JP2012138408A - Electrochemical device and manufacturing method thereof - Google Patents

Electrochemical device and manufacturing method thereof Download PDF

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JP2012138408A
JP2012138408A JP2010288212A JP2010288212A JP2012138408A JP 2012138408 A JP2012138408 A JP 2012138408A JP 2010288212 A JP2010288212 A JP 2010288212A JP 2010288212 A JP2010288212 A JP 2010288212A JP 2012138408 A JP2012138408 A JP 2012138408A
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current collector
active material
electrode plate
negative electrode
positive electrode
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Koji Maeda
光司 前田
Masako Oya
昌子 大家
Noriyuki Hado
之規 羽藤
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Tokin Corp
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NEC Tokin Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

PROBLEM TO BE SOLVED: To provide an electrochemical device which helps to reduce manufacturing costs and which is free of self-charge failure and exhibits low internal resistance and high capacity, and a manufacturing method therefor.SOLUTION: Open holes 11 are formed in an electrode plate on which an active material electrode sheet 16 is formed which has its active material disposed on the principal plane on at least one side of a current collector. Open holes 17 formed in the active material electrode sheet have a smaller aperture diameter than that of open holes 18 formed in the current collector, in which the aperture diameter of the open holes in the current collector is 0.01 mm to 5 mm, both ends inclusive, and the open area rate of the open holes in the current collector, relative to the area of the current collector, is 0.1% to 30%, both ends inclusive.

Description

本発明は、リチウムイオンキャパシタ、リチウムイオン二次電池などの電気化学デバイスおよびその製造方法に関するものである。   The present invention relates to an electrochemical device such as a lithium ion capacitor and a lithium ion secondary battery, and a method for producing the same.

ラミネートフィルムによる外装構造を有する充放電可能な電池機能を有する電気化学デバイスとしては、電気二重層キャパシタ、リチウムイオン二次電池などがあり、また近年は、電気二重層キャパシタの正極とリチウムイオン二次電池の負極とを組み合わせたハイブリッドタイプのキャパシタ（以下ハイブリッドキャパシタ）も知られている。   Electrochemical devices with a battery function that can be charged and discharged with an exterior structure made of a laminate film include electric double layer capacitors and lithium ion secondary batteries. Recently, positive electrodes and lithium ion secondary batteries of electric double layer capacitors are also included. A hybrid type capacitor (hereinafter referred to as a hybrid capacitor) in combination with a negative electrode of a battery is also known.

上述したような電気化学デバイスは、電気自動車などのモータ駆動用のエネルギー源、あるいはエネルギー回生システムのキーデバイスとして、さらには無停電電源装置、風力発電、太陽光発電への応用など、ＣＯ２排出量削減に寄与する様々な新しい用途への適用が検討されており、次世代のデバイスとしてその期待度の高いデバイスである。 Electrochemical devices such as those mentioned above are used as energy sources for driving motors such as electric vehicles, or as key devices for energy regeneration systems, as well as for CO 2 emissions such as uninterruptible power supplies, wind power generation, and solar power generation. Application to various new uses that contribute to volume reduction is being studied, and it is a highly anticipated device as a next-generation device.

近年、モータ駆動用のエネルギー源、エネルギー回生システム用途への適用において、電気化学デバイスへの更なる高エネルギー密度化および低抵抗化が求められている。   2. Description of the Related Art In recent years, there has been a demand for higher energy density and lower resistance for electrochemical devices in application to motor drive energy sources and energy regeneration system applications.

電気二重層キャパシタは、使用する電解液の種類により、水系電解液タイプと、非水系電解液タイプとに分類される。単一の電気二重層キャパシタの耐電圧は、水系電解液タイプの場合で１．２Ｖ程度、非水系電解液タイプの場合でも２．７Ｖ程度である。電気二重層キャパシタが蓄積可能なエネルギー容量を増加させるためには、この耐電圧をさらに高くすることが重要であるが、現状の構成では困難であるという課題がある。   Electric double layer capacitors are classified into an aqueous electrolyte type and a non-aqueous electrolyte type depending on the type of electrolyte used. The withstand voltage of a single electric double layer capacitor is about 1.2 V in the case of an aqueous electrolyte type, and about 2.7 V in the case of a non-aqueous electrolyte type. In order to increase the energy capacity that can be stored in the electric double layer capacitor, it is important to further increase the withstand voltage, but there is a problem that it is difficult with the current configuration.

一方、リチウムイオン二次電池は、リチウム含有遷移金属酸化物を主成分とする正極、リチウムイオンを吸蔵、脱離しうる炭素材料を主成分とする負極、およびリチウム塩を含む有機系電解液とから構成されている。リチウムイオン二次電池を充電すると、正極からリチウムイオンが脱離して負極の炭素材料に吸蔵され、放電したときは逆に負極からリチウムイオンが脱離して正極の金属酸化物に吸蔵される。リチウムイオン二次電池は電気二重層キャパシタに比べて高電圧、高容量であるという性質を有するが、一方でその内部抵抗が高く、低抵抗化が困難であるという課題がある。   On the other hand, a lithium ion secondary battery includes a positive electrode mainly composed of a lithium-containing transition metal oxide, a negative electrode mainly composed of a carbon material capable of occluding and desorbing lithium ions, and an organic electrolyte containing a lithium salt. It is configured. When the lithium ion secondary battery is charged, lithium ions are desorbed from the positive electrode and occluded in the carbon material of the negative electrode. Conversely, when discharged, lithium ions are desorbed from the negative electrode and occluded in the metal oxide of the positive electrode. Lithium ion secondary batteries have the properties of higher voltage and higher capacity than electric double layer capacitors, but have a problem that their internal resistance is high and it is difficult to reduce the resistance.

ハイブリッドキャパシタは、正極に活性炭を用い、負極にリチウムイオンを吸蔵、脱離しうる炭素材料を用いている。充放電時に負極においてリチウムイオンの吸蔵、脱離反応を伴うことから、キャパシタ内部で実際に生じる両電極間の電位差は、負極にリチウム金属を用いた場合により近い、より卑な値にて推移する。従って、従来の正極、負極に活性炭を用いた電気二重層キャパシタと比較してより高耐電圧化することができ、よって蓄積可能なエネルギー量を電気二重層キャパシタに比較して大きく増加させる（高エネルギー化）ことが可能であり、且つ低抵抗であることから、上記の課題を解決するデバイスとして有力である。   The hybrid capacitor uses activated carbon for the positive electrode and a carbon material that can occlude and desorb lithium ions for the negative electrode. The potential difference between the two electrodes that actually occurs inside the capacitor shifts to a more basic value that is closer to the case where lithium metal is used for the negative electrode because lithium ions are absorbed and desorbed in the negative electrode during charging and discharging. . Therefore, the withstand voltage can be further increased as compared with the conventional electric double layer capacitor using activated carbon for the positive electrode and the negative electrode, and the amount of energy that can be stored is greatly increased compared to the electric double layer capacitor (high Energy) and low resistance, it is promising as a device for solving the above problems.

電気化学デバイスの更なる高エネルギー化に関する解決策として、以下に示すような負極由来のリチウムを含有させる技術を応用することも行われている。   As a solution for further increasing the energy of electrochemical devices, a technique of incorporating lithium derived from the negative electrode as described below is also applied.

実用化されているリチウム二次電池は、グラファイト等の炭素材料を負極に、ＬｉＣｏＯ２、ＬｉＭｎ２Ｏ４等のリチウム含有金属酸化物を正極に用い、電池組立後、充電することにより正極のリチウム含有金属酸化物から負極にリチウムを供給し、更に放電では負極リチウムを正極に戻すという、ロッキングチェア型である。これは、予め電池内に正極由来、負極由来のリチウムを含有させ、このリチウムから正極または負極に挿入することによって高容量化、すなわち高エネルギー化が達成されている。具体的には、負極上にリチウム金属箔を貼り合わせ、正極およびセパレータとともに電池セル内に挿入し、電解液を注液し、負極とリチウム金属箔の電気的な接触により負極に予めリチウムを挿入する方法である。しかしながら、各負極にリチウム金属箔を貼り合わせしなければならないこと、またリチウム金属箔の厚み下限に限界があるため負極電極の厚みが厚くなり電池設計上の制約が出てしまうことが課題である。 The lithium secondary battery in practical use uses a carbon material such as graphite as a negative electrode and a lithium-containing metal oxide such as LiCoO 2 or LiMn 2 O 4 as a positive electrode. It is a rocking chair type in which lithium is supplied from the contained metal oxide to the negative electrode, and further, the negative electrode lithium is returned to the positive electrode in discharging. This is achieved by increasing the capacity, ie, increasing the energy, by previously containing lithium derived from the positive electrode and the negative electrode in the battery and inserting the lithium into the positive electrode or the negative electrode. Specifically, a lithium metal foil is bonded onto the negative electrode, inserted into the battery cell together with the positive electrode and the separator, an electrolyte solution is injected, and lithium is previously inserted into the negative electrode by electrical contact between the negative electrode and the lithium metal foil. It is a method to do. However, it is a problem that a lithium metal foil must be bonded to each negative electrode, and that there is a limit on the lower limit of the thickness of the lithium metal foil, so that the thickness of the negative electrode is increased and the battery design is restricted. .

上記の課題に対して、特許文献１には、正極、負極並びに電解液としてリチウム塩の非プロトン性有機溶媒溶液を備えた有機電解質電池であって、正極集電体および負極集電体が、それぞれ表裏面を貫通する孔を備え、負極由来のリチウムが負極あるいは正極と対向して配置されたリチウムとの電気化学的接触により担持されている有機電解質電池が記載されている。   In response to the above problem, Patent Document 1 discloses an organic electrolyte battery including a positive electrode, a negative electrode, and an aprotic organic solvent solution of a lithium salt as an electrolytic solution, and the positive electrode current collector and the negative electrode current collector include: There is described an organic electrolyte battery that has holes penetrating the front and back surfaces, and in which lithium derived from the negative electrode is supported by electrochemical contact with lithium disposed opposite to the negative electrode or the positive electrode.

特許文献１では、正極集電体および負極集電体に表裏面を貫通する孔を備えたパンチングメタルやエキスパンドメタルを用いている。負極由来のリチウムが負極あるいは正極と対向して配置されたリチウムとの電気化学的接触により複数枚の集電体間をリチウムイオンが積層方向に移動し挿入される。   In Patent Document 1, a punching metal or an expanded metal provided with a hole penetrating the front and back surfaces of the positive electrode current collector and the negative electrode current collector is used. Lithium ions move in the stacking direction between a plurality of current collectors and are inserted by electrochemical contact with lithium disposed opposite to the negative electrode or the positive electrode.

また、特許文献２には、正極および負極の少なくとも一方に孔または溝を設けた非水電解質二次電池が提案されている。特許文献２では、集電体の両面に電極ペーストを塗布した正極および負極を作製し、その後打ち抜きによって貫通孔を形成する構成となっている。   Patent Document 2 proposes a nonaqueous electrolyte secondary battery in which a hole or a groove is provided in at least one of a positive electrode and a negative electrode. In patent document 2, the positive electrode and negative electrode which apply | coated the electrode paste on both surfaces of the electrical power collector are produced, and it is the structure which forms a through-hole by punching after that.

上記の特許文献１や特許文献２に構成により、リチウム金属箔の厚みによる設計の制約や各電極の貼り合わせがないように改善がなされている。   With the configuration described in Patent Document 1 and Patent Document 2 described above, improvements have been made so that there is no design restriction due to the thickness of the lithium metal foil and bonding of the electrodes.

国際公開第１９９８／３３２２７号International Publication No. 1998/33227 特開平９−２８３１１６号公報JP-A-9-283116

今後期待される電気自動車などのモータ駆動用のエネルギー源、あるいはエネルギー回生システムにおいては高エネルギーが求められる上に高出力が必須であるため、電池の内部抵抗増加は大きな課題である。   In an energy source for driving a motor such as an electric vehicle or an energy regeneration system expected in the future, high energy is required and high output is indispensable.

特許文献１に記載の正極および負極の集電体に貫通孔を有するエキスパンドメタルやパンチングメタルを用いる工法は、積層した電極、捲回し複数枚重なりあった電極間も貫通孔を介してリチウムイオンが移動し各電極由来リチウムから各電極へ挿入が可能となるため高エネルギー化に有用な方法である。その一方で集電体に貫通孔を有するエキスパンドメタル、パンチングメタルを用いるため集電性悪化による電池の内部抵抗の増加が課題となる。   In the method of using an expanded metal or punching metal having through holes in the positive and negative electrode current collectors described in Patent Document 1, lithium ions are also transferred between the stacked electrodes and the electrodes that are wound and overlapped through the through holes. Since it moves and can be inserted into each electrode from lithium derived from each electrode, it is a useful method for increasing energy. On the other hand, since the expanded metal and punching metal which have a through-hole are used for an electrical power collector, the increase in the internal resistance of a battery by current collection deterioration becomes a subject.

またエキスパンドメタル、パンチングメタルの資材コストは貫通孔等の加工をしていない箔集電体に対して約１０倍であり、資材費、すなわち製品コストが高くなる。さらに、金型で成形する貫通孔の開孔径は大きく、塗工時片面塗工では電極スラリーが抜け落ちるため自己放電不良が多くなり、マルチコーター等による両面同時塗工が必須となる。両面同時塗工は、片面塗工と比較し塗工厚みの調整が難しくバラツキも大きくなることや、また塗工前の状態で集電体に貫通孔を有するため、集電体の強度が貫通孔の無い集電体と比較して著しく劣り、塗工時の加工スピードの調整等が必要となる。このため、電極製造工程が煩雑化し、製造コストが増大するという課題がある。   In addition, the material cost of expanded metal and punching metal is about 10 times that of a foil current collector that is not processed such as a through hole, and the material cost, that is, the product cost increases. Furthermore, the opening diameter of the through-holes formed by the mold is large, and electrode slurry falls off in single-side coating during coating, so that self-discharge failure increases, and simultaneous double-side coating with a multi coater or the like is essential. Double-sided simultaneous coating makes it difficult to adjust the coating thickness compared to single-sided coating, resulting in large variations, and the current collector has through holes before coating, so the strength of the current collector penetrates. The current collector is significantly inferior to a non-hole current collector, and it is necessary to adjust the processing speed during coating. For this reason, there exists a subject that an electrode manufacturing process becomes complicated and manufacturing cost increases.

