KR102031398B1 - Electrode film for electric double-layer capacitor and production method therefor - Google Patents
Electrode film for electric double-layer capacitor and production method therefor Download PDFInfo
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- KR102031398B1 KR102031398B1 KR1020147033715A KR20147033715A KR102031398B1 KR 102031398 B1 KR102031398 B1 KR 102031398B1 KR 1020147033715 A KR1020147033715 A KR 1020147033715A KR 20147033715 A KR20147033715 A KR 20147033715A KR 102031398 B1 KR102031398 B1 KR 102031398B1
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- electrode film
- electric double
- double layer
- fluorine atoms
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- 239000003990 capacitor Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 37
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 238000005096 rolling process Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000004020 conductor Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 abstract description 13
- 239000011737 fluorine Substances 0.000 abstract description 13
- 238000010294 electrolyte impregnation Methods 0.000 abstract 1
- 238000004611 spectroscopical analysis Methods 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 125000004429 atom Chemical group 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 238000009832 plasma treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 239000006232 furnace black Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- WQNTXSXCXGWOBT-UHFFFAOYSA-N C=C.C=C.F.F.F.F Chemical group C=C.C=C.F.F.F.F WQNTXSXCXGWOBT-UHFFFAOYSA-N 0.000 description 1
- 102100021785 ELL-associated factor 1 Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- 101000895942 Homo sapiens ELL-associated factor 1 Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009864 tensile test 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
- H01G11/22—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
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
An object of this invention is to provide the electrode film for electric double layer capacitors containing the fluorine resin of the grade similar to a conventional product, and having high electrolyte impregnation.
MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the electrode film for electric double layer capacitors of this invention is an electrode film for electric double layer capacitors containing an activated carbon and a fluororesin binder, A / B <= 7.0 in at least one surface (where A is X-ray photoelectron) The ratio of the number of fluorine atoms to the total number of fluorine atoms and carbon atoms on the surface of the electrode film measured by spectroscopy (ESCA), and B is the number of fluorine atoms to the total number of fluorine atoms and carbon atoms contained in the electrode film. Is a ratio).
Description
The present invention relates to an electrode film for an electric double layer capacitor and a method of manufacturing the same.
The electrode film for an electric double layer capacitor (hereinafter also referred to as "EDLC") is usually composed of a powdered electrode such as activated carbon, a conductive material, a binder such as a fluororesin, and the like (Japanese Patent Laid-Open No. 2004-2105 (Patent Document 1) ) Etc).
The performance of EDLC is influenced by the amount of electrolyte solution impregnation into this electrode film. Japanese Patent Application Laid-open No. 4-47449 (Patent Document 2) discloses a particularly tetrafluoroethylene resin (polytetrafluoroethylene, hereinafter referred to as "PTFE") on the surface of a sheet-like electrode in order to improve the impregnation of the electrolyte solution to the sheet-like electrode. It is described that the dense smooth layer containing a large number of layers is broken to scratch the surface of the sheet-like electrode.
However, in the case of using this technique, the sheet-like electrode may be destroyed, resulting in powder falling of the sheet-like electrode, a change in form (thickness and density, etc.), which may impair the electrical stability of the sheet-like electrode or the EDLC using the same.
The electrode film for EDLC can be manufactured by the method of shape | molding a raw material in a sheet form using a rolling roll.
The present inventors found that during this rolling, a large shear force is applied to the raw sheet in the vicinity of the surface of the raw sheet, in particular, the fiberization of the fluorine resin proceeds, thereby increasing the surface area of the fluorine resin, and as a result, the water repellency of the resulting EDLC electrode film becomes high. It was thought that the intrusion of the electrolyte into the electrode membrane would be hindered.
On the other hand, if the amount of the fluorine resin as the binder is reduced, the water repellency of the EDLC electrode film surface can be suppressed, but the shape of the EDLC electrode film cannot be stably maintained.
