JP2007158163A - Electrode sheet and its manufacturing method - Google Patents
Electrode sheet and its manufacturing method Download PDFInfo
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- JP2007158163A JP2007158163A JP2005353342A JP2005353342A JP2007158163A JP 2007158163 A JP2007158163 A JP 2007158163A JP 2005353342 A JP2005353342 A JP 2005353342A JP 2005353342 A JP2005353342 A JP 2005353342A JP 2007158163 A JP2007158163 A JP 2007158163A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 44
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 42
- 239000004760 aramid Substances 0.000 claims description 39
- 239000003990 capacitor Substances 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 4
- 238000005476 soldering Methods 0.000 abstract description 8
- 241000531908 Aramides Species 0.000 abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 29
- 238000000034 method Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- 239000000835 fiber Substances 0.000 description 5
- 229940125753 fibrate Drugs 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MKCDXXDWWZVCJG-UHFFFAOYSA-M lithium;4-methyl-1,3-dioxolan-2-one;perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O.CC1COC(=O)O1 MKCDXXDWWZVCJG-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
Classifications
-
- 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
Abstract
Description
本発明は電極シート及びその製造方法に関し、特に電気二重層キャパシタ用電極に適した電極シート及びその製造方法に関する。 The present invention relates to an electrode sheet and a manufacturing method thereof, and more particularly to an electrode sheet suitable for an electrode for an electric double layer capacitor and a manufacturing method thereof.
分極性電極と電解質界面で形成される電気二重層を利用した電気二重層キャパシタは、メモリバックアップ電源として近年急速に需要が伸びている。また、電気自動車用電源等の大容量を必要とされる用途への適用が注目されている。 In recent years, demand for an electric double layer capacitor using an electric double layer formed at a polarizable electrode and an electrolyte interface is rapidly increasing as a memory backup power source. In addition, application to applications requiring a large capacity, such as a power source for electric vehicles, has attracted attention.
電気二重層キャパシタの電極は、集電体に活性炭などの炭素質材料を含有する電極層を積層させた構造を有している。また、電極層は、炭素質材料とバインダーとからなるシートが使用されている。 The electrode of the electric double layer capacitor has a structure in which an electrode layer containing a carbonaceous material such as activated carbon is laminated on a current collector. The electrode layer uses a sheet made of a carbonaceous material and a binder.
かかる電極層に用いるシートとしては、例えば、繊維状活性炭及び粉末活性炭と、バインダーであるポリオレフィンパルプとからなり、これらを熱プレスして得られる活性炭シートが提案されている（引用文献１）。 As a sheet used for such an electrode layer, for example, an activated carbon sheet made of fibrous activated carbon and powdered activated carbon and polyolefin pulp as a binder and obtained by hot pressing these has been proposed (Cited Document 1).
しかしながら、上記活性炭シートは熱プレスの際、バインダーであるポリオレフィンが溶融して活性炭表面のかなりの部分を覆ってしまい、その結果、活性炭の比表面積が低下し、容量密度も低くなる問題がある。 However, the activated carbon sheet has a problem that the polyolefin as a binder melts and covers a considerable part of the activated carbon surface during hot pressing, resulting in a decrease in the specific surface area of the activated carbon and a decrease in capacity density.
さらに、近年、鉛フリーはんだがよく用いられるようになってきたが、はんだ付けの際には、従来のものよりも高温ではんだ付け作業が行わている。例えば、ハイブリッド自動車及び電気自動車用の電源などを電子基板上に組み込む際の、鉛フリーはんだのリフロー工程では雰囲気温度がかなり高温となるが、上記のような従来の電極シートでは十分にこれに耐えられない。
本発明は上記の問題を解決すべくなされたものであり、その目的は、鉛フリーはんだのような高温のはんだ付けでも変形や穴あきがなく、しかも容量密度が大きく、抵抗の小さい電極シート及びその製造方法体を提供することにある。 The present invention has been made to solve the above-mentioned problems, and its purpose is to provide an electrode sheet that is free from deformation and perforation even at high-temperature soldering such as lead-free solder, and has a large capacity density and low resistance. It is in providing the manufacturing method body.