一方、特許文献２に記載の電極に貫通孔を形成する方法は、製造も容易で、資材費も低減できるが、電極ペーストを塗布した集電体からなる電極を打ち抜き貫通孔を形成する構成であるので、貫通孔の内壁に集電体が露出している状態となる。この露出部分は抵抗が低いため、充放電の際に露出部分に電流が集中し、露出部分付近にリチウムのデンドライドが生成しやすく、デンドライドの成長により、正極、負極間の内部短絡を招き、自己放電不良の発生によって製品寿命が短くなる可能性がある。   On the other hand, the method of forming a through-hole in the electrode described in Patent Document 2 is easy to manufacture and can reduce material costs, but it has a configuration in which a through-hole is formed by punching an electrode made of a current collector coated with an electrode paste. Therefore, the current collector is exposed on the inner wall of the through hole. Since the exposed portion has low resistance, current concentrates on the exposed portion during charge and discharge, and lithium dendrites are likely to be generated near the exposed portion, and the dendride growth causes an internal short circuit between the positive and negative electrodes. Product life may be shortened by the occurrence of defective discharge.

従って、本発明の目的は、製造コストを低減し、自己放電不良がなく、且つ内部抵抗が低く、高容量である電気化学デバイスおよびその製造方法を提供することにある。   Accordingly, it is an object of the present invention to provide an electrochemical device that has a reduced manufacturing cost, has no self-discharge failure, has a low internal resistance, and has a high capacity, and a method for manufacturing the same.

本発明の電気化学デバイスは、上記の課題を解決するためになされたもので、集電体の少なくとも一方の主面に活物質を配した活物質電極シートを形成した電極板に貫通孔を形成し、前記活物質電極シートの貫通孔の開孔径が前記集電体の貫通孔の開孔径よりも小さくし、前記集電体の内壁を覆う構造となっている。   The electrochemical device of the present invention was made in order to solve the above problems, and formed a through-hole in an electrode plate on which an active material electrode sheet having an active material arranged on at least one main surface of a current collector was formed. And the opening diameter of the through-hole of the said active material electrode sheet is made smaller than the opening diameter of the through-hole of the said collector, and it has the structure which covers the inner wall of the said collector.

すなわち、本発明によれば、金属箔からなる集電体の少なくとも一方の主面に活物質を配した活物質電極シートが形成された正極電極板および負極電極板と、前記正極電極板と前記負極電極板の間に積層されたセパレータを有する電気化学素子と、前記正極電極板および前記負極電極板にそれぞれ電気的に接続された正極外部端子板および負極外部端子板と、前記電気化学素子を内蔵し、電解液を充填し、密閉する外装フィルムシートを備える電気化学デバイスであって、前記正極電極板および前記負極電極板の少なくとも一方には、前記集電体および活物質電極シートを貫通する複数の貫通孔を有し、前記活物質電極シートの貫通孔の開孔径が前記集電体の貫通孔の開孔径よりも小さいことを特徴とする電気化学デバイスが得られる。   That is, according to the present invention, a positive electrode plate and a negative electrode plate on which an active material electrode sheet in which an active material is arranged on at least one main surface of a current collector made of a metal foil, the positive electrode plate, An electrochemical element having a separator laminated between negative electrode plates, a positive electrode external terminal plate and a negative electrode external terminal plate electrically connected to the positive electrode plate and the negative electrode plate, respectively, and the electrochemical element are incorporated. An electrochemical device comprising an exterior film sheet that is filled with an electrolyte solution and hermetically sealed, wherein at least one of the positive electrode plate and the negative electrode plate includes a plurality of electrodes that penetrate the current collector and the active material electrode sheet An electrochemical device having a through hole, wherein an opening diameter of the through hole of the active material electrode sheet is smaller than an opening diameter of the through hole of the current collector is obtained.

また、本発明によれば、前記集電体の貫通孔の内壁は、前記活物質で覆われていることを特徴とする上記の電気化学デバイスが得られる。   In addition, according to the present invention, there is obtained the above electrochemical device characterized in that an inner wall of the through hole of the current collector is covered with the active material.

また、本発明によれば、前記集電体の貫通孔の開孔径は、０．０１ｍｍ以上５ｍｍ以下であることを特徴とする上記の電気化学デバイスが得られる。   In addition, according to the present invention, there is obtained the above electrochemical device characterized in that the diameter of the through hole of the current collector is 0.01 mm or more and 5 mm or less.

また、本発明によれば、前記集電体の貫通孔の開孔率は、前記集電体の面積に対して０．１％以上３０％以下であることを特徴とする上記の電気化学デバイスが得られる。   According to the present invention, the opening ratio of the through holes of the current collector is 0.1% or more and 30% or less with respect to the area of the current collector. Is obtained.

また、本発明によれば、金属箔からなる集電体の少なくとも一方の主面に、活物質を配した活物質電極シートを形成した正極電極板および負極電極板と、前記正極電極板および前記負極電極板の間に積層するセパレータとを有する電気化学素子と、前記正極電極板および前記負極電極板にそれぞれ電気的に接続される正極外部端子板および負極外部端子板と、前記電気化学素子を内蔵し、電解液を充填し、密閉する外装フィルムシートを備える電気化学デバイスの製造方法であって、前記正極電極板および負極電極板の少なくとも一方には、前記集電体および活物質電極シートを貫通する複数の貫通孔を形成し、前記貫通孔を形成後に、前記活物質電極シートの貫通孔の開孔径が前記集電体の貫通孔の開孔径よりも小さくなるように加工することを特徴とする電気化学デバイスの製造方法が得られる。   Further, according to the present invention, a positive electrode plate and a negative electrode plate in which an active material electrode sheet in which an active material is arranged is formed on at least one main surface of a current collector made of metal foil, the positive electrode plate and the positive electrode plate An electrochemical element having a separator laminated between the negative electrode plates, a positive electrode external terminal plate and a negative electrode external terminal plate electrically connected to the positive electrode plate and the negative electrode plate, respectively, and the electrochemical element incorporated therein A method for producing an electrochemical device comprising an exterior film sheet that is filled with an electrolyte solution and hermetically sealed, wherein at least one of the positive electrode plate and the negative electrode plate penetrates the current collector and the active material electrode sheet A plurality of through holes are formed, and after the through holes are formed, the opening diameter of the through holes of the active material electrode sheet is processed to be smaller than the opening diameter of the through holes of the current collector. Method for producing an electrochemical device, wherein the door is obtained.

また、本発明によれば、前記集電体の貫通孔の内壁を、前記活物質で覆うことを特徴とする上記の電気化学デバイスの製造方法が得られる。   In addition, according to the present invention, there is obtained the method for producing an electrochemical device described above, wherein an inner wall of the through hole of the current collector is covered with the active material.

また、本発明によれば、前記集電体の貫通孔の開孔径を、０．０１ｍｍ以上５ｍｍ以下とすることを特徴とする上記の電気化学デバイスの製造方法が得られる。   In addition, according to the present invention, the electrochemical device manufacturing method described above is characterized in that the diameter of the through hole of the current collector is 0.01 mm or more and 5 mm or less.

また、本発明によれば、前記集電体の貫通孔の開孔率を、前記集電体の面積に対して０．１％以上３０％以下とすることを特徴とする上記の電気化学デバイスの製造方法が得られる。   In addition, according to the present invention, the opening ratio of the through holes of the current collector is 0.1% to 30% with respect to the area of the current collector. The manufacturing method is obtained.

また、本発明によれば、前記電気化学デバイスが、リチウムイオン二次電池またはハイブリッドキャパシタであることを特徴とする上記の電気化学デバイスが得られる。   In addition, according to the present invention, the electrochemical device described above is obtained, wherein the electrochemical device is a lithium ion secondary battery or a hybrid capacitor.

本発明の電気化学デバイスでは、貫通孔を有する高価なエキスパンドメタルやパンチングメタル等を集電体に用いず、金属箔を用いることで資材費の低減、電極塗工の製造コスト低減、さらには集電性の悪化による内部抵抗の増加を抑制することができる。正極電極板および負極電極板に貫通孔を形成し、その貫通孔を介し、予めリチウム挿入用電極板から負極活物質電極シートにリチウムを挿入することで、高容量化が可能となる。また集電体の貫通孔の開孔径より活物質電極シートの貫通孔の開孔径を小さくすることで、自己放電不良の改善ができる。   The electrochemical device of the present invention does not use expensive expanded metal or punching metal having through-holes as a current collector, but uses metal foil to reduce material costs, reduce manufacturing costs for electrode coating, and collect It is possible to suppress an increase in internal resistance due to deterioration in electrical properties. By forming through holes in the positive electrode plate and the negative electrode plate, and inserting lithium from the lithium insertion electrode plate into the negative electrode active material electrode sheet in advance through the through holes, the capacity can be increased. Moreover, the self-discharge failure can be improved by making the diameter of the through hole of the active material electrode sheet smaller than the diameter of the through hole of the current collector.

本発明により、製造コストを低減し、自己放電不良がなく、且つ内部抵抗が低く、高容量である電気化学デバイスおよびその製造方法の提供が可能となる。   According to the present invention, it is possible to provide an electrochemical device and a method for manufacturing the same that reduce manufacturing costs, have no self-discharge failure, have low internal resistance, and high capacity.

本発明のハイブリッドキャパシタの形状および内部構成を示す図で、図１（ａ）は平面図、図１（ｂ）は正面図、図１（ｃ）は図１（ａ）のＡーＡ線断面図。FIG. 1A is a plan view, FIG. 1B is a front view, and FIG. 1C is a cross-sectional view taken along line AA of FIG. 1A. Figure. 本発明のハイブリッドキャパシタの内部の電気化学素子の構成を示す図で、図２（ａ）は正極電極板の平面図、図２（ｂ）はセパレータの平面図、図２（ｃ）は負極電極板の平面図。2A and 2B are diagrams showing the configuration of an electrochemical element inside the hybrid capacitor of the present invention, FIG. 2A is a plan view of a positive electrode plate, FIG. 2B is a plan view of a separator, and FIG. 2C is a negative electrode. The top view of a board. 本発明のハイブリッドキャパシタの電気化学素子の斜視図。The perspective view of the electrochemical element of the hybrid capacitor of this invention. 本発明のハイブリッドキャパシタの外部端子板を取り付けた電気化学素子の斜視図。The perspective view of the electrochemical element which attached the external terminal board of the hybrid capacitor of this invention. 本発明のハイブリッドキャパシタの負極にリチウムを挿入するリチウム挿入用電極板とリチウム挿入用外部端子の平面図。The top view of the electrode plate for lithium insertion which inserts lithium in the negative electrode of the hybrid capacitor of this invention, and the external terminal for lithium insertion. 本発明のハイブリッドキャパシタの電気化学素子にリチウム挿入用電極板をセットした状態の斜視図。The perspective view of the state which set the electrode plate for lithium insertion to the electrochemical element of the hybrid capacitor of this invention. 本発明のハイブリッドキャパシタのリチウム挿入用電極板を内蔵した平面図。The top view which incorporated the electrode plate for lithium insertion of the hybrid capacitor of this invention. 本発明の電気化学デバイスの電極板について詳細に説明する図で、図８（ａ）は平面図、図８（ｂ）はＡ部拡大図。It is a figure explaining in detail the electrode plate of the electrochemical device of this invention, FIG. 8 (a) is a top view, FIG.8 (b) is A part enlarged view. 従来のハイブリッドキャパシタの円状パンチングメタルに活物質電極シートを形成した電極板の平面図。The top view of the electrode plate which formed the active material electrode sheet in the circular punching metal of the conventional hybrid capacitor. 従来のハイブリッドキャパシタのエキスパンドメタルに活物質電極シートを形成した電極板の平面図。The top view of the electrode plate which formed the active material electrode sheet in the expanded metal of the conventional hybrid capacitor.

本発明の電気化学デバイスは、セパレータを介して対向する正極活物質電極シートと正極集電体を備える正極電極板と、リチウムを可逆的に吸蔵、脱離可能な負極活物質電極シートと負極集電体を備える負極電極板と、リチウム塩含有の有機電解液を含む電気化学素子と、正極電極板および負極電極板にそれぞれ電気的に接続される正極外部端子板および負極外部端子板と、電気化学素子を内蔵し周縁部にて密閉する外装フィルムシートを有している。負極活物質電極シートには、電気化学素子に対して積層方向に配置するリチウム挿入用電極板から電気化学的手法によりリチウムが挿入される。また、正極電極板および負極電極板の活物質電極シートが形成されている部分に、少なくとも１つの貫通孔が形成されている。正極電極板および負極電極板に形成された貫通孔を介し負極活物質電極シートにリチウムが挿入される。   The electrochemical device of the present invention includes a positive electrode active material electrode sheet and a positive electrode plate provided with a positive electrode current collector facing each other through a separator, a negative electrode active material electrode sheet capable of reversibly inserting and extracting lithium, and a negative electrode current collector. A negative electrode plate including an electric body; an electrochemical element including an organic electrolyte containing a lithium salt; a positive electrode external terminal plate and a negative electrode external terminal plate electrically connected to the positive electrode plate and the negative electrode plate, respectively; It has an exterior film sheet containing a chemical element and hermetically sealed at the periphery. Lithium is inserted into the negative electrode active material electrode sheet by an electrochemical method from an electrode plate for lithium insertion arranged in the stacking direction with respect to the electrochemical element. Further, at least one through hole is formed in a portion of the positive electrode plate and the negative electrode plate where the active material electrode sheet is formed. Lithium is inserted into the negative electrode active material electrode sheet through the through holes formed in the positive electrode plate and the negative electrode plate.