In view of these problems, an object of the present invention is to provide an electrode film for EDLC having a higher impregnation property of an electrolyte solution than a conventional product containing a fluorine resin of the same degree and a method for producing the same.
The present invention relates to the following [1] to [9], for example.
[One]
An electrode film for an electric double layer capacitor comprising activated carbon and a fluororesin binder,
A / B ≤ 7.0 (where A is the ratio of the number of fluorine atoms to the total number of fluorine atoms and carbon atoms on the surface of the electrode film measured by X-ray photoelectron spectroscopy (ESCA), where B is The ratio of the number of fluorine atoms to the total number of fluorine atoms and carbon atoms contained in the electrode film.
[2]
The content of the fluororesin binder is 1% by weight or more,
The ratio of the number of fluorine atoms to the total number of fluorine atoms, carbon atoms and oxygen atoms measured by X-ray photoelectron spectroscopy (ESCA) on at least one surface is 15 atomic% or less
The electrode film for electric double layer capacitors as described in said [1] characterized by the above-mentioned.
[3]
[1] or [2], wherein the ratio of the number of fluorine atoms to the total number of fluorine atoms, carbon atoms and oxygen atoms measured by X-ray photoelectron spectroscopy (ESCA) on at least one surface is 7 atomic% or more. The electrode film for electric double layer capacitors of description.
[4]
[1] to [3], wherein the ratio of the number of oxygen atoms to the total number of fluorine atoms, carbon atoms and oxygen atoms measured by X-ray photoelectron spectroscopy (ESCA) on at least one surface is 40 atomic% or less. The electrode film for electric double layer capacitors in any one of them.
[5]
An electrode film for an electric double layer capacitor according to any one of the above [1] to [4], further comprising a carbon conductive material.
[6]
Process 1 which obtains a kneaded material by stirring the composition containing activated carbon and a fluororesin binder under the conditions of following (i) and / or (ii), and
Process 2 which rolls the kneaded material with a roll and obtains an electrode film
Method for producing an electrode film for an electric double layer capacitor comprising a;
(i) the stirring speed is 50-180 rpm,
(ii) The stirring time is 10 to 60 seconds.
[7]
The said process 2 is a process of rolling the said kneaded material with a roll on condition of following (iii) and / or (iv), and obtaining an electrode film, The manufacturing method of the electrode film for electric double layer capacitors of said [6] characterized by the above-mentioned;
(iii) the roll speed is 3 m / min or less,
(iv) The number of rolling is three times or less.
[8]
The method for producing an electrode for an electric double layer capacitor according to the above [6] or [7], wherein the composition further contains a carbon conductive material.
[9]
The electrode film for electric double layer capacitors manufactured by the manufacturing method in any one of said [6]-[8].
The electrode film for EDLC of this invention has higher impregnation property of electrolyte solution than the conventional product containing a fluorine resin of the same grade.
In addition, according to the method for producing an EDLC electrode film of the present invention, an EDLC electrode film having higher impregnation of an electrolyte solution than a conventional product containing a fluorine resin of the same degree is produced.
The present invention is described in more detail below.
[ EDLC for Electrode film ]
The electrode film for EDLC of the present invention is an electrode film for an electric double layer capacitor containing activated carbon, a fluororesin binder and optionally a carbon conductive material (except the activated carbon).
In at least one surface of the electrode film, preferably the ratio of the number of fluorine atoms to the total number of fluorine atoms and carbon atoms on the surface of the electrode film measured by X-ray photoelectron spectroscopy (ESCA) on both surfaces thereof is A, If the ratio of fluorine atoms to the total of fluorine atoms and carbon atoms contained in the electrode film is B, the value of A / B is 7.0 or less, preferably 6.0 or less, and more preferably 5.0 or less. to be. In addition, the lower limit of said A / B is 2.0, for example.
In the conventional EDLC electrode film, the ratio of fluorine atoms on the surface of the electrode film is relatively high due to the rolling molding to the roll, and the water repellency on the surface of the electrode film is high, which is thought to prevent the intrusion of the electrolyte into the electrode film. .