本発明者らは鋭意検討の結果、アラミドフィブリッドをバインダーとして用いることによって、活性炭などの粉体を高混率で保持でき、かつ活性炭の表面を覆うことないため、容量密度が大きく、抵抗の小さい電極シートが得られることを見出した。また、この電極シートは耐熱性の面でも極めて優れており、鉛フリーはんだにも十分耐えられるものであった。ものため、この電極シートは電気二重層キャパシタ電極層として十分な性能を具備していることがわかった。 As a result of intensive studies, the present inventors can use aramid fibrids as a binder to hold a powder such as activated carbon at a high mixing ratio and do not cover the surface of the activated carbon, so that the capacity density is large and the resistance is small. It has been found that an electrode sheet can be obtained. Further, this electrode sheet was extremely excellent in heat resistance, and could withstand lead-free solder sufficiently. Therefore, it was found that this electrode sheet had sufficient performance as an electric double layer capacitor electrode layer.
かくして本発明によれば、アラミドフィブリットと炭素質材料とからなる電極シートであって、該アラミドフィブリットにより該炭素質材料が保持されており、該アラミドフィブリットの含有量が該電極シートを基準として０．５〜３０重量％であることを特徴とする電極シートが提供される。 Thus, according to the present invention, an electrode sheet composed of an aramid fibrite and a carbonaceous material, the carbonaceous material being held by the aramid fibrit, and the content of the aramid fibrit is the electrode sheet. An electrode sheet characterized by being 0.5 to 30% by weight as a reference is provided.
また、本発明によれば、アラミドフィブリッド、炭素質素材、及び水を、アラミドフィブリッド：炭素質素材の重量比率が０．５：９９．５〜３０：７０となるように混合してスラリーとし、これを湿式抄造してシートとすることを特徴とする電極シートの製造方法が提供される。 Further, according to the present invention, an aramid fibrid, a carbonaceous material, and water are mixed and slurried so that the weight ratio of aramid fibrid: carbonaceous material is 0.5: 99.5 to 30:70. A method for producing an electrode sheet is provided, wherein the sheet is formed by wet papermaking.
本発明によれば、鉛フリーはんだのような高温のはんだ付けでも変形や穴あきがなく、しかも容量密度が大きく、抵抗の小さい電極シートを提供することができる。このため、電気二重層キャパシタ用電極に用いて優れた性能を発揮する。また、本発明の製造方法によれば、上記電極シートを容易にしかも安定して製造することができる。 According to the present invention, it is possible to provide an electrode sheet that is free from deformation or perforation even at high temperature soldering such as lead-free solder, has a large capacity density, and has low resistance. For this reason, it exhibits excellent performance when used for an electrode for an electric double layer capacitor. Moreover, according to the manufacturing method of this invention, the said electrode sheet can be manufactured easily and stably.
本発明の電極シートは、アラミドフィブリットと炭素質材料とからなる電極シートであり、特に電気二重層キャパシタ用電極に適した電極シートである。
本発明において、アラミドとは全芳香族ポリアミドをいい、例えば、ポリ−ｐ−フェニレンテレフタルアミド、ポリ−ｐ−ベンズアミド、ポリ−ｐ−アミドヒドラジド、ポリ−ｐ−フェニレンテレフタルアミド−３，４−ジフェニルエーテルテレフタルアミドなどが挙げられる。
The electrode sheet of the present invention is an electrode sheet made of an aramid fibrite and a carbonaceous material, and is particularly an electrode sheet suitable for an electric double layer capacitor electrode.
In the present invention, aramid refers to wholly aromatic polyamide, such as poly-p-phenylene terephthalamide, poly-p-benzamide, poly-p-amide hydrazide, poly-p-phenylene terephthalamide-3,4-diphenyl ether. Examples include terephthalamide.