さらに、本発明の電気化学デバイスは、アルミニウム、ステンレス等の正極集電体上に正極活物質電極シートが形成された正極電極板と、銅、ニッケル、ステンレス等の負極集電体上に負極活物質電極シートが形成された負極電極板に、予めレーザマーカによるレーザ加工、又は金型によるプレス加工、ロールパンチング装置等で貫通孔が形成される。   Furthermore, the electrochemical device of the present invention includes a positive electrode plate in which a positive electrode active material electrode sheet is formed on a positive electrode current collector such as aluminum and stainless steel, and a negative electrode active material on a negative electrode current collector such as copper, nickel and stainless steel. A through-hole is previously formed in the negative electrode plate on which the material electrode sheet is formed by laser processing using a laser marker, press processing using a mold, a roll punching device, or the like.

ここで、正極電極板と負極電極板は、集電体の材質および表面処理方法、活物質電極シートの材質が異なるが、集電体に活物質電極シートを形成し、さらに貫通孔を形成するという構成に違いは無いので、どちらにも適用できる場合には、単に集電体、活物質電極シート、電極板と記載して説明する。即ち、集電体は、正極集電体および負極集電体を表し、活物質電極シートは、正極活物質シートおよび負極活物質シートを表すものとする。また、電極板は、正極電極板および負極電極板を表すものとする。   Here, the material of the current collector, the surface treatment method, and the material of the active material electrode sheet are different between the positive electrode plate and the negative electrode plate, but an active material electrode sheet is formed on the current collector, and a through hole is further formed. Since there is no difference in the configuration, when it can be applied to both, it will be described simply as a current collector, an active material electrode sheet, and an electrode plate. That is, the current collector represents a positive electrode current collector and a negative electrode current collector, and the active material electrode sheet represents a positive electrode active material sheet and a negative electrode active material sheet. Moreover, an electrode plate shall represent a positive electrode plate and a negative electrode plate.

電極板に貫通孔を形成後、圧延ロールプレス加工、又は金型によるプレス加工により、活物質電極シートに形成された貫通孔の開孔径が集電体の貫通孔の開孔径よりも小さく、さらに集電体の貫通孔の内壁を覆うように、即ち集電体の露出が無く形成されている。また、あらかじめ集電体に貫通孔を形成し、電極をパターン印刷することにより活物質電極シートを形成する方法でも、集電体の露出がなく貫通孔を形成した電極板を作製することも可能であるが、製造の容易さや加工コストを考慮して、前述の電極板に貫通孔を形成後にプレス成形をして、集電体の内壁を活物質電極シートで覆う方法が好ましい。   After forming the through-hole in the electrode plate, the diameter of the through-hole formed in the active material electrode sheet is smaller than the diameter of the through-hole of the current collector by rolling roll press processing or pressing with a die, and It is formed so as to cover the inner wall of the through hole of the current collector, that is, without exposing the current collector. It is also possible to produce an electrode plate with through holes without exposing the current collector even by forming an active material electrode sheet by forming through holes in the current collector in advance and pattern printing the electrodes. However, in consideration of ease of manufacture and processing cost, a method of forming the through hole in the above-mentioned electrode plate and press-molding and covering the inner wall of the current collector with the active material electrode sheet is preferable.

以下に、本発明の実施の形態について図面を参照して詳細に説明する。   Embodiments of the present invention will be described below in detail with reference to the drawings.

図１は、本発明のハイブリッドキャパシタの形状および内部構成を示す図で、図１（ａ）は平面図、図１（ｂ）は正面図、図１（ｃ）は図１（ａ）のＡーＡ線断面図である。図１（ａ）に示す通りハイブリッドキャパシタ１は外装フィルムシート４によって被覆されており、一方の短辺から正極外部端子板２および負極外部端子板３がそれぞれ延出している。また、図１（ｂ）に示す通り、負極外部端子板３は上側および下側の外装フィルムシート４の間から外部に導出している。図示しないが正極外部端子板２も同様に外装フィルムシート４から外部に導出している。さらに、図１（ｃ）に示す通りハイブリッドキャパシタ１の内部には、後述する電気化学素子５が内蔵されている。正極電極板は、正極集電体に正極活物質電極シートが形成されている。負極電極板は、負極集電体に負極活物質電極シートが形成されている。正極電極板と負極電極板には、それぞれ正極外部端子板２と負極外部端子板３が接続されている。上側と下側の外装フィルムシート４の間には電解液が充填されており、電気化学素子５は電解液に浸漬された状態となっている。   FIG. 1 is a diagram showing the shape and internal configuration of a hybrid capacitor of the present invention, in which FIG. 1A is a plan view, FIG. 1B is a front view, and FIG. 1C is A in FIG. FIG. As shown in FIG. 1A, the hybrid capacitor 1 is covered with an exterior film sheet 4, and a positive external terminal plate 2 and a negative external terminal plate 3 extend from one short side. Moreover, as shown in FIG.1 (b), the negative electrode external terminal board 3 is derived | led-out outside from between the upper and lower exterior film sheets 4. Although not shown, the positive external terminal plate 2 is similarly led out from the exterior film sheet 4 to the outside. Further, as shown in FIG. 1C, an electrochemical element 5 described later is built in the hybrid capacitor 1. In the positive electrode plate, a positive electrode active material electrode sheet is formed on a positive electrode current collector. In the negative electrode plate, a negative electrode active material electrode sheet is formed on a negative electrode current collector. A positive electrode external terminal plate 2 and a negative electrode external terminal plate 3 are connected to the positive electrode plate and the negative electrode plate, respectively. An electrolyte solution is filled between the upper and lower exterior film sheets 4, and the electrochemical element 5 is immersed in the electrolyte solution.

外装フィルムシート４は、上側と下側から電気化学素子５を内蔵しているが、周縁部では上側と下側の外装フィルムシート４同士が互いに接着して電解液を含む内容物を密封し、その漏出を防ぐ構成となっている。また、正極外部端子板２および負極外部端子板３が外部に導出する位置（接合部）では、各外部端子板の周囲を被覆して封止する構成となっている。従って、ハイブリッドキャパシタ１は、外装フィルムシート４同士の接着、および外装フィルムシート４による正極外部端子板２と負極外部端子板３の接合部の周囲の被覆によって完全に密封されている。   The exterior film sheet 4 incorporates the electrochemical element 5 from the upper side and the lower side, but at the peripheral part, the upper and lower exterior film sheets 4 adhere to each other and seal the contents containing the electrolyte, The structure prevents the leakage. In addition, at the position where the positive electrode external terminal plate 2 and the negative electrode external terminal plate 3 lead out to the outside (joining portion), the periphery of each external terminal plate is covered and sealed. Therefore, the hybrid capacitor 1 is completely sealed by adhesion between the exterior film sheets 4 and covering around the joint between the positive external terminal plate 2 and the negative external terminal plate 3 by the external film sheet 4.

図２は、本発明のハイブリッドキャパシタの内部の電気化学素子の構成を示す図で、図２（ａ）は正極電極板の平面図、図２（ｂ）はセパレータの平面図、図２（ｃ）は負極電極板の平面図である。図２（ａ）に示す正極電極板は、正極集電体とその主面に形成された正極活物質電極シート８からなる。ここで正極集電体には、正極活物質電極シート８が形成されているため図には示されていない。正極活物質電極シート８は、一般的にはアルミニウムやアルミニウム合金などの金属箔からなる正極集電体の片面もしくは両面に形成され、炭素材料を主成分とする活物質を多量に含む電極合剤層であって、バインダおよび導電剤を含むことが多い。正極電極板延出部６は、一般には正極活物質電極シート８が形成された正極集電体の一部を延出させたものであるが、何らかの薄い金属体を正極集電体に溶接や圧着などの方法により固定したものでもよい。正極電極板には、レーザ加工等により両面が貫通する貫通孔１１が形成されている。   2A and 2B are diagrams showing the structure of the electrochemical element inside the hybrid capacitor of the present invention. FIG. 2A is a plan view of the positive electrode plate, FIG. 2B is a plan view of the separator, and FIG. ) Is a plan view of the negative electrode plate. The positive electrode plate shown in FIG. 2A includes a positive electrode current collector and a positive electrode active material electrode sheet 8 formed on the main surface thereof. Here, since the positive electrode active material electrode sheet 8 is formed on the positive electrode current collector, it is not shown in the drawing. The positive electrode active material electrode sheet 8 is generally formed on one or both sides of a positive electrode current collector made of a metal foil such as aluminum or aluminum alloy, and includes an electrode mixture containing a large amount of an active material mainly composed of a carbon material. Often includes a binder and a conductive agent. The positive electrode plate extension portion 6 is generally a part of the positive electrode current collector on which the positive electrode active material electrode sheet 8 is formed, but some thin metal body is welded to the positive electrode current collector. It may be fixed by a method such as pressure bonding. The positive electrode plate is formed with a through hole 11 through which both surfaces penetrate by laser processing or the like.

図２（ｂ）に示すセパレータ１０は絶縁性の薄板であり、一般には正極活物質電極シート８、負極活物質電極シート９よりもやや大きく構成され、電解液が浸透しやすい素材であることが必要である。   The separator 10 shown in FIG. 2 (b) is an insulating thin plate, and is generally configured to be slightly larger than the positive electrode active material electrode sheet 8 and the negative electrode active material electrode sheet 9, and is a material that easily penetrates the electrolytic solution. is necessary.

図２（ｃ）に示す負極電極板は、負極集電体とその主面に形成された負極活物質電極シート９からなる。ここで負極集電体には、負極活物質電極シート９が形成されているため図には示されていない。負極活物質電極シート９は、一般的には銅や銅合金などの金属箔からなる負極集電体の片面もしくは両面に、炭素材料を主成分とする活物質を多量に含む電極合剤層であって、バインダおよび導電剤を含むことが多い。負極電極板延出部７は、一般には負極活物質電極シート９が形成された負極集電体の一部を延出させたものであるが、何らかの薄い金属体を負極集電体に溶接や圧着などの方法により固定したものでもよい。負極電極板には、レーザ加工により両面が貫通する貫通孔１１が形成されている。なお、図２（ｃ）では正極活物質電極シート８と同一形状とした場合を示しているが、両者の面積や形状は同一でなくても構わない。さらに、正極活物質電極シート８および負極活物質電極シート９の寸法形状や枚数は、必ずしも同一である必要はない。   The negative electrode plate shown in FIG. 2 (c) includes a negative electrode current collector and a negative electrode active material electrode sheet 9 formed on the main surface thereof. Here, since the negative electrode active material electrode sheet 9 is formed on the negative electrode current collector, it is not shown in the drawing. The negative electrode active material electrode sheet 9 is an electrode mixture layer containing a large amount of an active material mainly composed of a carbon material on one side or both sides of a negative electrode current collector made of a metal foil such as copper or a copper alloy. In many cases, a binder and a conductive agent are included. The negative electrode plate extension portion 7 is generally formed by extending a part of the negative electrode current collector on which the negative electrode active material electrode sheet 9 is formed, but some thin metal body is welded to the negative electrode current collector. It may be fixed by a method such as pressure bonding. The negative electrode plate is formed with a through hole 11 through which both surfaces penetrate by laser processing. In addition, although the case where it is set as the same shape as the positive electrode active material electrode sheet 8 is shown in FIG.2 (c), the area and shape of both may not be the same. Further, the dimensions and number of the positive electrode active material electrode sheet 8 and the negative electrode active material electrode sheet 9 are not necessarily the same.

図１に示した電気化学素子５は、例えば、上から図２（ｂ）に示すセパレータ、図２（ｃ）に示す負極電極板、図２（ｂ）に示すセパレータ、図２（ａ）に示す正極電極板の順で積層したものである。上側の外装フィルムシート４の内部の接着層と最上部の負極電極板の間、正極電極板と負極電極板の間および最下部の負極電極板と下側の外装フィルムシートの４内部の接着層の間には、必ずセパレータが１枚ずつ挿入されている。すなわち、外装フィルムシート４内において電気化学素子５の構成は、セパレータ／負極電極板／セパレータ／正極電極板／セパレータ／・・／セパレータ／正極電極板／セパレータ／負極電極板／セパレータとなっている。   The electrochemical element 5 shown in FIG. 1 includes, for example, the separator shown in FIG. 2B from the top, the negative electrode plate shown in FIG. 2C, the separator shown in FIG. 2B, and the separator shown in FIG. The positive electrode plates shown are stacked in this order. Between the adhesive layer inside the upper exterior film sheet 4 and the uppermost negative electrode plate, between the positive electrode plate and the negative electrode plate, and between the lowermost negative electrode plate and the inner adhesive layer 4 of the lower exterior film sheet The separators are always inserted one by one. That is, the structure of the electrochemical element 5 in the exterior film sheet 4 is separator / negative electrode plate / separator / positive electrode plate / separator /.../ separator / positive electrode plate / separator / negative electrode plate / separator. .

図３は、本発明のハイブリッドキャパシタの電気化学素子の斜視図である。電気化学素子５は、上述したようにセパレータを介して正極電極板と負極電極板を積層して構成されている。この正極電極板と負極電極板の一方の短辺から、正極電極板延出部６および負極電極板延出部７がそれぞれ引き出されている。   FIG. 3 is a perspective view of the electrochemical element of the hybrid capacitor of the present invention. As described above, the electrochemical element 5 is configured by laminating a positive electrode plate and a negative electrode plate via a separator. From one short side of the positive electrode plate and the negative electrode plate, a positive electrode plate extension portion 6 and a negative electrode plate extension portion 7 are drawn out, respectively.