On the other hand, in the electrode film of the present invention, the value of A / B is 7.0 or less, although the ratio of fluorine atoms in atoms on the surface of the electrode film is large compared to the ratio of fluorine atoms in atoms in the entire electrode film. It is not excessively large. Therefore, in the electrode film of the present invention, the water repellency of the surface is low as compared with the conventional products containing the same degree of fluorine resin, and therefore, the electrolyte solution (for example, an aqueous electrolyte solution) is likely to invade the electrode film. do.
In the manufacturing process of an electrode film, it is thought that the said A / B of the electrode film obtained will become a some large value exceeding 1 as fiberization of a fluororesin binder advances especially in the vicinity of the surface of the sheet-like rolled material containing a raw material mixture. Therefore, in the electrode film of this invention in which the value of A / B is not too big | large, it is thought that the fiberization of the fluororesin binder in the surface vicinity does not progress excessively.
In addition, in this specification, the ratio of each atom of the surface of an electrode film measured by X-ray photoelectron spectroscopy (ESCA) is a case where the measurement is performed on the conditions employ | adopted in the Example mentioned later, or equivalent conditions.
As said activated carbon, the said carbon conductive material, and the said fluororesin binder, what is conventionally used in the electrode film for EDLC can be used.
As said activated carbon, if it is a commercial item, YP50F (made by Kuraray Chemical Co., Ltd.), Maxsorb (manufactured by Kansai Thermochemical Co., Ltd.), etc. are mentioned.
The specific surface area of the said activated carbon may be 1,000-2,500 m <2> / g, for example.
As said carbon conductive material, acetylene black, channel black, furnace black, Ketjen black, etc. are mentioned, These may be used individually by 1 type, or may use 2 or more types together. If it is a commercial product, Continex CF (made by Continental Carbon, conductive furnace black), Ketjen Black ECP600JD (manufactured by Lion Co., Ltd.), Ketjen Black EC (Ketjen Black International, manufactured conductive black), Balkan C (manufactured by Cabot) , Conductive furnace black), BLACL PEARLS 2000 (manufactured by Cabot, conductive furnace black), denca acetylene black (manufactured by Electrochemical Industry Co., Ltd., acetylene black) and the like can be suitably used.
The fluorine resin is easily fibrous and copolymerizes ethylene tetrafluoride ethylene resin (PTFE) and modified PTFE (e.g. tetrafluoroethylene and other monomers in small amounts (e.g. 0.5 mol% or less) in view of its high ability as a binder. Modified PTFE obtained by the use thereof is preferred, and PTFE is more preferred.
In the case where the EDLC electrode film does not contain the carbon conductive material, the proportion of the activated carbon is, for example, 99 wt% or less, preferably 90 to 96 wt%, in the EDLC electrode film, and the EDLC electrode film is the carbon conductive material. In the case of containing ash, the ratio of the activated carbon is, for example, 98 wt% or less, preferably 60 to 90 wt%, in the EDLC electrode film, and the ratio of the carbon conductive material is, for example, in the EDLC electrode film. 0.1 weight% or more, Preferably it is 1 weight% or more, More preferably, it is 5-30 weight%. Moreover, the ratio of the said fluororesin binder is 1 weight% or more, for example, Preferably it is 4-10 weight% from a viewpoint of an electrode film strength.
The EDLC electrode film of the present invention may contain a small amount (for example, 1 wt% or less in the EDLC electrode film) of additives (metal oxides, metal catalysts, etc.) which are usually included in the EDLC electrode film.
The ratio of the number of fluorine atoms to the total number of fluorine atoms, carbon atoms and oxygen atoms on the surface of the electrode film measured by X-ray photoelectron spectroscopy (ESCA) on at least one side of the electrode film, preferably on both sides thereof, From the standpoint of no fall (no powder adheres to the finger when the finger is touched on the surface of the electrode film), it is preferably 7 atomic% or more, and more preferably 10 atomic% or more. The ratio is preferably 15 atomic% or less, more preferably 12 atomic% or less from the viewpoint of suppressing the water repellency of the electrode film surface.