本発明でいうフィブリッドとは、湿式抄造工程において、バインダー性能を有する微小のフィブリルを有する薄葉状、鱗片状の小片、又は、ランダムにフィブリル化した微小短繊維の総称であり、例えば、ＷＯ２００４／０９９４７６Ａ１、特公昭３５−１１８５１号公報、特公昭３７−５７３２号公報等に記載された方法により、有機系高分子重合体溶液を該高分子重合体溶液の沈澱剤と剪断力の存在する系において混合することにより製造されるフィブリッドや、あるいは、特公昭５９−６０３号公報に記載された方法により、光学的異方性を示す高分子重合体溶液から成形した分子配向性を有する成形物に叩解等の機械的剪断力を与えてランダムにフィブリル化させたフィブリッドをいい、中でも前者の方法によるものが最適である。なお、上記のフィブリッドは、紡糸工程や短繊維にカットする工程を経ずに製造される点において、アラミド短繊維とは異なるものである。 Fibrid as referred to in the present invention is a generic term for thin leaf-like, scaly small pieces having fine fibrils having binder performance in the wet papermaking process, or fine short fibers randomly fibrillated, for example, WO2004 / 099476A1. The organic polymer solution is mixed in a system in which a shearing force is present with the precipitant of the polymer solution by the method described in JP-B-35-11851, JP-B-37-5732, etc. Or the like, or a molded product having molecular orientation formed from a polymer solution exhibiting optical anisotropy by a method described in JP-B-59-603. These are fibrils that are randomly fibrillated by applying mechanical shearing force, and the former method is the best. The above-mentioned fibrid is different from an aramid short fiber in that it is manufactured without a spinning process or a process of cutting into short fibers.
一方、本発明において炭素質材料とは、それぞれ炭素質物質からなる「活物質」と「導電性付与剤」とからなるものをいう。
上記の「活物質」としては、活性炭、ポリアセンなどが挙げられ、比表面積が２００〜３５００ｍ２／ｇである粉末、また、カーボンファイバ、カーボンウィスカ、グラファイト等の繊維、または粉末で比表面積が２００〜３５００ｍ２／ｇであるものが好ましい。活性炭としては、フェノール系、レーヨン系、ピッチ系、またはヤシガラ系等を使用することができる。活物質の粒子径が０．１〜１００μｍ、さらに好ましくは１〜２０μｍであると、電極する際、特にキャパシタ用電極とする際、薄膜化が容易で、容量密度も高くできるので好ましい。
On the other hand, the carbonaceous material in the present invention refers to a material composed of an “active material” and a “conductivity imparting agent” each composed of a carbonaceous material.
Examples of the “active material” include activated carbon, polyacene, and the like, a powder having a specific surface area of 200 to 3500 m 2 / g, a fiber such as carbon fiber, carbon whisker, and graphite, or a powder having a specific surface area of 200. What is -3500m < 2 > / g is preferable. As the activated carbon, phenol, rayon, pitch, or coconut shell can be used. When the particle diameter of the active material is 0.1 to 100 μm, more preferably 1 to 20 μm, it is preferable when forming an electrode, particularly when forming an electrode for a capacitor, because it is easy to make a thin film and the capacity density can be increased.
また、「導電性付与剤」としては、アセチレンブラック、ケチェンブラック、カーボンブラックなどが挙げられ、上記活物質と混合して使用する。導電性付与剤の好ましい粒子径は０．１〜１００μｍである。導電性付与剤を併用することにより、前記活物質同士の電気的接触が一段と向上し、電極シートの抵抗を低くし、かつ容量密度を高くすることができる。
活物質と導電性付与剤との配合比率は、活物質１００質量部に対し、導電性付与剤が０．１〜２０質量部、好ましくは２〜１５質量部である。
Examples of the “conductivity imparting agent” include acetylene black, ketjen black, and carbon black, which are used by mixing with the above active material. The preferable particle diameter of the conductivity-imparting agent is 0.1 to 100 μm. By using a conductivity imparting agent in combination, the electrical contact between the active materials can be further improved, the resistance of the electrode sheet can be lowered, and the capacity density can be increased.