図４は、本発明のハイブリッドキャパシタの外部端子板を取り付けた電気化学素子の斜視図である。電気化学素子５に、正極外部端子板２と負極外部端子板３とを取り付けた構成となっている。電気化学素子５の一方の短辺から延出している複数枚の正極電極板延出部６と正極外部端子板２が、また同じく延出している複数枚の負極電極板延出部７と負極外部端子板３が超音波溶接により接合されている。接合方法は、超音波溶接に限られるものではなく、抵抗溶接、レーザ溶接などでもよい。   FIG. 4 is a perspective view of an electrochemical element to which an external terminal plate of the hybrid capacitor of the present invention is attached. The electrochemical element 5 has a positive external terminal plate 2 and a negative external terminal plate 3 attached thereto. The plurality of positive electrode plate extension portions 6 and the positive electrode external terminal plate 2 extending from one short side of the electrochemical element 5 are also extended, and the plurality of negative electrode plate extension portions 7 and the negative electrode are also extended. The external terminal plate 3 is joined by ultrasonic welding. The joining method is not limited to ultrasonic welding, but may be resistance welding, laser welding, or the like.

図５は、本発明のハイブリッドキャパシタの負極にリチウムを挿入するリチウム挿入用電極板とリチウム挿入用外部端子の平面図である。リチウム挿入用電極板１２は、銅などの金属箔からなる集電体に延出している一部を除き、金属リチウム１３を貼り合わせ固定されている。またリチウム挿入用電極板１２とリチウム挿入用外部端子１４とが超音波溶接により接合されている。接合方法は、超音波溶接に限られるものではなく、抵抗溶接、レーザ溶接などでもよい。負極活物質電極シートへのリチウム挿入後は、リチウム挿入用電極板を取り出すことが望ましいが、挿入量にあわせた金属リチウムを用い消費させればリチウム挿入用電極板１２から延伸している電極板部分を最終的に切断してもよい。   FIG. 5 is a plan view of a lithium insertion electrode plate for inserting lithium into the negative electrode of the hybrid capacitor of the present invention and an external terminal for lithium insertion. The lithium insertion electrode plate 12 is bonded and fixed to a metal lithium 13 except for a part extending to a current collector made of a metal foil such as copper. The lithium insertion electrode plate 12 and the lithium insertion external terminal 14 are joined by ultrasonic welding. The joining method is not limited to ultrasonic welding, but may be resistance welding, laser welding, or the like. After inserting lithium into the negative electrode active material electrode sheet, it is desirable to take out the electrode plate for lithium insertion, but if it is consumed using metallic lithium according to the amount of insertion, the electrode plate extended from the electrode plate for lithium insertion 12 The part may be finally cut.

図６は、本発明のハイブリッドキャパシタの電気化学素子にリチウム挿入用電極板をセットした状態の斜視図である。リチウム挿入用外部端子１４を取り付けたリチウム挿入用電極板１２の金属リチウムを貼り合わせした面と、正極外部端子板２、負極外部端子板３を取り付けた電気化学素子５が対向するように配置した。本実施の形態では、リチウム挿入用電極板１２を、電気化学素子５の片面に対向するように配置したが、複数のリチウム挿入用電極板１２を両面に配置しても良いし、金属リチウムを両面に貼り合わせ、電気化学素子の内部に配置してもよい。リチウム挿入用電極板１２の集電体として、貫通孔を有するパンチングメタルやエキスパンドメタル等を用いれば金属リチウムを貼り合わせした面を必ずしも電気化学素子と対向する方向にする必要はないが、電気化学素子と対向する方がリチウム挿入の効率がよいため好ましい。   FIG. 6 is a perspective view showing a state in which a lithium insertion electrode plate is set on the electrochemical element of the hybrid capacitor of the present invention. The surface of the lithium insertion electrode plate 12 to which the lithium insertion external terminal 14 is attached is disposed so that the surface of the metal lithium bonded to the electrochemical element 5 to which the positive external terminal plate 2 and the negative external terminal plate 3 are attached. . In the present embodiment, the lithium insertion electrode plate 12 is disposed so as to face one surface of the electrochemical element 5, but a plurality of lithium insertion electrode plates 12 may be disposed on both surfaces, or metal lithium may be used. You may affix on both surfaces and arrange | position inside an electrochemical element. If a punching metal or an expanded metal having a through hole is used as a current collector of the electrode plate 12 for inserting lithium, the surface on which the metal lithium is bonded is not necessarily directed to face the electrochemical element. It is preferable to face the element because lithium insertion efficiency is good.

図７は、本発明のハイブリッドキャパシタのリチウム挿入用電極板を内蔵した平面図である。リチウム挿入用外部端子１４を取り付けたリチウム挿入用電極板の金属リチウムを貼り合わせした面と、正極外部端子板２、負極外部端子板３を取り付けた電気化学素子が対向するように配置し、電気化学素子を外装フィルムシート４に内蔵し、電解液を注入して密閉している。外装フィルムシート４は、金属箔とポリオレフィン系フィルムを貼り合わせたラミネートフィルムを使用できる。外装フィルムシート４の内側には熱可塑性樹脂が形成され、熱可塑性樹脂としては、ポリエチレン、ポリプロピレン、酸変性プロピレン、エチレンーメタクリル酸共重合体等が使用できる。   FIG. 7 is a plan view incorporating a lithium insertion electrode plate of the hybrid capacitor of the present invention. The surface of the electrode plate for lithium insertion to which the external terminal for lithium insertion 14 is bonded is arranged so that the electrochemical element to which the positive electrode external terminal plate 2 and the negative electrode external terminal plate 3 are attached faces each other. The chemical element is built in the exterior film sheet 4 and sealed by injecting an electrolytic solution. As the exterior film sheet 4, a laminate film in which a metal foil and a polyolefin film are bonded together can be used. A thermoplastic resin is formed inside the exterior film sheet 4, and polyethylene, polypropylene, acid-modified propylene, an ethylene-methacrylic acid copolymer, or the like can be used as the thermoplastic resin.

図８は、本発明の電気化学デバイスの電極板について詳細に説明する図で、図８（ａ）は平面図、図８（ｂ）はＡ部拡大図である。図８（ａ）に示すように、電極板には集電体に活物質電極シート１６が形成され、複数の貫通孔１１が形成されている。また、図８（ｂ）に示すように、活物質電極シートに形成された貫通孔１７は、集電体（図示せず）に形成された貫通孔１８よりも開孔径が小さくなっている。さらに集電体に形成された貫通孔１８の内壁が、活物質電極シート１６で被覆されているのが好ましい。電極板延出部１５は、正極電極板と負極電極板を積層したときに交互に配置される。   FIG. 8 is a diagram for explaining in detail the electrode plate of the electrochemical device of the present invention. FIG. 8 (a) is a plan view and FIG. 8 (b) is an enlarged view of part A. As shown to Fig.8 (a), the active material electrode sheet 16 is formed in the collector at the electrode plate, and the several through-hole 11 is formed. Moreover, as shown in FIG.8 (b), the opening diameter of the through-hole 17 formed in the active material electrode sheet is smaller than the through-hole 18 formed in the electrical power collector (not shown). Furthermore, it is preferable that the inner wall of the through hole 18 formed in the current collector is covered with the active material electrode sheet 16. The electrode plate extending portions 15 are alternately arranged when the positive electrode plate and the negative electrode plate are laminated.

次に、本発明の実施の形態における、正極電極板、負極電極板、セパレータ、正極電極板および負極電極板に形成する貫通孔の製造方法の例を以下に説明する。   Next, the example of the manufacturing method of the through-hole formed in the positive electrode plate, the negative electrode plate, a separator, a positive electrode plate, and a negative electrode plate in embodiment of this invention is demonstrated below.

（正極電極板）
正極電極板は、アルミニウム箔またはステンレス箔等からなる金属箔の正極集電体に、炭素材料を主成分とする活物質とバインダ、および導電剤を混合してシート状にした正極活物質電極シートを、一体化させたものである。この活物質となる炭素原料としては、木材、鋸屑、椰子殻、パルプ廃液などの植物系物質、石炭、石油重質油、またはそれらを熱分解して得られる石炭系および石油系ピッチ、石油コークス、カーボンエアロゲル、タールピッチなどの化石燃料系物質、フェノール樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデンなどの合成高分子系物質など各種のものが用いられる。これらの炭素原料を炭化した後に、ガス賦活法もしくは薬品賦活法によって賦活し、比表面積が７００ｍ２／ｇ〜３０００ｍ２／ｇの炭素系活物質を得る。この活物質の比表面積はとくに１０００ｍ２／ｇ〜２０００ｍ２／ｇの場合が好ましい。 (Positive electrode plate)
The positive electrode plate is a positive electrode active material electrode sheet formed by mixing a positive electrode current collector of a metal foil made of aluminum foil or stainless steel foil, etc., with an active material mainly composed of a carbon material, a binder, and a conductive agent. Are integrated. The carbon raw material used as the active material includes plant materials such as wood, sawdust, coconut husk and pulp waste liquid, coal, heavy petroleum oil, coal-based and petroleum-based pitch obtained by pyrolyzing them, and petroleum coke. Various materials such as fossil fuel materials such as carbon aerogel and tar pitch, and synthetic polymer materials such as phenol resin, polyvinyl chloride resin, and polyvinylidene chloride are used. These carbon material after carbonization, and activating the gas activation method or chemical activation method, the specific surface area to obtain a carbon-based active material of 700m 2 / g~3000m 2 / g. The specific surface area of the active material is particularly preferred if the 1000m 2 / g~2000m 2 / g.

また、バインダとしては、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、フルオロオレフィン共重合体架橋ポリマー等の含フッ素系樹脂、スチレン−ブタジエンゴム等のゴム系バインダ、ポリプロピレン、ポリエチレン等の熱可塑性樹脂などが用いられ、正極活物質電極シートの全体の３質量％〜２０質量％程度のバインダを含んで作製するのが好ましい。上記の物質の中では特に、ポリテトラフルオロエチレンが耐熱性、耐薬品性、作製されるシート状の分極性電極層の強度の観点から好ましい。さらに、導電剤としては、アセチレンブラック、ケッチェンブラックなどのカーボンブラック、天然黒鉛、熱膨張黒鉛炭素繊維などから選択される物質を、正極活物質電極シートの全体の５質量％〜３０質量％程度添加することが好ましい。   As the binder, fluorine-containing resins such as polytetrafluoroethylene, polyvinylidene fluoride and fluoroolefin copolymer cross-linked polymers, rubber binders such as styrene-butadiene rubber, thermoplastic resins such as polypropylene and polyethylene, etc. are used. In addition, it is preferable to produce the positive electrode active material electrode sheet by including a binder of about 3% by mass to 20% by mass. Among the above substances, polytetrafluoroethylene is particularly preferable from the viewpoint of heat resistance, chemical resistance, and strength of the sheet-like polarizable electrode layer to be produced. Furthermore, as the conductive agent, a material selected from carbon black such as acetylene black and ketjen black, natural graphite, thermally expanded graphite carbon fiber, etc., is about 5% by mass to 30% by mass of the whole positive electrode active material electrode sheet. It is preferable to add.

次に、正極電極板を作製する方法の例について説明する。以下の例では活物質となる炭素原料としてフェノール樹脂を用い、バインダ物質としてポリテトラフルオロエチレン、また導電剤としてケッチェンブラックを選択している。まず、フェノール樹脂を炭化し、賦活して作製した活性炭粉末とポリテトラフルオロエチレンからなるバインダ、およびケッチェンブラックの三者を混練し、次いで圧延を行ってシート状の活物質電極層を成形する。こうして得られた正極活物質電極シートを、アルミニウムまたはステンレスの粗面化された集電体箔に導電性カーボンペーストを用いて接着する。さらに加熱乾燥することで一体化し、これを正極電極板とする。この際に集電体箔に予め延出部を１箇所形成しておき、そこには正極活物質電極シートを接着しないようにすれば、正極外部端子板に接続する正極電極板延出部を形成することができる。   Next, an example of a method for producing a positive electrode plate will be described. In the following example, a phenol resin is used as a carbon raw material to be an active material, polytetrafluoroethylene is selected as a binder material, and ketjen black is selected as a conductive agent. First, the activated carbon powder obtained by carbonizing and activating the phenol resin, a binder made of polytetrafluoroethylene, and a ketjen black are kneaded and then rolled to form a sheet-like active material electrode layer . The positive electrode active material electrode sheet thus obtained is bonded to a roughened current collector foil of aluminum or stainless steel using a conductive carbon paste. Furthermore, it integrates by heating-drying and makes this a positive electrode plate. At this time, if one extension portion is formed in advance on the current collector foil and the positive electrode active material electrode sheet is not adhered thereto, the positive electrode plate extension portion connected to the positive electrode external terminal plate is provided. Can be formed.

正極電極板は、上記の方法ではなく、正極活物質電極シートと正極集電体とを重ね合わせて、これらを互いに圧着させる方法で作製してもよい。またこの正極活物質電極シートは正極集電体の片面に接着してもよいし、両面に接着してもよい。さらに、メチルセルロースやポリフッ化ビニリデンなどのバインダを溶媒に溶解した溶液に、上記活物質や導電剤を混合、分散させてスラリーとし、このスラリーを正極集電体の片面あるいは両面に塗工する方法により、正極電極板を作製してもよい。   The positive electrode plate may be produced by a method in which the positive electrode active material electrode sheet and the positive electrode current collector are overlapped and bonded to each other instead of the above method. Moreover, this positive electrode active material electrode sheet may be adhered to one surface of the positive electrode current collector, or may be adhered to both surfaces. Further, by mixing and dispersing the above active material and conductive agent in a solution in which a binder such as methylcellulose or polyvinylidene fluoride is dissolved in a solvent, a slurry is formed, and this slurry is applied to one or both sides of the positive electrode current collector. A positive electrode plate may be produced.