Plasma treatment or the like on the surface of the electrode film tends to increase the proportion of the number of oxygen atoms on the surface. It is thought that this oxygen atom is derived from a functional group formed on the surface of the electrode film by plasma treatment or the like. An electrode film having an excessively large amount of such functional groups causes decomposition of the electrolyte solution and generation of gas by electrochemical reaction during charge and discharge. There is a risk of adversely affecting the durability and lifespan of the electric double layer capacitor. For this reason, in view of suppressing such adverse effects, at least one side of the electrode film, preferably both surfaces thereof, fluorine atoms, carbon atoms, and oxygen on the surface of the electrode film measured under the above conditions by X-ray photoelectron spectroscopy (ESCA). The ratio of the number of oxygen atoms to the total number of atoms is preferably 40 atomic% or less, more preferably 30 atomic% or less.
[ EDLC for Electrode Manufacturing method]
As a manufacturing method of the EDLC electrode film of this invention mentioned above, the following manufacturing method A, the manufacturing method B, and the manufacturing method C are mentioned, for example.
<Manufacturing method A>
Manufacturing method A is a step 1 to obtain a kneaded material by stirring the mixture for forming the electrode film for EDLC and
Process 2 which rolls the kneaded material with a roll and obtains an electrode film
As a method for producing an electrode film comprising a, it is a manufacturing method that adopts the conditions of (i) or (ii) below in step 1, preferably both of conditions (i) and (ii);
(i) stirring speed (rotator's rotational speed): 50-180 rpm, preferably 120-170 rpm,
(ii) Stirring time: 10 to 60 seconds, preferably 20 to 50 seconds.
<Production Method B>
Production method B is a step 1 to obtain a kneaded material by stirring the mixture for forming the electrode film for EDLC and
Process 2 which rolls the kneaded material with a roll and obtains an electrode film
As a method for producing an electrode film, the process 1 is the same as the process 1 of the manufacturing method A, and in the process 2, the conditions of (iii) or (iv) below, preferably both of the conditions of (iii) and (iv) It is a manufacturing method which employ | adopts;
(iii) roll speed: 3 m / min or less, preferably 2 m / min to 0.8 m / min,
(iv) Number of rollings: 3 times or less, preferably 2 times or less.
<Manufacturing method C>
Manufacturing method C is a step 1 to obtain a kneaded material by stirring the mixture for forming the electrode film for EDLC,
Process 2 'of rolling the kneaded material with a roll, and
Process 3 which obtains an electrode film by plasma-processing or excimer laser-processing the surface of the rolling material obtained in process 2 '.
It is a manufacturing method of an electrode film containing a. In the step 1 and the step 2 'of the manufacturing method C, conventional conditions may be employ | adopted, and process 1 of the said manufacturing method A may be employ | adopted as process 1, and process 2 of the said manufacturing method B may be employ | adopted as process 2'.
In step 1 of the manufacturing method A, since the stirring conditions are slower than before, that is, the stirring speed is slower and the stirring time is shorter, the fiberization of the fluorine resin does not proceed much, and as a result, the surface area of the fluorine resin in the obtained electrode film is smaller than that of the conventional products. It is considered that the proportion of fluorine atoms on the lower electrode film surface becomes smaller than before.
In the production method B, in step 2 of the production method A, by slowing the roll speed or decreasing the number of rolling, the fiberization of the surface of the electrode film is resulted without excessively promoting the fiberization of fluorine near the surface of the electrode film during roll rolling. It is considered that the amount of the fluorine resin thus obtained is not excessively increased, thereby preventing the ratio of the fluorine atoms (or the value of A / B) on the surface of the electrode film from being excessively large.