The compounding ratio of the active material and the conductivity-imparting agent is 0.1 to 20 parts by mass, preferably 2 to 15 parts by mass with respect to 100 parts by mass of the active material.
本発明においては、電極シートが、上述した炭素質材料とアラミドフィブリットとからなり、該炭素質材料が該アラミドフィブリットに保持されていること、また、該アラミドフィブリットの含有量が後述する範囲であることが肝要である。これにより、ポリオレフィンなどのバインダー樹脂を用いた場合のように樹脂が炭素質材料の表面を覆ってしまうことや、炭素質材料同士の接触を阻害することがないため、活性質が本来有する高い比表面積を維持することができ、容積密度が大きく、しかも抵抗が小さい電極シートを得ることができる。しかも、アラミドフィブリットは、非常に細かくフィブリル化した繊維であり、これが炭素質材料の隙間に入り込み、炭素質材料を強固に保持し、さらに電極として実用に耐えるシート強度を維持することができる。 In the present invention, the electrode sheet is composed of the above-described carbonaceous material and aramid fibrates, the carbonaceous material is held by the aramid fibrates, and the content of the aramid fibrates will be described later. It is important to be in range. As a result, the resin does not cover the surface of the carbonaceous material as in the case of using a binder resin such as polyolefin, and the contact between the carbonaceous materials is not hindered. An electrode sheet that can maintain the surface area, has a large volume density, and has a low resistance can be obtained. In addition, the aramid fibrils are very finely fibrillated fibers, which enter the gaps between the carbonaceous materials, firmly hold the carbonaceous materials, and can maintain sheet strength that can be practically used as electrodes.
さらに、驚くべきことに炭素質材料の含有量を電極シート重量を基準として７０重量％以上と高くしても、上記のアラミドフィブリットは炭素質材料を十分に保持できることがわかった。ただし、あまりフィブリットの含有量が少なすぎても、十分に炭素質材料を保持するのが難しくなり、シートの機械的強度及び取り扱い性などが悪くなる。一方で、フィブリットの含有量が多すぎると、容積密度が小さくなり、抵抗も大きくなる。このため、フィブリットの含有量は、電極シートの全重量を基準として０．５〜３０重量％、好ましくは２〜２０重量％、より好ましくは５〜１５重量％とする必要がある。 Furthermore, it was surprisingly found that the aramid fibrite can sufficiently hold the carbonaceous material even when the content of the carbonaceous material is as high as 70% by weight or more based on the weight of the electrode sheet. However, even if the fibril content is too small, it becomes difficult to sufficiently hold the carbonaceous material, and the mechanical strength and handleability of the sheet are deteriorated. On the other hand, when there is too much fibrite content, volume density will become small and resistance will also become large. For this reason, the fibrit content needs to be 0.5 to 30% by weight, preferably 2 to 20% by weight, more preferably 5 to 15% by weight, based on the total weight of the electrode sheet.
また、上記のアラミドフィブリットのバインダー効果を高くする上で、該アラミドフィブリットの一部が溶融し、炭素質材料に融着していることが好ましい。
さらに、電極シートが、加圧により、圧縮または圧延されていることが、炭素質材料同士をより接触し易くし、電極シートの抵抗をさらに低くすることができる点で好ましい。かかる観点から、シートの比重が高いこと、具体的には比重が０．５〜１．０であることが好ましく、より好ましくは０．５〜０．９である。
In order to enhance the binder effect of the aramid fibrates, it is preferable that a part of the aramid fibrates is melted and fused to the carbonaceous material.
Furthermore, it is preferable that the electrode sheet is compressed or rolled by pressurization in that the carbonaceous materials can be more easily brought into contact with each other and the resistance of the electrode sheet can be further reduced. From such a viewpoint, the specific gravity of the sheet is high, specifically, the specific gravity is preferably 0.5 to 1.0, more preferably 0.5 to 0.9.
