the binding agent of claim 1 or claim 2 wherein, is carrying out heat treated by hot pressing between pair of plates or between metallic roll.
8. the electrode sheet of claim 2, wherein, solvent is N, N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-or their mixture; The N-N-methyl-2-2-pyrrolidone N-be abbreviated as NMP.
9. electric storage means, described electric storage means has used the electrode sheet of claim 2.
10. capacitor, described capacitor has used the electrode sheet of claim 2.
11. battery, described battery has used the electrode sheet of claim 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP346660/2006 | 2006-12-22 | ||
| JP2006346660A JP5015579B2 (en) | 2006-12-22 | 2006-12-22 | Capacitor electrode binder |
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| CN101578676A true CN101578676A (en) | 2009-11-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2007800479777A Pending CN101578676A (en) | 2006-12-22 | 2007-12-13 | Binder for capacitor electrode |
Country Status (5)
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| JP (1) | JP5015579B2 (en) |
| KR (1) | KR101381069B1 (en) |
| CN (1) | CN101578676A (en) |
| TW (1) | TW200838015A (en) |
| WO (1) | WO2008078634A1 (en) |
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| KR20110034031A (en) * | 2008-10-31 | 2011-04-04 | 히다치 막셀 가부시키가이샤 | Nonaqueous secondary battery |
| JP5670759B2 (en) * | 2011-01-06 | 2015-02-18 | 帝人株式会社 | Binder for electrode mixture and electrode sheet comprising aromatic polyamide |
| KR101710231B1 (en) | 2014-04-29 | 2017-02-27 | 황철주 | machine of folding and sealing paper |
| CN111420853A (en) * | 2020-03-27 | 2020-07-17 | 天目湖先进储能技术研究院有限公司 | Pole piece drying method for inhibiting adhesive migration, pole piece and battery |
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| JP3154714B2 (en) * | 1990-08-29 | 2001-04-09 | 三菱化学株式会社 | Electrodes for secondary batteries |
| JPH10312791A (en) * | 1997-03-13 | 1998-11-24 | Mitsui Chem Inc | Electrode material for nonaqueous electrolyte secondary battery |
| JP2001345103A (en) * | 2000-03-29 | 2001-12-14 | Toyo Tanso Kk | Negative electrode material for secondary battery, lithium ion secondary battery using it, and manufacturing method of negative electrode material for secondary battery |
| JP2003068284A (en) * | 2001-08-27 | 2003-03-07 | Mitsubishi Cable Ind Ltd | Negative electrode for use in lithium secondary battery and is producing method, and lithium secondary battery |
| JP4204380B2 (en) * | 2003-05-14 | 2009-01-07 | Ｔｄｋ株式会社 | Composite particle for electrode and method for producing composite particle for electrode |
| JP2006339092A (en) * | 2005-06-06 | 2006-12-14 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery and its negative electrode |
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2007
- 2007-12-13 WO PCT/JP2007/074472 patent/WO2008078634A1/en active Application Filing
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| KR101381069B1 (en) | 2014-04-04 |
| JP5015579B2 (en) | 2012-08-29 |
| TW200838015A (en) | 2008-09-16 |
| KR20090105938A (en) | 2009-10-07 |
| WO2008078634A1 (en) | 2008-07-03 |
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Application publication date: 20091111 |