In the production method C, it is thought that the proportion of the fluorine atoms on the surface of the film is reduced by step 3.
The mixture for EDLC electrode film formation contains activated carbon, a fluororesin binder, and optionally a carbon conductive material, and any mixture conventionally used for forming the electrode film for EDLC can be used. The detail of activated carbon, a carbon conductive material, a fluororesin binder, and these ratio is as above-mentioned.
The fluororesin binder contained in the mixture is usually in particulate form, and at least a part thereof is fiberized by kneading or rolling the mixture.
The said composition may contain shaping | molding adjuvant, such as water and alcohol, in the process 1-the process 2. The amount of the molding aid is preferably 80 parts by weight or more, and more preferably 100 to 600 parts by weight based on 100 parts by weight of the total of the activated carbon, the carbon conductive material, and the fluororesin binder. This molding aid is removed during the process 2 and / or after the process 2 by heating or the like.
Example
The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited to these Examples in any way.
<Measurement method>
(Ratio of each atom on the film surface)
For each electrode film prepared in Examples and Comparative Examples, the ratio of fluorine atoms, carbon atoms and oxygen atoms on the electrode film surface was measured by X-ray photoelectron spectroscopy (ESCA).
The detail of the measurement conditions by X-ray photoelectron spectroscopy is as follows.
Measurement point:
An area of 1 cm in all directions near the center of the electrode film was cut out, and the area of 1 mm 의 near the center of one side thereof (the surface of the electrode film subjected to plasma treatment or the like in Examples 3 and 4) was measured.
Measuring instrument:
Nippon Electronics Co., Ltd. product | photoelectron spectroscopy apparatus JPS9010 MX was used.
Measuring conditions:
X-ray source: MgKα (output: 10 kV, 10 mA)
Optoelectronic extraction angle: 45 °
Pass Energy: 50 eV
Sweep Number: 1 time
Step size: 0.1 eV
Relate the spectrum to the ratio of each atom:
The ratio (atomic%) of each atom was computed from the peak area (the area integrated intensity after background correction) of the spectrum obtained by performing a narrow scan. However, in advance, the surfaces of polytetrafluoroethylene (PTFE) and polymethyl methacrylate (PMMA) as standard samples were measured, and carbon atoms: fluorine atoms = 1: 1 (molar ratio) in PTFE, and carbon in PMMA. The peak area of the spectrum and the ratio of each atom were related so that atoms: oxygen atoms = 5: 2 (molar ratio).
(Impregnation)
Each electrode film prepared in Example or Comparative Example was left at 150 ° C. for 30 to 90 minutes and dried. After cooling to room temperature, 9 µL of a PC-based electrolyte solution (LIPASTE-P / EAF1 manufactured by Toyama Pharmaceutical Co., Ltd.) was added dropwise to the electrode film (the surface on which the electrode film was subjected to plasma treatment or the like in Examples 3 and 4). The time until the electrolyte solution soaked into the electrode film and the glossiness of the surface of the electrode film disappeared was measured.
(Powder falling property)
Each electrode film produced in Examples or Comparative Examples (however, in Examples 3 and 4, the surface of the electrode film subjected to plasma treatment, etc.) was touched with a finger, and evaluation was performed based on the following criteria.
(Circle): powder hardly adheres to a finger
(Triangle | delta): A small amount of powder adheres to a finger
X: A finger adheres to the point of saccharification with powder
(Strength and Formability of Electrode Film)
Each electrode film manufactured in the example or the comparative example was punched with dumbbell No. 1, and a tensile test was carried out at a speed of 50 mm / min to evaluate based on the following criteria.
(Circle): The stress at the time of fracture of a test piece is 1 N or more
X: stress when the test piece was broken is less than 1 N
Example 1
Activated carbon (Kurare Chemical Co., Ltd. YP50F), conductive carbon (Lion Co., Ltd. Kechen Black ECP600JD), and PTFE (Daikin Industries, Ltd. Polypron D-1E) were used in a weight ratio of activated carbon: conductive carbon: PTFE = 88: 6: 6. In addition, it weighed so that a total amount might be 1.5 kg.