以上に説明した、電極シートは次の方法により製造することができる。すなわち、本発明の電極シートは、アラミドフィブリッド、炭素質素材、及び水を、アラミドフィブリッド：炭素質素材の重量比が０．５：９９．５〜３０：７０となるように混合してスラリーとし、これを湿式抄造することにより製造することができる。 The electrode sheet described above can be manufactured by the following method. That is, in the electrode sheet of the present invention, aramid fibrid, a carbonaceous material, and water are mixed so that the weight ratio of aramid fibrid: carbonaceous material is 0.5: 99.5 to 30:70. It can be manufactured by making a slurry and wet-making it.
さらに詳細に説明するが、本発明はこれに限定されるものではない。まず、スラリーの作成は、上記アラミドフィブリッドを０．５〜３０質量部、好ましくは２〜２０質量部、より好ましくは５〜１５質量部と、炭素質成分を７０〜９９．５質量部、好ましくは８０〜９８質量部、より好ましくは８５〜９６質量部（内、活物質と導電性付与剤との配合比率は、活物質１００質量部に対し、導電性付与剤が０．１〜２０質量部、好ましくは２〜１５質量部）に水５０００〜１００００質量部を加え、ミキサー及び混練器等を用いてアラミドフィブリッドと炭素質成分を均一に混合し、スラリーを作成する。これにより炭素質材料をアラミドフィブリッドの微小フィブリルに絡合させることができる。さらに、湿式抄造は、上記スラリーを公知の抄造装置により抄造し、必要に応じて公知の乾燥機を用いて乾燥し、シートとすることができる。 Although described in more detail, the present invention is not limited to this. First, the slurry is prepared by 0.5 to 30 parts by mass of the aramid fibrid, preferably 2 to 20 parts by mass, more preferably 5 to 15 parts by mass, and 70 to 99.5 parts by mass of the carbonaceous component. Preferably it is 80-98 mass parts, More preferably, it is 85-96 mass parts (Inside, the compounding ratio of an active material and an electroconductivity imparting agent is 0.1-20 electroconductivity imparting agent with respect to 100 mass parts of active material. 5,000 to 10000 parts by mass of water is added to (parts by mass, preferably 2 to 15 parts by mass), and the aramid fibrid and the carbonaceous component are uniformly mixed using a mixer and a kneader to prepare a slurry. Thereby, the carbonaceous material can be entangled with the microfibrils of the aramid fibrils. Furthermore, in wet papermaking, the slurry can be made with a known papermaking apparatus and dried using a known dryer as necessary to obtain a sheet.
上記の抄造工程により得られたシートは、加熱カレンダーロール等を用いて熱ローラープレス処理し加熱及び加圧することにより、アラミドフィブリッドが軟化し、該アラミドフィブリッドの炭素質材料へのアンカー効果が大きくなり、両者の結着がより強くなる。また、加圧及び加熱処理はシート中での炭素質材料同士の接触を向上させる。この際、線圧を制御することにより適切な厚みの電極シートが得ることができる。 The sheet obtained by the above paper making process is heated and pressed using a heated calender roll or the like, so that the aramid fibrids are softened, and the anchor effect of the aramid fibrids on the carbonaceous material is improved. It becomes larger and the binding between the two becomes stronger. Moreover, pressurization and heat treatment improve the contact between the carbonaceous materials in the sheet. At this time, an electrode sheet having an appropriate thickness can be obtained by controlling the linear pressure.