（負極電極板）
負極電極板は、銅箔、ニッケル箔またはステンレス箔等からなる金属箔の負極集電体に、炭素材料を主成分とする活物質とバインダ、および導電剤を混合してシート状にした負極活物質電極シートを、一体化させたものである。炭素材料を主成分とする活物質としては、リチウムイオンのドープ、脱ドープが可能な、グラファイト、不定形炭素などの炭素系材料を用いることができる。 (Negative electrode plate)
The negative electrode plate is a negative electrode active material obtained by mixing a negative electrode current collector made of a metal foil made of copper foil, nickel foil, stainless steel foil, or the like with an active material mainly composed of a carbon material, a binder, and a conductive agent. The material electrode sheet is integrated. As an active material mainly composed of a carbon material, a carbon-based material such as graphite or amorphous carbon that can be doped or dedoped with lithium ions can be used.

また、バインダとしては、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、フルオロオレフィン共重合体架橋ポリマー等の含フッ素系樹脂、ポリブタジエンゴム、スチレン−ブタジエンゴム等のゴム系バインダ、ポリプロピレン、ポリエチレン等の熱可塑性樹脂などが用いられ、負極活物質電極シートの全体の３〜２０質量％程度のバインダを含んで作製するのが好ましい。上記の物質の中では特に、ポリフッ化ビニリデンが耐熱性、耐薬品性、シート強度の観点から好ましい。さらに、導電剤としては、アセチレンブラック、ケッチェンブラックのようなカーボンブラック、天然黒鉛、熱膨張黒鉛炭素繊維が好ましく、負極活物質電極シートの全体の５〜３０質量％程度添加するのが好ましい。   The binder includes fluorine-containing resins such as polytetrafluoroethylene, polyvinylidene fluoride and fluoroolefin copolymer crosslinked polymers, rubber binders such as polybutadiene rubber and styrene-butadiene rubber, and thermoplastic resins such as polypropylene and polyethylene. It is preferable that the negative electrode active material electrode sheet is produced by including about 3 to 20% by mass of a binder. Among the above substances, polyvinylidene fluoride is particularly preferable from the viewpoints of heat resistance, chemical resistance, and sheet strength. Further, as the conductive agent, carbon black such as acetylene black and ketjen black, natural graphite, and thermally expanded graphite carbon fiber are preferable, and it is preferable to add about 5 to 30% by mass of the whole negative electrode active material electrode sheet.

次に、負極電極板を作製する方法の例について説明する。以下の例では活物質となる炭素原料として難黒鉛化炭素材料を用い、バインダ物質としてポリテトラフルオロエチレン、また導電剤としてケッチェンブラックを選択している。まず難黒鉛化炭素材粉末と上記ポリテトラフルオロエチレンからなるバインダ、およびケッチェンブラックの三者を混練し、次いで圧延を行ってシート状の活物質電極層を成形する。こうして得られた負極活物質電極シートを、銅、ニッケルまたはステンレス集電体箔に導電性カーボンペーストを用いて接着する。さらに加熱乾燥することで一体化し、これを負極電極板とする。この際に集電体箔に予め延出部を１箇所形成しておき、そこには負極活物質電極シートを接着しないようにすれば、負極外部端子板に接続する負極電極板延出部を形成することができる。   Next, an example of a method for producing a negative electrode plate will be described. In the following example, a non-graphitizable carbon material is used as a carbon raw material as an active material, polytetrafluoroethylene is selected as a binder material, and ketjen black is selected as a conductive agent. First, the three components of the non-graphitizable carbon material powder, the binder made of the above polytetrafluoroethylene, and ketjen black are kneaded, and then rolled to form a sheet-like active material electrode layer. The negative electrode active material electrode sheet thus obtained is bonded to a copper, nickel or stainless steel current collector foil using a conductive carbon paste. Furthermore, it integrates by heating-drying and makes this a negative electrode plate. At this time, if one extension part is formed in the current collector foil in advance and the negative electrode active material electrode sheet is not adhered thereto, the negative electrode plate extension part connected to the negative electrode external terminal plate is provided. Can be formed.

負極電極板は、上記の方法ではなく、負極活物質電極シートと負極集電体とを重ね合わせて、これらを互いに圧着させる方法で作製してもよい。またこの負極活物質電極シートは負極集電体の片面に接着してもよいし、両面に接着してもよい。さらに、メチルセルロースやポリフッ化ビニリデンなどのバインダを溶媒に溶解した溶液に、上記活物質や導電剤を混合、分散させてスラリーとし、このスラリーを負極集電体の片面あるいは両面に塗工する方法により、負極電極板を作製してもよい。   The negative electrode plate may be produced by a method in which the negative electrode active material electrode sheet and the negative electrode current collector are superposed and pressure-bonded to each other instead of the above method. Moreover, this negative electrode active material electrode sheet may be adhered to one surface of the negative electrode current collector, or may be adhered to both surfaces. Further, by mixing and dispersing the above active material and conductive agent in a solution in which a binder such as methylcellulose or polyvinylidene fluoride is dissolved in a solvent, a slurry is obtained, and this slurry is applied to one or both sides of the negative electrode current collector. A negative electrode plate may be produced.

本発明に使用する正極集電体および負極集電体である金属箔は、従来使用していたパンチングメタルやエキスパンドメタルと価格を比べると、１０分の１以下であり、資材費を低減することが可能となる。   The metal foil as the positive electrode current collector and the negative electrode current collector used in the present invention is less than one-tenth of the price compared with the punching metal and the expanded metal used conventionally, and the material cost is reduced. Is possible.

（セパレータ）
また、正極電極板と負極電極板の間や、外装フィルムシートと負極電極板の間に設置されるセパレータは、厚さが薄く、しかも電子絶縁性およびイオン透過性が高い材料が好ましい。セパレータの構成材料はとくに限定されるものではないが、たとえば、ポリエチレンやポリプロピレンなどの不織布、もしくはビスコースレーヨンや天然セルロースの抄紙などが好適に使用される。セパレータは作製する電気化学デバイスの種別に応じてその構成材料を選定することが好ましい。 (Separator)
Moreover, the separator installed between the positive electrode plate and the negative electrode plate or between the exterior film sheet and the negative electrode plate is preferably made of a material having a small thickness and high electronic insulation and ion permeability. Although the constituent material of a separator is not specifically limited, For example, nonwoven fabrics, such as polyethylene and a polypropylene, or the papermaking of a viscose rayon or a natural cellulose is used suitably. The constituent material of the separator is preferably selected according to the type of electrochemical device to be produced.

（貫通孔）
次に、正極電極板および負極電極板の貫通孔の形成方法の例を説明する。本実施の形態においては、市販のグリーンレーザマーカなどを用い、ドライルーム中で電極板にレーザ加工で複数の貫通孔を形成した。レーザ加工による貫通孔形成の際には、基材が高温になるため、不活性ガス雰囲気やドライエアー環境下で加工することが望ましい。貫通孔の円心間距離に応じ、加工順序を調整することが好ましい。使用するレーザマーカは、波長１０６４ｎｍのＹＡＧ・ＹＶＯ４レーザでも加工が可能であるが、波長が短く（一例として５３２ｎｍ）、光レーザの吸収率が良いグリーンレーザを用いることが好ましい。また、プレス加工によっても貫通孔を形成でき、電極板の形状、貫通孔の形状に合わせて金型を作製し、油圧式のプレス機を用いるのが好ましい。 (Through hole)
Next, an example of a method for forming the through holes of the positive electrode plate and the negative electrode plate will be described. In the present embodiment, a plurality of through holes are formed in the electrode plate by laser processing in a dry room using a commercially available green laser marker or the like. When the through hole is formed by laser processing, the base material becomes high temperature, so that it is desirable to process in an inert gas atmosphere or a dry air environment. It is preferable to adjust the processing order according to the distance between the centers of the through holes. The laser marker used can be processed by a YAG / YVO 4 laser having a wavelength of 1064 nm, but it is preferable to use a green laser having a short wavelength (as an example, 532 nm) and a good optical laser absorptance. Further, it is preferable to form a through-hole by press working, and to prepare a mold according to the shape of the electrode plate and the shape of the through-hole, and use a hydraulic press.

電極板にレーザ加工あるいはプレス加工し貫通孔を形成した後、電極板にロールプレス装置等でプレス加工することによって、活物質電極シートのみが圧縮され、集電体の貫通孔の開孔径よりも活物質電極シートの貫通孔の開孔径を小さくすることができ、さらには、集電体の貫通孔の内壁を被覆することもできる。また、集電体にレーザ加工、プレス加工し貫通孔を形成した後に、活物質等からなるスラリーパターン塗工することにより、前述と同様の貫通孔を形成することができるが、製造コストを考慮すると前者の工法が好ましい。   After forming a through hole by laser processing or press processing on the electrode plate, only the active material electrode sheet is compressed by pressing the electrode plate with a roll press device or the like, and the diameter of the through hole of the current collector is smaller than the opening diameter. The diameter of the through hole of the active material electrode sheet can be reduced, and further, the inner wall of the through hole of the current collector can be covered. In addition, by forming a through hole in the current collector by laser processing and pressing, a through pattern similar to that described above can be formed by applying a slurry pattern made of an active material or the like, but considering the manufacturing cost. Then, the former construction method is preferable.

以上、本発明の実施の形態に係る電気化学デバイスの例として、ハイブリッドキャパシタの場合について示したものである。ハイブリッドキャパシタ以外の電気化学デバイスであるリチウムイオン二次電池の場合であっても、用いられる正極活物質電極シート、負極活物質電極シートの配置や外部端子板に設けた構成、金属箔を内蔵した外装フィルムシートの構成には特段の相違はなく、いずれの場合であっても適用できる。   As described above, the case of a hybrid capacitor is shown as an example of the electrochemical device according to the embodiment of the present invention. Even in the case of a lithium ion secondary battery that is an electrochemical device other than a hybrid capacitor, the arrangement of the positive electrode active material electrode sheet, the arrangement of the negative electrode active material electrode sheet, the configuration provided on the external terminal plate, and a metal foil are incorporated. There is no particular difference in the configuration of the exterior film sheet, and it can be applied in any case.

以下、実施例および比較例について説明する。なお実施例１〜２１および比較例１〜３は電気化学デバイスとしてハイブリッドキャパシタを、実施例２２および比較例４はリチウムイオン二次電池をそれぞれ作製し、各種評価を行ったものである。   Hereinafter, examples and comparative examples will be described. In addition, Examples 1-21 and Comparative Examples 1-3 produced a hybrid capacitor as an electrochemical device, and Example 22 and Comparative Example 4 produced lithium ion secondary batteries, respectively, and performed various evaluations.

（実施例１）
正極活物質である比表面積が１５００ｍ２／ｇのフェノール系活性炭の粉末９２質量部と、導電剤として黒鉛８質量部混合した粉末に対し、バインダとしてスチレン−ブタジエンゴム３質量部、カルボキシルメチルセルロース３質量部、溶媒として水２００質量部となるように加え、混練してスラリーを得た。次いでエッチング処理により両表面が粗面化された厚さ２０μｍのアルミニウム箔を正極集電体として、その両面に上記スラリーを均一に塗布し、その後乾燥させて圧延プレスし、正極活物質電極シートを得た。また正極活物質電極シートの端面の一部は正極集電体がタブ状に延出して取り出せるようにし、その部分の正極集電体の両面には正極活物質電極シートを形成せず、アルミニウム箔を露出させた。作製した正極電極板の正極活物質電極シート面にレーザマーカにて、ドライエアー環境下で開孔径０．０５ｍｍ、正極電極板の面積に対し、開孔率が５％になるように貫通孔の数量を調整し、貫通孔の配列は６０°千鳥型とし加工を施し、正極電極板を貫通する貫通孔を形成した。このときの貫通孔の円心間距離は約０．２１ｍｍであった。 Example 1
With respect to a powder obtained by mixing 92 parts by mass of a phenol-based activated carbon powder having a specific surface area of 1500 m 2 / g as a positive electrode active material and 8 parts by mass of graphite as a conductive agent, 3 parts by mass of styrene-butadiene rubber as a binder and 3 parts by mass of carboxymethyl cellulose And 200 parts by mass of water as a solvent and kneaded to obtain a slurry. Next, an aluminum foil having a thickness of 20 μm whose both surfaces are roughened by etching treatment is used as a positive electrode current collector, and the above slurry is uniformly applied to both surfaces thereof, and then dried and rolled and pressed. Obtained. In addition, a part of the end face of the positive electrode active material electrode sheet allows the positive electrode current collector to be taken out in a tab shape, and the positive electrode active material electrode sheet is not formed on both sides of the positive electrode current collector in that part, and the aluminum foil Was exposed. The number of through-holes in the positive electrode active material electrode sheet surface of the prepared positive electrode plate with a laser marker so that the hole diameter is 0.05 mm in a dry air environment and the area of the positive electrode plate is 5%. The through holes were arranged in a 60 ° staggered pattern to form a through hole penetrating the positive electrode plate. The distance between the circle centers of the through holes at this time was about 0.21 mm.

貫通孔を形成した正極電極板をロールプレス機にてプレス加工を施し、正極活物質電極シートを圧縮加工することで、厚みが両側にそれぞれ３０μｍの正極活物質電極シートを得た。この正極電極板の厚みは８０μｍであった。正極活物質電極シートを圧縮加工することで、正極集電体の貫通孔の開孔径よりも小さい貫通孔を形成した。貫通孔の大きさは、正極集電体の開孔径が０．０５ｍｍに対して、正極活物質電極シートの開孔径は約０．０４ｍｍであった。さらに、プレス加工にて正極活物質電極シートを圧縮したとき、正極活物質は、正極集電体の貫通孔に挿入し正極集電体の内壁を被覆した。   The positive electrode plate in which the through holes were formed was pressed by a roll press machine, and the positive electrode active material electrode sheet was compressed to obtain a positive electrode active material electrode sheet having a thickness of 30 μm on both sides. The thickness of this positive electrode plate was 80 μm. By compressing the positive electrode active material electrode sheet, a through hole smaller than the opening diameter of the through hole of the positive electrode current collector was formed. Regarding the size of the through hole, the aperture diameter of the positive electrode current collector was about 0.04 mm, while the aperture diameter of the positive electrode current collector was 0.05 mm. Further, when the positive electrode active material electrode sheet was compressed by press working, the positive electrode active material was inserted into the through hole of the positive electrode current collector to cover the inner wall of the positive electrode current collector.