370 parts by weight of ion-exchanged water was mixed with respect to 100 parts by weight of these activated carbons, conductive carbon and PTFE in total, and stirred for 30 seconds at a low speed (140 rpm) to obtain a kneaded product.
The kneaded material was first rolled to a thickness of about 520 to 530 µm at a roll speed of 1 m / min using a rolling roll. Subsequently, secondary rolling was performed at a roll speed of 2 m / min to obtain an electrode film having a thickness of 500 µm.
Table 1 shows the evaluation results of this electrode film.
Moreover, since the electrode film was manufactured using the rolling roll, it is thought that fibrosis of the fluororesin advanced similarly on both surfaces of the electrode film. Therefore, it is thought that the surface of the side which did not measure the atomic ratio of this electrode film also had each atom in the same ratio as the surface of the side which measured.
Example 2
An electrode film having a thickness of 500 µm was obtained in the same manner as in Example 1 except that the roll speed in the primary rolling was changed from 1 m / min to 0.8 m / min and the secondary rolling was not performed.
Table 1 shows the evaluation results of this electrode film.
Comparative Example 1
An electrode film having a thickness of 500 μm was obtained by the same operation as in Example 1 except that the medium speed (190 rpm) and the stirring for 30 seconds were further performed after the stirring at low speed (140 rpm) and 30 seconds.
Table 1 shows the evaluation results of this electrode film.
Example 3
An electrode film was obtained by the same operation as in Comparative Example 1, and further, plasma treatment was performed on the surface of the electrode film under the following conditions to obtain an electrode film.
(Plasma treatment conditions)
Gas species: He, Gas flow rate: 3 L / min, Plasma frequency: 5 kHz, Output power: 120 W, Irradiation time: 300 seconds
Table 1 shows the evaluation results of this electrode film.
Example 4
The electrode film was obtained by operation similar to the comparative example 1, and the excimer laser process was further performed on the surface of this electrode film on the following conditions, and the electrode film was obtained.
(Excimer laser treatment condition)
Atmosphere: Atmosphere containing 99% by volume of N 2 and 1% by volume of O 2 .
Irradiation energy: 3000 mJ / ㎠
Table 1 shows the evaluation results of this electrode film.
Example 5
An electrode film was obtained by the same operation as in Example 1 except that the weight ratio of each raw material was changed to activated carbon: conductive carbon: PTFE = 94: 0: 6.
Table 1 shows the evaluation results of this electrode film.
Comparative Example 2
An electrode film was obtained in the same manner as in Comparative Example 1 except that the weight ratio of each raw material was changed to activated carbon: conductive carbon: PTFE = 91: 6: 3.
Table 1 shows the evaluation results of this electrode film.
Claims (9)
In at least one surface, A / B≤7.0 (where A is the ratio of the number of fluorine atoms to the total number of fluorine atoms and carbon atoms on the surface of the electrode film measured by X-ray photoelectron spectroscopy (ESCA), where B is Is a ratio of the number of fluorine atoms to the total number of fluorine atoms and carbon atoms contained in the electrode film.
Electrode film for an electric double layer capacitor, characterized in that.
Content of the said fluororesin binder is 1 weight% or more,
The ratio of the number of fluorine atoms to the total number of fluorine atoms, carbon atoms and oxygen atoms measured by X-ray photoelectron spectroscopy (ESCA) on at least one surface is 15 atomic% or less
Electrode film for an electric double layer capacitor, characterized in that.
An electrode film for an electric double layer capacitor, wherein a ratio of the number of fluorine atoms to the total number of fluorine atoms, carbon atoms, and oxygen atoms measured by X-ray photoelectron spectroscopy (ESCA) on at least one surface is 7 atomic% or more.