以下に本発明を実施例に基づき具体的に説明する。なお本発明はこれらに限定されるものではない。なお、電極シートの物性評価は次のように行った。
１）比重
電極シートの体積および重量から算出した。
２）抵抗
電極シートの抵抗はＪＩＳ Ｋ７１９４に準拠して測定した。
３）比表面積
電極シートの比表面積はＮ２ガスによるＢＥＴ法を用いて測定した。
使用機器；フローソーブIII２３１０（島津製作所製）
予備乾燥；２００℃×３０分
４）耐はんだ性
はんだごてを２６０℃に昇温し、これを１０ｃｍ×１０ｃｍの電極シートに、縦横それぞれ３ｃｍ間隔で９箇所押し当て、該電極シートの変形や穴あきを目視で確認した。シート変形や穴あきのないものを「良好」、変形や穴あきのあるものを「不良」とした。
５）容量
得られた電極シートを両極に使用したコイン型のキャパシタを試作し、電極シートのキャパシタ容量を測定した。コイン型キャパシタの直径は２ｃｍであり、電解液として１ｍｏｌ／リットルの過塩素酸リチウムプロピレンカーボネート溶液を使用した。電解液は電極シートに真空含浸をした。
The present invention will be specifically described below based on examples. The present invention is not limited to these. The physical properties of the electrode sheet were evaluated as follows.
1) Specific gravity It calculated from the volume and weight of the electrode sheet.
2) Resistance The resistance of the electrode sheet was measured according to JIS K7194.
3) Specific surface area The specific surface area of the electrode sheet was measured using the BET method with N2 gas.
Equipment used: Flowsorb III 2310 (manufactured by Shimadzu Corporation)
Pre-drying; 200 ° C. × 30 minutes 4) Solder resistance The soldering iron was heated to 260 ° C., and this was pressed against a 10 cm × 10 cm electrode sheet at nine locations at intervals of 3 cm in length and width respectively. The perforation was confirmed visually. The sheet without deformation or perforation was defined as “good”, and the sheet with deformation or perforation was defined as “bad”.
5) Capacity A coin-type capacitor using the obtained electrode sheet for both electrodes was made as a prototype, and the capacitor capacity of the electrode sheet was measured. The coin type capacitor had a diameter of 2 cm, and a 1 mol / liter lithium perchlorate propylene carbonate solution was used as the electrolyte. The electrolyte solution was vacuum impregnated into the electrode sheet.
［実施例１］
アラミドフィブリッド１０質量部と、高純度活性炭（クラレケミカル製ＲＰ―１５）およびケッチェンブラック（ケッチェン・ブラック・インターナショナル（株）製ＥＣ−３００Ｊ）からなる炭素質材料（活性炭：ケッチェンブラック＝９：１（重量比））１００質量部とを水５０００質量部とともにＪＩＳ標準離解機にて３０００ｒｐｍで３分間混合して、スラリーを得た。さらにこのスラリーを、ＴＡＰＰＩ式角型抄紙機で抄造し、プレス脱水した後、１２０℃の乾燥機で２時間乾燥させることで、紙状物を得た。なお、表１において示すアラミドフィブリットと炭素質材料の重量比は、抄造工程で流出したフィブリットと炭素質材料の重量を測定し、それからシートを構成するフィブリットと炭素質材料の重量をそれぞれ求め、それらの重量比を計算したものである。以下の実施例及び比較例でも同様にして算出した重量比を表１に示す。さらに上記シートに熱ローラープレスにより、温度１００℃、線圧４００ｋｇｆ／ｃｍで加熱、加圧処理を施して電極シートを得た。結果を表１に示す。
[Example 1]
Carbonaceous material (activated carbon: Ketjen Black = 9) consisting of 10 parts by mass of aramid fibrids, high-purity activated carbon (RP-15 made by Kuraray Chemical) and Ketjen Black (EC-300J made by Ketjen Black International Co., Ltd.) : 1 (weight ratio)) 100 parts by mass and 5000 parts by mass of water were mixed for 3 minutes at 3000 rpm with a JIS standard disintegrator to obtain a slurry. Further, this slurry was made with a TAPPI square paper machine, press dehydrated, and then dried with a dryer at 120 ° C. for 2 hours to obtain a paper. In addition, the weight ratio of the aramid fibrite and the carbonaceous material shown in Table 1 is the weight of the fibrit and the carbonaceous material that flowed out in the paper making process, and then the weight of the fibrit and the carbonaceous material constituting the sheet is determined respectively. It is obtained and the weight ratio thereof is calculated. Table 1 shows the weight ratios calculated in the same manner in the following Examples and Comparative Examples. Further, the sheet was heated and pressurized by a hot roller press at a temperature of 100 ° C. and a linear pressure of 400 kgf / cm to obtain an electrode sheet. The results are shown in Table 1.