負極活物質である難黒鉛化材料粉末８８質量部と、導電剤としてアセチレンブラック６質量部混合した粉末に対し、バインダとしてスチレン−ブタジエンゴム５質量部、カルボキシルメチルセルロース４質量部、溶媒として水２００質量部となるように加え、混練してスラリーを得た。次いで厚さ１０μｍの銅箔を負極集電体として、その両面に上記スラリーを均一に塗布し、その後乾燥させて圧延プレスし、負極活物質電極シートを得た。また負極活物質電極シートの端面の一部は負極集電体がタブ状に延出して取り出せるようにし、その部分の負極集電体の両面には負極活物質電極シートを形成せず、銅箔を露出させた。正極電極板と同様に、作製した負極電極板の負極活物質電極シート面にレーザマーカにて、ドライエアー環境下で開孔径０．０５ｍｍ、負極電極板の面積に対し、開孔率が５％になるように貫通孔の数量を調整し、貫通孔の配列は６０°千鳥型とし加工を施し、負極電極板を貫通する貫通孔を形成した。このときの円心間距離は正極電極板と同様に約０．２１ｍｍであった。   With respect to the powder obtained by mixing 88 parts by mass of the non-graphitizable material powder as the negative electrode active material and 6 parts by mass of acetylene black as a conductive agent, 5 parts by mass of styrene-butadiene rubber, 4 parts by mass of carboxymethyl cellulose, and 200 parts by mass of water as a solvent. And kneaded to obtain a slurry. Next, using a copper foil having a thickness of 10 μm as a negative electrode current collector, the slurry was uniformly applied on both sides thereof, then dried and rolled and pressed to obtain a negative electrode active material electrode sheet. In addition, a part of the end face of the negative electrode active material electrode sheet allows the negative electrode current collector to be taken out in a tab shape, and the negative electrode active material electrode sheet is not formed on both sides of the negative electrode current collector in that part, and the copper foil Was exposed. As with the positive electrode plate, the negative electrode active material electrode sheet surface of the prepared negative electrode plate was laser-marked with a hole diameter of 0.05 mm in a dry air environment, and the open area ratio was 5% with respect to the area of the negative electrode plate The number of through-holes was adjusted so that the arrangement of the through-holes was a 60 ° staggered pattern, and the through-holes penetrating the negative electrode plate were formed. The distance between the centers of the circles at this time was about 0.21 mm like the positive electrode plate.

貫通孔を形成した負極電極板をロールプレス機にてプレス加工を施し、負極活物質電極シートを圧縮加工することで、厚みが両側にそれぞれ２０μｍの負極活物質電極シートを得た。この負極電極板の厚みは５０μｍであった。負極活物質電極シートを圧縮加工することで、負極集電体の貫通孔の開孔径よりも小さい貫通孔を形成した。貫通孔の大きさは、正極集電体の開孔径が０．０５ｍｍに対して、正極活物質電極シートの開孔径は約０．０４ｍｍであった。さらに、プレス加工にて負極活物質電極シートを圧縮したとき、負極活物質は、負極集電体の貫通孔に挿入し負極集電体の内壁を被覆した。   The negative electrode plate in which the through holes were formed was pressed by a roll press machine, and the negative electrode active material electrode sheet was compressed to obtain a negative electrode active material electrode sheet having a thickness of 20 μm on both sides. The thickness of this negative electrode plate was 50 μm. By compressing the negative electrode active material electrode sheet, a through hole smaller than the opening diameter of the through hole of the negative electrode current collector was formed. Regarding the size of the through hole, the aperture diameter of the positive electrode current collector was about 0.04 mm, while the aperture diameter of the positive electrode current collector was 0.05 mm. Furthermore, when the negative electrode active material electrode sheet was compressed by press working, the negative electrode active material was inserted into the through hole of the negative electrode current collector to cover the inner wall of the negative electrode current collector.

セパレータとして、厚さ３５μｍの天然セルロース材の薄板を使用した。このセパレータの寸法形状は、上記正極電極板延出部および負極電極板延出部を除いた形状よりも寸法が大きくなるように構成した。   As a separator, a thin plate of a natural cellulose material having a thickness of 35 μm was used. The size and shape of the separator was configured to be larger than the shape excluding the positive electrode plate extension and the negative electrode plate extension.

次いで、セパレータ、負極電極板、セパレータ、正極電極板、セパレータの順番でこれら三者を積層し、電気化学素子を得た。この電気化学素子の最上部と最下部にはそれぞれ必ずセパレータが１枚ずつ配置されるようにした。本実施例では、１試料あたりの積層した正極電極板は４枚、負極電極板は５枚、セパレータは１０枚とし、電極板延出部を除いたその寸法は、正極電極板が５３ｍｍ×７０ｍｍ、負極電極板が５５ｍｍ×７２ｍｍ、セパレータが５７ｍｍ×７４ｍｍとした。また、電極板延出部は、それぞれの活物質電極シートの同一短辺から延出し、電極板延出部の寸法は、それぞれ９ｍｍ×１２ｍｍとした。   Subsequently, these three were laminated | stacked in order of the separator, the negative electrode plate, the separator, the positive electrode plate, and the separator, and the electrochemical element was obtained. One separator was always arranged at the top and bottom of the electrochemical device. In this example, 4 positive electrode plates laminated per sample, 5 negative electrode plates, 10 separators, and the dimensions excluding the electrode plate extension were 53 mm × 70 mm for the positive electrode plate. The negative electrode plate was 55 mm × 72 mm, and the separator was 57 mm × 74 mm. Moreover, the electrode plate extension part extended from the same short side of each active material electrode sheet, and the dimension of the electrode plate extension part was 9 mm x 12 mm, respectively.

正極外部端子板は、長さ２０ｍｍ×幅１０ｍｍ×厚さ０．２ｍｍのアルミニウム材を使用し、負極外部端子板は、長さ２０ｍｍ×幅１０ｍｍ×厚さ０．２ｍｍのニッケル材を使用した。外装フィルムシートから導出している領域は、長さ１０ｍｍ×幅１０ｍｍであった。外装フィルムシートと熱接着する面には、酸変性ポリオレフィン樹脂からなるシーラントが両面に施されているものを使用した。   The positive electrode external terminal plate was made of an aluminum material having a length of 20 mm × width of 10 mm × thickness of 0.2 mm, and the negative electrode external terminal plate was made of a nickel material having a length of 20 mm × width of 10 mm × thickness of 0.2 mm. The area derived from the exterior film sheet was 10 mm long × 10 mm wide. As the surface to be thermally bonded to the exterior film sheet, one having a sealant made of an acid-modified polyolefin resin on both sides was used.

次に、電気化学素子から延出している正極電極板延出部および負極電極板延出部を各々束ね、一括して外部端子板の端部にそれぞれ超音波溶接により固定した。   Next, the positive electrode plate extending portion and the negative electrode plate extending portion extending from the electrochemical element were bundled, and collectively fixed to the end portion of the external terminal plate by ultrasonic welding.

また、銅箔に金属リチウムを貼り合わせリチウム挿入用電極板を作製し、延出させた銅箔にリチウム挿入用外部端子を超音波溶接により固定した。このリチウム挿入用電極板を、外部端子板を溶接した電気化学素子の片面に、金属リチウムが電気化学素子と対向するように配置させた。   Moreover, metal lithium was bonded to the copper foil to prepare an electrode plate for lithium insertion, and the external terminal for lithium insertion was fixed to the extended copper foil by ultrasonic welding. This lithium insertion electrode plate was arranged on one side of the electrochemical element welded with the external terminal plate so that the metallic lithium faced the electrochemical element.

上述の電気化学素子および金属リチウム挿入用電極板を、２枚の外装フィルムシートで包み込み、正極外部端子板、負極外部端子板、リチウム挿入用外部端子が配置された二つの短辺と、一つの長辺の三辺の周縁部を熱圧着し、内面に形成した酸変性ポリオレフィン樹脂からなる熱可塑性樹脂層を接合させて袋状とした。この外装フィルムシートの内面の熱可塑性樹脂層の厚みは４０μｍとした。   The electrochemical element and the electrode plate for inserting metal lithium are wrapped in two exterior film sheets, two short sides on which a positive electrode external terminal plate, a negative electrode external terminal plate, and an external terminal for lithium insertion are arranged, and one The three peripheral edges of the long side were thermocompression bonded, and a thermoplastic resin layer made of acid-modified polyolefin resin formed on the inner surface was joined to form a bag. The thickness of the thermoplastic resin layer on the inner surface of the exterior film sheet was 40 μm.

次に、電気化学素子および金属リチウム挿入用電極板を内蔵した、袋状の２枚の外装フィルムシートの内部に電解液を注入した。電解液は、六フッ化リン酸リチウムをプロピレンカーボネートとジエチルカーボネートを１：１の割合で混合させた混合溶媒に溶解させ、１．０ｍｏｌ／ｌの濃度に調製したものを使用した。電解液を注入した後に、２枚の外装フィルムシートの残る一辺を、真空雰囲気中にて熱圧着により封止した。   Next, an electrolytic solution was injected into the two bag-shaped exterior film sheets containing the electrochemical element and the metal lithium insertion electrode plate. As the electrolytic solution, a solution prepared by dissolving lithium hexafluorophosphate in a mixed solvent in which propylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1 and adjusted to a concentration of 1.0 mol / l was used. After injecting the electrolytic solution, the remaining one side of the two exterior film sheets was sealed by thermocompression bonding in a vacuum atmosphere.

最後に、電気化学的手法によりリチウム挿入用電極板から負極の活物質電極シートにリチウムを挿入した。挿入量は、負極活物質重量に対し４００ｍＡｈ／ｇとした。リチウム挿入完了後、ラミネート短辺を開封し、リチウム挿入用電極板を取り出した。開封したラミネート辺を真空雰囲気中にて再度熱圧着し封止した。   Finally, lithium was inserted into the negative electrode active material electrode sheet from the electrode plate for lithium insertion by an electrochemical method. The amount of insertion was 400 mAh / g based on the weight of the negative electrode active material. After completing the lithium insertion, the short side of the laminate was opened, and the lithium insertion electrode plate was taken out. The opened laminate side was thermocompression-bonded again in a vacuum atmosphere and sealed.

以上の方法により、積層型のハイブリッドキャパシタを得た。この方法により作製したハイブリッドキャパシタは５０個であった。   A multilayer hybrid capacitor was obtained by the above method. There were 50 hybrid capacitors produced by this method.

（比較例１〜３：従来技術による場合）
実施例１と同様の方法により、ハイブリッドキャパシタ５０個を、以下に説明するそれぞれの条件ごとに作製した。作製したハイブリッドキャパシタの寸法形状は実施例１の場合と全く同一である。 (Comparative Examples 1-3: Case of conventional technology)
In the same manner as in Example 1, 50 hybrid capacitors were produced for each condition described below. The dimensions and shape of the fabricated hybrid capacitor are exactly the same as in the first embodiment.

比較例１〜３では、従来のハイブリッドキャパシタを作製した。図９は、従来のハイブリッドキャパシタの円状パンチングメタルに活物質電極シートを形成した電極板の平面図である。図１０は、従来のハイブリッドキャパシタのエキスパンドメタルに活物質電極シートを形成した電極板の平面図である。比較例１、２は図９に示すように、集電体にプレス加工したパンチングメタルを使用し、電極板延出部２５は、集電体と一体に形成した。比較例３は図１０に示すように、集電体に箔を網目（菱型）状に機械加工したエキスパンドメタルを使用し、電極板延出部３５は、集電体と一体に形成した。それぞれの集電体に、実施例１と同じ活物質含有スラリーを用い、マルチコーターにより塗工を施し、活物質電極シート２６、３６を形成し、正極電極板および負極電極板を得た。比較例１〜３において、正極集電体は厚み２０μｍのアルミニウムとし、正極活物質電極シートの厚みを両側にそれぞれ３０μｍとして、正極電極板の厚みは８０μｍにした。負極集電体は厚み１０μｍの銅とし、負極活物質電極シートの厚みを両側にそれぞれ２０μｍとして、負極電極板の厚みは５０μｍにした。   In Comparative Examples 1 to 3, conventional hybrid capacitors were produced. FIG. 9 is a plan view of an electrode plate in which an active material electrode sheet is formed on a circular punching metal of a conventional hybrid capacitor. FIG. 10 is a plan view of an electrode plate in which an active material electrode sheet is formed on an expanded metal of a conventional hybrid capacitor. In Comparative Examples 1 and 2, as shown in FIG. 9, punched metal pressed into the current collector was used, and the electrode plate extension 25 was formed integrally with the current collector. In Comparative Example 3, as shown in FIG. 10, an expanded metal obtained by machining a foil into a mesh (diamond shape) was used for the current collector, and the electrode plate extension 35 was formed integrally with the current collector. Each current collector was coated with a multi-coater using the same active material-containing slurry as in Example 1 to form active material electrode sheets 26 and 36 to obtain a positive electrode plate and a negative electrode plate. In Comparative Examples 1 to 3, the positive electrode current collector was aluminum having a thickness of 20 μm, the thickness of the positive electrode active material electrode sheet was 30 μm on each side, and the thickness of the positive electrode plate was 80 μm. The negative electrode current collector was copper having a thickness of 10 μm, the thickness of the negative electrode active material electrode sheet was 20 μm on each side, and the thickness of the negative electrode plate was 50 μm.