An electrode film for an electric double layer capacitor, wherein a ratio of the number of oxygen atoms to the total number of fluorine atoms, carbon atoms, and oxygen atoms measured by X-ray photoelectron spectroscopy (ESCA) on at least one surface is 40 atomic% or less.
An electrode film for electric double layer capacitors, further comprising a carbon conductive material.
Process 2 which rolls the kneaded material with a roll and obtains an electrode film
Including,
At least a part of the fluororesin binder is fiberized by passing through step 1 or step 2.
Manufacturing method of electrode film for electric double layer capacitor;
(i) the stirring speed is 50-180 rpm,
(ii) The stirring time is 10 to 60 seconds.
The said process 2 is a process of rolling the said kneaded material with a roll on condition of following (iii), (iv) or (iii) and (iv), and obtaining an electrode film, The manufacturing method of the electrode film for electric double layer capacitor characterized by the above-mentioned;
(iii) the roll speed is 3 m / min or less,
(iv) The number of rolling is three times or less.
A method for producing an electrode for an electric double layer capacitor, characterized in that the composition further contains a carbon conductive material.
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| PCT/JP2013/063034 WO2013168762A1 (en) | 2012-05-11 | 2013-05-09 | Electrode film for electric double-layer capacitor and production method therefor |
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| JP2000150321A (en) * | 1998-08-31 | 2000-05-30 | Hokushin Ind Inc | Manufacture of polarized electrode for electric double layer capacitor |
| JP2007035769A (en) * | 2005-07-25 | 2007-02-08 | Tdk Corp | Manufacturing method of electrode for electrochemical element and manufacturing method of electrochemical element |
| JP2007180251A (en) * | 2005-12-27 | 2007-07-12 | Tdk Corp | Manufacturing method and manufacturing apparatus of electrode for electrochemical capacitor |
| JP2008060457A (en) * | 2006-09-01 | 2008-03-13 | Japan Gore Tex Inc | Electric double layer capacitor |
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| JPH0447449A (en) | 1990-06-13 | 1992-02-17 | Hitachi Ltd | Document preparing device |
| JPH0613264A (en) * | 1992-06-26 | 1994-01-21 | Matsushita Electric Ind Co Ltd | Electric double layer capacitor |
| JP3561780B2 (en) * | 2002-01-29 | 2004-09-02 | 潤二 伊藤 | Electrode mixture for polarizable electrode, method for producing the same, and polarizable electrode using the electrode mixture |
| JP4080244B2 (en) | 2002-05-31 | 2008-04-23 | 株式会社クラレ | Activated carbon sheet and manufacturing method thereof, polarizable electrode and electric double layer capacitor |
| WO2006070617A1 (en) * | 2004-12-27 | 2006-07-06 | Matsushita Electric Industrial Co., Ltd. | Polarizable electrode member, process for producing the same, and electrochemical capacitor utilizing the member |
| CN101685710B (en) * | 2008-09-26 | 2012-07-04 | 通用电气公司 | Methods for preparing composition and sheet containing composition as well as electrode containing sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000150321A (en) * | 1998-08-31 | 2000-05-30 | Hokushin Ind Inc | Manufacture of polarized electrode for electric double layer capacitor |
| JP2007035769A (en) * | 2005-07-25 | 2007-02-08 | Tdk Corp | Manufacturing method of electrode for electrochemical element and manufacturing method of electrochemical element |
| JP2007180251A (en) * | 2005-12-27 | 2007-07-12 | Tdk Corp | Manufacturing method and manufacturing apparatus of electrode for electrochemical capacitor |
| JP2008060457A (en) * | 2006-09-01 | 2008-03-13 | Japan Gore Tex Inc | Electric double layer capacitor |
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| CN104272410A (en) | 2015-01-07 |
| WO2013168762A1 (en) | 2013-11-14 |
| CN104272410B (en) | 2018-03-02 |
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| JPWO2013168762A1 (en) | 2016-01-07 |
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