［実施例２］
アラミドフィブリッドの量を５質量部、炭素質材料の量を１１０質量部に変更した以外は実施例１と同様にして電極シートを得た。結果を表１に示す。
[Example 2]
An electrode sheet was obtained in the same manner as in Example 1 except that the amount of aramid fibrid was changed to 5 parts by mass and the amount of the carbonaceous material was changed to 110 parts by mass. The results are shown in Table 1.
［実施例３］
アラミドフィブリッドの量を２０質量部、上記炭素質材料の量を８５質量部に変更した以外は実施例１と同様にして電極シートを得た。結果を表１に示す。
[Example 3]
An electrode sheet was obtained in the same manner as in Example 1 except that the amount of aramid fibrid was changed to 20 parts by mass and the amount of the carbonaceous material was changed to 85 parts by mass. The results are shown in Table 1.
［実施例４］
熱ローラープレス処理を省いた以外は実施例１と同様にして電極シートを得た。結果を表１に示す。
[Example 4]
An electrode sheet was obtained in the same manner as in Example 1 except that the hot roller press treatment was omitted. The results are shown in Table 1.
［比較例１］
アラミドフィブリッドの量を４０質量部、炭素質材料の量を６３質量部に変更した以外は実施例１と同様にして電極シートを得た。結果を表１に示す。
[Comparative Example 1]
An electrode sheet was obtained in the same manner as in Example 1 except that the amount of aramid fibrid was changed to 40 parts by mass and the amount of the carbonaceous material was changed to 63 parts by mass. The results are shown in Table 1.
［比較例２］
アラミドフィブリッドの代わりにアラミドパルプ（帝人テクノプロダクツ製トワロン１０９５）１０質量部を用い、炭素質材料の量を１２０質量部に変更した以外は実施例１と同様にして電極シートを得た。結果を表１に示す。なお、抄造時に、アラミドフィブリットを用いたときは炭素質材料の流出があまりなかったが、本比較例では炭素質材料の流出が多く認められた。
[Comparative Example 2]
An electrode sheet was obtained in the same manner as in Example 1, except that 10 parts by mass of aramid pulp (Twaron 1095 manufactured by Teijin Techno Products) was used instead of aramid fibrid, and the amount of the carbonaceous material was changed to 120 parts by mass. The results are shown in Table 1. When aramid fibrite was used during paper making, the carbonaceous material did not flow out much, but in this comparative example, a large amount of carbonaceous material flowed out.
［比較例３］
実施例１においてアラミドフィブリッドの代わりにポリエチレンパルプ（（株）三井石油化学工業製ＳＷＰＥ６２０）１０質量部を用い、炭素質材料の量を１２５質量部に変更した以外は実施例１と同様にして電極シートを得た。結果を表１に示す。なお、本比較例でも、比較例３と同様に抄造時に炭素質材料の流出が多く認められた。
In Example 1, 10 parts by mass of polyethylene pulp (SWPE620 manufactured by Mitsui Petrochemical Co., Ltd.) was used instead of aramid fibrid, and the amount of the carbonaceous material was changed to 125 parts by mass. An electrode sheet was obtained. The results are shown in Table 1. In this comparative example, as in Comparative Example 3, a large amount of carbonaceous material flowed out during paper making.