また、比較例１では、開孔径１ｍｍ、開孔率１０％、貫通孔配列を６０°千鳥型とした。このときの円心間距離は約３．０１ｍｍとした。比較例２では、開孔径１ｍｍ、開孔率３０％、貫通孔配列を６０°と、円心間距離は１．７３ｍｍとした。集電体と活物質電極シートの形成方法以外は、実施例１と同様の条件で、ハイブリッドキャパシタ５０個ずつ作製した。   In Comparative Example 1, the aperture diameter was 1 mm, the aperture ratio was 10%, and the through-hole arrangement was a 60 ° staggered type. The distance between the circle centers at this time was about 3.01 mm. In Comparative Example 2, the aperture diameter was 1 mm, the aperture ratio was 30%, the through-hole arrangement was 60 °, and the distance between the circle centers was 1.73 mm. 50 hybrid capacitors were manufactured under the same conditions as in Example 1 except for the method of forming the current collector and the active material electrode sheet.

比較例３は、網目状の貫通孔を有するエキスパンドメタルを集電体として使用し、比較例２と同じ開孔率が３０％のものを使用した。活物質電極シートの形成方法は、比較例１、２と同様の方法で行い、またそれ以外の構成および製造方法は実施例１と同様での条件とし、ハイブリッドキャパシタを５０個作製した。   The comparative example 3 used the expanded metal which has a mesh-shaped through-hole as a collector, and used the thing with the same open area rate as the comparative example 2 30%. The active material electrode sheet was formed by the same method as in Comparative Examples 1 and 2, and the other configuration and manufacturing method were the same as in Example 1, and 50 hybrid capacitors were produced.

（実施例２〜８、比較例４、５：開孔率）
実施例１と同様の方法により、ハイブリッドキャパシタ５０個を、以下に説明するそれぞれの条件ごとに作製した。作製したハイブリッドキャパシタの寸法形状は実施例１の場合と全く同一とした。 (Examples 2-8, Comparative Examples 4, 5: Opening ratio)
In the same manner as in Example 1, 50 hybrid capacitors were produced for each condition described below. The dimensions and shape of the fabricated hybrid capacitor were exactly the same as those in Example 1.

実施例１の試料と、実施例２〜８、比較例４、５の試料の異なる点は、電極板に形成された貫通孔の各電極板の面積に対する開孔率である。比較例４では０．０５％、実施例２では０．１％、実施例３では０．５％、実施例４では１％、実施例５では２％、実施例６では１０％、実施例７では２０％、実施例８では３０％、比較例５では４０％とした。これらの試料によって、開孔率による違いの評価を行った。なお、電極板に貫通孔を形成した後、ロールプレスにより圧縮し、活物質電極シートの貫通孔は集電体の貫通孔よりも小さくなるため、活物質電極シートの開孔率は、上記に示したものよりも小さい値となる。   The difference between the sample of Example 1 and the samples of Examples 2 to 8 and Comparative Examples 4 and 5 is the hole area ratio of the through holes formed in the electrode plate to the area of each electrode plate. 0.05% in Comparative Example 4, 0.1% in Example 2, 0.5% in Example 3, 1% in Example 4, 2% in Example 5, 10% in Example 6, Example 7 was 20%, Example 8 was 30%, and Comparative Example 5 was 40%. With these samples, the difference due to the hole area ratio was evaluated. In addition, after forming the through hole in the electrode plate, it is compressed by a roll press, and the through hole of the active material electrode sheet is smaller than the through hole of the current collector. The value is smaller than that shown.

（実施例９〜１５、比較例６、７：開孔径）
実施例１と同様の方法により、ハイブリッドキャパシタ５０個を、以下に説明するそれぞれの条件ごとに作製した。作製したハイブリッドキャパシタの寸法形状は実施例１の場合と全く同一とした。 (Examples 9-15, Comparative Examples 6 and 7: Opening Diameter)
In the same manner as in Example 1, 50 hybrid capacitors were produced for each condition described below. The dimensions and shape of the fabricated hybrid capacitor were exactly the same as those in Example 1.

実施例１の試料と、実施例９〜１５、比較例６、７の試料の異なる点は、電極板に形成した開孔径だけである。比較例６では０．００５ｍｍ、実施例９では０．０１ｍｍ、実施例１０では０．０３ｍｍ、実施例１１では０．１ｍｍ、実施例１２では０．２ｍｍ、実施例１３では１ｍｍ、実施例１４では２ｍｍ、実施例１５では５ｍｍ、比較例７では７ｍｍであった。これらの試料によって、開孔径による違いの評価を行った。なお、電極板に貫通孔を形成した後、ロールプレスにより圧縮し、活物質電極シートの貫通孔は集電体の貫通孔よりも小さくなるため、活物質電極シートの開孔径は、上記に示したものよりも平均０．００５ｍｍ程度小さい値となるが、開孔径が０、すなわち貫通孔が閉塞されることはなかった。   The difference between the sample of Example 1 and the samples of Examples 9 to 15 and Comparative Examples 6 and 7 is only the aperture diameter formed in the electrode plate. Comparative Example 6 is 0.005 mm, Example 9 is 0.01 mm, Example 10 is 0.03 mm, Example 11 is 0.1 mm, Example 12 is 0.2 mm, Example 13 is 1 mm, and Example 14 is 2 mm, 5 mm in Example 15, and 7 mm in Comparative Example 7. With these samples, the difference due to the hole diameter was evaluated. In addition, after forming a through-hole in an electrode plate, it compresses with a roll press, and since the through-hole of an active material electrode sheet becomes smaller than the through-hole of an electrical power collector, the opening diameter of an active material electrode sheet is shown above. Although the average value was about 0.005 mm smaller than the above, the opening diameter was 0, that is, the through hole was not blocked.

（実施例１６〜１８：貫通孔の形成方法）
実施例１３と同様の方法により、ハイブリッドキャパシタ５０個を、以下に説明するそれぞれの条件ごとに作製した。作製したハイブリッドキャパシタの寸法形状は実施例１３の場合と全く同一である。 (Examples 16-18: Formation method of a through-hole)
In the same manner as in Example 13, 50 hybrid capacitors were produced for each condition described below. The dimensions and shape of the fabricated hybrid capacitor are exactly the same as those in Example 13.

実施例１３の試料と、実施例１６、１７の試料の異なる点は、電極板に形成した貫通孔の形成方法である。実施例１６では金型を使用したプレス加工とし、実施例１８ではドラム式金型を使用したロールパンチングとした。また、実施例１８の試料の異なる点は、電極板に形成した貫通孔の形成方法と、活物質電極シートの作製方法である。   The difference between the sample of Example 13 and the samples of Examples 16 and 17 is the method of forming the through hole formed in the electrode plate. In Example 16, press working using a mold was used, and in Example 18, roll punching using a drum mold was used. Further, the sample of Example 18 is different in a method for forming a through hole formed in an electrode plate and a method for producing an active material electrode sheet.

実施例１８では、まず集電体の貫通孔をレーザ加工で形成し、実施例１と同じ活物質含有スラリーを用い、凹版印刷により集電体の両面に塗工を施し、各電極板を得た。実施例１８において、正極集電体は厚み２０μｍのアルミニウムを使用し、正極活物質電極シートの厚みを両側にそれぞれ３０μｍとし、正極電極板の厚みは８０μｍとなった。また、負極集電体は厚み１０μｍの銅を使用し、負極活物質電極シートの厚みを両側にそれぞれ２０μｍとし、負極電極板の厚みは５０μｍとなった。版の設計を、集電体の貫通孔の開孔径よりも活物質の貫通孔の開孔径が小さくなるようにし、このとき集電体の貫通孔の内壁が活物質電極シートで被覆されるようにした。これらの試料によって、貫通孔の形成方法の違いの評価を行った。   In Example 18, first, through holes of the current collector were formed by laser processing, and the same active material-containing slurry as in Example 1 was used, and coating was performed on both sides of the current collector by intaglio printing to obtain each electrode plate. It was. In Example 18, the positive electrode current collector used aluminum having a thickness of 20 μm, the thickness of the positive electrode active material electrode sheet was 30 μm on each side, and the thickness of the positive electrode plate was 80 μm. Moreover, the negative electrode current collector used copper having a thickness of 10 μm, the thickness of the negative electrode active material electrode sheet was 20 μm on each side, and the thickness of the negative electrode plate was 50 μm. The plate is designed so that the opening diameter of the through hole of the active material is smaller than the opening diameter of the through hole of the current collector, and at this time, the inner wall of the through hole of the current collector is covered with the active material electrode sheet. I made it. By using these samples, the difference in the formation method of the through holes was evaluated.

（実施例１９、比較例８：電気化学デバイスの種類）
実施例１と同様の方法により、ハイブリッドキャパシタ５０個を、以下に説明するそれぞれの条件ごとに作製した。実施例１９における試料と、実施例１の試料の異なる点は、電気化学デバイスの種類である。実施例１９では、正極活物質に実施例１のフェノール系活性炭ではなくコバルト酸リチウム（ＬｉＣｏＯ２）を、セパレータに実施例１のセルロース系ではなくポリエチレン系セパレータを用いた。これら以外に関しては、実施例１と同じ材料を用い同様の工法でリチウムイオン二次電池を５０個作製した。 (Example 19, Comparative Example 8: Type of electrochemical device)
In the same manner as in Example 1, 50 hybrid capacitors were produced for each condition described below. The difference between the sample in Example 19 and the sample in Example 1 is the type of electrochemical device. In Example 19, lithium cobaltate (LiCoO 2 ) was used as the positive electrode active material instead of the phenol-based activated carbon of Example 1, and a polyethylene-based separator instead of the cellulose-based material of Example 1 was used as the separator. Except for these, 50 lithium ion secondary batteries were manufactured in the same manner using the same materials as in Example 1.

比較例８は、比較例３と同じエキスパンドメタルを用いた集電体に、実施例１９と同じ活物質含有スラリーを用い、マルチコーターにより塗工を施し、各活物質電極シートを得た。比較例８において、正極集電体は厚み２０μｍのアルミニウムを使用し、正極活物質電極シートの厚みを両側にそれぞれ３０μｍとし、正極電極板の厚みは８０μｍとなった。また、負極集電体は厚み１０μｍの銅を使用し、負極活物質電極シートの厚みを両側にそれぞれ２０μｍとし、負極電極板の厚みは５０μｍとなった。各集電体以外は、実施例１９と同様の条件でリチウムイオン二次電池を５０個作製した。   In Comparative Example 8, the same active material-containing slurry as in Example 19 was applied to a current collector using the same expanded metal as in Comparative Example 3, and coating was performed with a multicoater to obtain each active material electrode sheet. In Comparative Example 8, the positive electrode current collector used aluminum having a thickness of 20 μm, the thickness of the positive electrode active material electrode sheet was 30 μm on each side, and the thickness of the positive electrode plate was 80 μm. Moreover, the negative electrode current collector used copper having a thickness of 10 μm, the thickness of the negative electrode active material electrode sheet was 20 μm on each side, and the thickness of the negative electrode plate was 50 μm. Except for each current collector, 50 lithium ion secondary batteries were produced under the same conditions as in Example 19.

（評価方法）
実施例１〜１９、および比較例１〜８において作製した電気化学デバイスは、それぞれ以下の評価を行った。評価項目は、絶縁抵抗、内部抵抗として直流抵抗（以下ＤＣ−Ｒともいう）、容量、自己放電（以下ＳＤともいう）の４種類である。実施例１〜１９、および比較例１〜８では電気化学デバイスを各５０個ずつ作製した。 (Evaluation methods)
The electrochemical devices produced in Examples 1 to 19 and Comparative Examples 1 to 8 were evaluated as follows. There are four types of evaluation items: insulation resistance, internal resistance, DC resistance (hereinafter also referred to as DC-R), capacity, and self-discharge (hereinafter also referred to as SD). In Examples 1 to 19 and Comparative Examples 1 to 8, 50 electrochemical devices were produced.

絶縁抵抗の評価について以下に示す。溶接により外部端子板を取り付けた電気化学素子に、単位面積当たり１ｋｇ／ｃｍ２の接圧をかけた状態で、絶縁抵抗測定機を用い、正極外部端子板と負極外部端子板の間に測定電圧１００Ｖを印加し、絶縁抵抗を測定した。絶縁抵抗の合否判定は２００ＭΩ以上を合格とした。評価数に対する不良数から不良率を算出した。 The evaluation of insulation resistance is shown below. A measurement voltage of 100 V is applied between the positive external terminal plate and the negative external terminal plate using an insulation resistance measuring machine in a state where a contact pressure of 1 kg / cm 2 per unit area is applied to the electrochemical element to which the external terminal plate is attached by welding. And the insulation resistance was measured. The pass / fail judgment of the insulation resistance was determined to be 200 MΩ or higher. The defect rate was calculated from the number of defects relative to the number of evaluations.

直流抵抗測定の評価について以下に示す。電気化学デバイスを充放電装置にて所定の定電圧で１時間充電した後、電流値２０Ｃで放電した際のＤＣ−Ｒを測定した。ＤＣ−Ｒの選別規格は、従来技術である比較例１の測定結果に対し、明らかな不良値を除いた正規分布から±３σに入る試料２０個を任意で抜き取り、この２０個の試料の平均値＋３σの値を基準値とし、基準値以下を合格とした。選別規格より大きいものは不良とし、評価数に対する不良数から不良率を算出した。実施例１９および比較例８は、リチウムイオン二次電池であるため不良選別の対象外とした。   The evaluation of DC resistance measurement is shown below. After charging the electrochemical device at a predetermined constant voltage for 1 hour with a charging / discharging device, the DC-R when discharged at a current value of 20 C was measured. The DC-R selection standard is based on the measurement result of Comparative Example 1 which is a prior art, and arbitrarily selected 20 samples that fall within ± 3σ from a normal distribution excluding an apparent defective value, and the average of the 20 samples. The value + 3σ was set as a reference value, and the value below the reference value was determined as pass. Those larger than the screening standard were regarded as defective, and the defect rate was calculated from the number of defects relative to the evaluation number. Since Example 19 and Comparative Example 8 were lithium ion secondary batteries, they were excluded from defective screening.