本発明の電極シートは、鉛フリーはんだのような高温のはんだ付けでも変形や穴あきがなく、しかも容量密度が大きく、抵抗の小さいといった従来にない優れた性能を有している。電極シートを提供することができる。このため、電気二重層キャパシタ用電極などに好適に用いることができ、その産業上の利用価値が極めて高いものである。また、本発明の製造方法によれば、上記電極シートを容易にしかも安定して製造することができる。 The electrode sheet of the present invention has unprecedented excellent performances such as no deformation or perforation even at high temperature soldering such as lead-free solder, and has a large capacity density and low resistance. An electrode sheet can be provided. For this reason, it can be used suitably for an electrode for an electric double layer capacitor or the like, and its industrial utility value is extremely high. Moreover, according to the manufacturing method of this invention, the said electrode sheet can be manufactured easily and stably.
Claims (7)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010150534A1 (en) * | 2009-06-23 | 2010-12-29 | クラレケミカル株式会社 | Flow-through capacitor, method for producing deionized water, and device for producing deionized water |
| CN108831752A (en) * | 2018-06-20 | 2018-11-16 | 苏州大学 | A kind of aramid fiber electrochemical capacitor and preparation method thereof |
| WO2020012990A1 (en) | 2018-07-10 | 2020-01-16 | 帝人株式会社 | Nonaqueous secondary battery binder and liquid dispersion thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04109555A (en) * | 1990-08-29 | 1992-04-10 | Mitsubishi Petrochem Co Ltd | Manufacture of electrode of secondary battery |
| JPH08119615A (en) * | 1994-10-14 | 1996-05-14 | Kuraray Co Ltd | Activated-carbon sheet and electric-double-layer capacitor |
| JP2003217981A (en) * | 2002-01-25 | 2003-07-31 | Japan Vilene Co Ltd | Method for manufacturing electric double-layer capacitor electrode material |
| JP2004193569A (en) * | 2002-11-29 | 2004-07-08 | Honda Motor Co Ltd | Polarizable electrode for electric double layer capacitor and electric double layer capacitor using it |
-
2005
- 2005-12-07 JP JP2005353342A patent/JP4734103B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04109555A (en) * | 1990-08-29 | 1992-04-10 | Mitsubishi Petrochem Co Ltd | Manufacture of electrode of secondary battery |
| JPH08119615A (en) * | 1994-10-14 | 1996-05-14 | Kuraray Co Ltd | Activated-carbon sheet and electric-double-layer capacitor |
| JP2003217981A (en) * | 2002-01-25 | 2003-07-31 | Japan Vilene Co Ltd | Method for manufacturing electric double-layer capacitor electrode material |
| JP2004193569A (en) * | 2002-11-29 | 2004-07-08 | Honda Motor Co Ltd | Polarizable electrode for electric double layer capacitor and electric double layer capacitor using it |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010150534A1 (en) * | 2009-06-23 | 2010-12-29 | クラレケミカル株式会社 | Flow-through capacitor, method for producing deionized water, and device for producing deionized water |
| JPWO2010150534A1 (en) * | 2009-06-23 | 2012-12-06 | クラレケミカル株式会社 | Liquid-permeable capacitor, deionized water production method, and deionized water production apparatus |
| JP5687620B2 (en) * | 2009-06-23 | 2015-03-18 | クラレケミカル株式会社 | Liquid-permeable capacitor, deionized water production method, and deionized water production apparatus |
| CN108831752A (en) * | 2018-06-20 | 2018-11-16 | 苏州大学 | A kind of aramid fiber electrochemical capacitor and preparation method thereof |
| WO2020012990A1 (en) | 2018-07-10 | 2020-01-16 | 帝人株式会社 | Nonaqueous secondary battery binder and liquid dispersion thereof |
| KR20210028684A (en) | 2018-07-10 | 2021-03-12 | 데이진 가부시키가이샤 | Binder for non-aqueous secondary battery and dispersion thereof |
| US20210194006A1 (en) * | 2018-07-10 | 2021-06-24 | Teijin Limited | Binder for non-aqueous secondary battery and dispersion thereof |
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