容量測定は、電気化学デバイスを充放電装置にて所定の定電圧で１時間充電した後、電流値２０Ｃで使用下限電圧まで放電した際の電流容量を測定した。容量の選別規格は、従来技術である比較例１の測定結果に対し、明らかな不良値を除いた正規分布から±３σに入る試料２０個を任意で抜き取り、この２０個の試料の容量平均値の９０％値とした。選別規格より小さいものは不良とし、評価数に対する不良数から不良率を算出した。実施例２３および比較例４は、リチウムイオン二次電池であるため不良選別の対象外とした。   In the capacity measurement, the electrochemical device was charged at a predetermined constant voltage for 1 hour with a charging / discharging device, and then the current capacity was measured when the electrochemical device was discharged at a current value of 20 C to the lower limit voltage. For the capacity selection standard, 20 samples that fall within ± 3σ from a normal distribution excluding an apparent defect value are arbitrarily extracted from the measurement result of Comparative Example 1 which is a conventional technique, and the volume average value of these 20 samples. Of 90%. Those smaller than the screening standard were regarded as defective, and the defect rate was calculated from the number of defects relative to the evaluation number. Since Example 23 and Comparative Example 4 are lithium ion secondary batteries, they were excluded from defective selection.

自己放電測定評価は、電気化学デバイスを充放電装置にて所定の定電圧で１時間充電した後、端子間を開回路にした状態で、高温槽にて６０℃で７２時間放置した後の端子間電圧を測定した。自己放電の選別規格は、従来技術である比較例１の測定結果に対し、明らかな不良値を除いた正規分布から±３σに入る試料１０個を任意で抜き取り、この１０個の試料の平均値−３σの値を基準とし、基準値以上を合格とした。選別規格より小さいものは不良とし、評価数に対する不良数から不良率を算出した。   Self-discharge measurement evaluation is performed after charging an electrochemical device at a predetermined constant voltage with a charging / discharging device for 1 hour, and then leaving the terminals open circuited and leaving the terminals at 60 ° C. for 72 hours in a high temperature bath The inter-voltage was measured. The selection standard for self-discharge is that 10 samples that fall within ± 3σ from a normal distribution excluding an apparent defect value are arbitrarily extracted from the measurement result of Comparative Example 1 which is a conventional technique, and the average value of these 10 samples. A value of −3σ was used as a reference, and a value above the reference value was determined to be acceptable. Those smaller than the screening standard were regarded as defective, and the defect rate was calculated from the number of defects relative to the evaluation number.

以上の方法により、実施例１〜１９、比較例１〜８における各々の試料の条件ごとに、絶縁抵抗測定評価、ＤＣ−Ｒ測定評価、容量測定評価、自己放電測定評価の４種類の評価をそれぞれ行った。平均容量、平均ＤＣ−Ｒ、総合不良率、総合評価結果、ＤＣ−Ｒ不良、絶縁不良、自己放電不良を表１に示す。   According to the above method, for each sample condition in Examples 1 to 19 and Comparative Examples 1 to 8, four types of evaluations of insulation resistance measurement evaluation, DC-R measurement evaluation, capacity measurement evaluation, and self-discharge measurement evaluation were performed. Each went. Table 1 shows the average capacity, average DC-R, overall failure rate, overall evaluation result, DC-R failure, insulation failure, and self-discharge failure.

Figure 2012138408
Figure 2012138408

表１に示された、各々の試料に対する４種類の試験の評価結果から、以下のことが分かった。即ち、本発明の電気化学デバイスによると、絶縁抵抗、ＤＣ−Ｒ、容量、自己放電の評価において、いずれも良好な結果が得られた。特に実施例１の平均ＤＣ−Ｒの値は、比較例１に対し約１５％の低抵抗化と良好な結果が得られた。これは、外部端子板と複数枚の延出部に貫通孔が無く、集電性、接触抵抗が比較例１より優れているためであると考えられる。また実施例１では、内部抵抗低減により放電時の電圧ドロップが改善されるため容量の減少量も比較的少なく、比較例１と同等の容量が得られた。比較例１〜３に関しては、複数枚の電極板部分（活物質電極シートが形成されない部分である延出部）に機械加工で形成した貫通孔のバリがセパレータを介して電極板間の絶縁不良が発生した。またＤＣ−Ｒのばらつきも大きく、ＤＣ−Ｒ不良が発生した。   From the evaluation results of four types of tests for each sample shown in Table 1, the following was found. That is, according to the electrochemical device of the present invention, good results were obtained in all of the evaluations of insulation resistance, DC-R, capacity, and self-discharge. In particular, the average DC-R value of Example 1 was about 15% lower than that of Comparative Example 1, and good results were obtained. This is considered to be because the external terminal plate and the plurality of extending portions have no through holes, and the current collecting property and contact resistance are superior to those of Comparative Example 1. In Example 1, since the voltage drop during discharge was improved by reducing the internal resistance, the amount of decrease in the capacity was relatively small, and a capacity equivalent to that in Comparative Example 1 was obtained. Regarding Comparative Examples 1 to 3, burrs of through holes formed by machining in a plurality of electrode plate portions (extension portions where active material electrode sheets are not formed) are poorly insulated between the electrode plates via the separator There has occurred. Moreover, the variation of DC-R was large, and a DC-R defect occurred.

集電体の貫通孔の開孔率は、それぞれの電極板の面積に対して０．１％以上３０％以下であると容量不良、ＤＣ−Ｒ不良、絶縁不良、自己放電不良が発生せず好適であることがわかった（実施例２〜８、比較例４、５）。開孔率が０．１％より小さい場合には、リチウム挿入用電極板から負極活物質電極シートへのリチウム挿入の際、リチウム挿入が不均一となる恐れがあり、負極活物質電極シート表面上へのリチウムデンドライドが発生し、セパレータを介して電極間の微細ショートによる自己放電不良が発生したと考えられる（比較例４）。開孔率が１０％よりも大きい場合には、容量が減少する傾向があることが確認された。さらに、比較例５に示す開口率が３０％よりも大きい場合には、正極電極板および負極電極板にレーザ加工を行う際に、加工不良が発生した。加工箇所距離が非常に短くなるためであると考えられる。加工順序等を検討すれば改善が見込まれるが、製造の容易さを考慮すると開口率は３０％以下が望ましい。   When the aperture ratio of the through holes of the current collector is 0.1% or more and 30% or less with respect to the area of each electrode plate, capacity defect, DC-R defect, insulation defect, and self-discharge defect do not occur. It turned out that it is suitable (Examples 2-8, Comparative Examples 4 and 5). When the open area ratio is less than 0.1%, there is a possibility that the lithium insertion may be non-uniform when the lithium is inserted from the lithium insertion electrode plate into the negative electrode active material electrode sheet. It is considered that lithium dendriide was generated and a self-discharge failure was caused by a fine short between the electrodes via the separator (Comparative Example 4). It was confirmed that the capacity tends to decrease when the open area ratio is larger than 10%. Furthermore, when the aperture ratio shown in Comparative Example 5 was greater than 30%, processing defects occurred when laser processing was performed on the positive electrode plate and the negative electrode plate. This is thought to be because the distance between the machining points becomes very short. Although improvement is expected if the processing order is examined, the aperture ratio is preferably 30% or less in consideration of ease of manufacture.

また、集電体の貫通孔の開孔径は、０．０１ｍｍ以上５ｍｍ以下であると容量不良、ＤＣ−Ｒ不良、絶縁不良、自己放電不良が発生せず好適であることがわかった（実施例１、実施例９〜１５、比較例６、７）。開孔径が０．０１ｍｍより小さい場合には、レーザ加工による貫通孔形成の工程において、レーザマーカ装置の印字加工分解能よりも小さくなるため制御が難しく電極への加工時の不良が発生した（比較例６）。したがって、印字加工分解能が上がれば、開孔径が０．０１ｍｍより小さい場合であっても好適である可能性がある。一方、開孔径が５ｍｍよりも大きい場合、一定の開孔率としたときの貫通孔の円心間距離が大きくなるため、リチウム挿入用電極板から負極活物質電極シートへのリチウム挿入の際、リチウム挿入が不均一となる恐れがあり、負極活物質電極シート表面上へのリチウムデンドライド形成によりセパレータを介して電極間の微細ショートによる自己放電不良が発生することが考えられる。開孔径が５ｍｍ以上の場合でも、開孔率を上げれば円心間距離を短くすることが可能ではあるが、集電性が悪くなることもと考えられるため、開孔径は５ｍｍ以下が好ましい（比較例７）。   In addition, it was found that the opening diameter of the through hole of the current collector is preferably 0.01 mm or more and 5 mm or less because no capacity failure, DC-R failure, insulation failure, or self-discharge failure occurs (Example) 1, Examples 9 to 15 and Comparative Examples 6 and 7). When the hole diameter is smaller than 0.01 mm, in the process of forming a through hole by laser processing, the printing processing resolution of the laser marker device is smaller than that of the laser marker device, so that it is difficult to control and a defect occurs when processing the electrode (Comparative Example 6). ). Therefore, if the printing processing resolution is improved, it may be suitable even if the aperture diameter is smaller than 0.01 mm. On the other hand, when the opening diameter is larger than 5 mm, the distance between the centers of the through holes when the opening ratio is constant increases, so when inserting lithium from the lithium insertion electrode plate to the negative electrode active material electrode sheet, Lithium insertion may be non-uniform, and formation of lithium dendride on the surface of the negative electrode active material electrode sheet may cause a self-discharge failure due to a fine short between the electrodes via the separator. Even when the hole diameter is 5 mm or more, it is possible to shorten the distance between the circle centers if the hole area ratio is increased, but it is considered that the current collecting property is deteriorated, and therefore the hole diameter is preferably 5 mm or less ( Comparative Example 7).

なお、電極板に形成する貫通孔の加工方法としては、金型を用いたプレス加工、ロールパンチングによる加工においても良好な結果が得られた（実施例１６、１７）。金型を用いたプレス加工、ロールパンチングによる加工は、今回結果は掲載していないが開孔径０．５ｍｍ以下となる加工は困難であり、小さな開孔径とする場合はレーザ加工が好適であると考える。このように開孔径、開孔率に合わせ適切な加工方法を選択することが望ましい。   In addition, as a processing method of the through-hole formed in the electrode plate, good results were obtained even in press processing using a mold and processing by roll punching (Examples 16 and 17). The press processing using a die and the processing by roll punching are not shown here, but it is difficult to process the hole diameter to be 0.5 mm or less, and laser processing is suitable for a small hole diameter. Think. As described above, it is desirable to select an appropriate processing method in accordance with the hole diameter and the hole area ratio.

また、集電体にレーザ加工で貫通孔を形成し、その後凹版印刷で活物質電極シートを形成した試料においても良好な結果が得られた（実施例１８）。   In addition, good results were also obtained in a sample in which through holes were formed in the current collector by laser processing and then an active material electrode sheet was formed by intaglio printing (Example 18).

さらに、電気化学デバイスであれば、ハイブリッドキャパシタの他にリチウムイオン二次電池にも本発明を適用することが可能であり、ハイブリッドキャパシタと同様に容量不良、ＤＣ−Ｒ不良、絶縁不良、自己放電不良が発生せず好適であることを確認した（実施例１、１９）。   Furthermore, in the case of an electrochemical device, the present invention can be applied to a lithium ion secondary battery in addition to a hybrid capacitor. As in the case of a hybrid capacitor, capacity failure, DC-R failure, insulation failure, self-discharge It was confirmed that no defects occurred and it was preferable (Examples 1 and 19).

これより、製造コストを低減し、自己放電不良がなく、且つ内部抵抗が低く、高容量である電気化学デバイスおよびその製造方法を提供ができることが確認できた。   From this, it was confirmed that the manufacturing cost can be reduced, an electrochemical device having no self-discharge failure, low internal resistance, and high capacity and a manufacturing method thereof can be provided.

上記の各実施例の説明は、本発明の実施の形態に係る場合の効果について説明するためのものであって、これによって特許請求の範囲に記載の発明を限定し、あるいは請求の範囲を減縮するものではない。また、本発明の各部構成は上記の実施の形態に限らず、特許請求の範囲に記載の技術的範囲内で種々の変形が可能である。   The description of each example described above is for explaining the effects in the case of the embodiment of the present invention, thereby limiting the invention described in the scope of claims or reducing the scope of claims. Not what you want. Moreover, each part structure of this invention is not restricted to said embodiment, A various deformation | transformation is possible within the technical scope as described in a claim.

１ ハイブリッドキャパシタ
２ 正極外部端子板
３ 負極外部端子板
４ 外装フィルムシート
５ 電気化学素子
６ 正極電極板延出部
７ 負極電極板延出部
８ 正極活物質電極シート
９ 負極活物質電極シート
１０ セパレータ
１１ 貫通孔
１２ リチウム挿入用電極板
１３ 金属リチウム
１４ リチウム挿入用外部端子
１５、２５、３５ 電極板延出部
１６、２６、３６ 活物質電極シート
１７ 活物質電極シートに形成された貫通孔
１８ 集電体に形成された貫通孔 DESCRIPTION OF SYMBOLS 1 Hybrid capacitor 2 Positive electrode external terminal board 3 Negative electrode external terminal board 4 Exterior film sheet 5 Electrochemical element 6 Positive electrode plate extension part 7 Negative electrode plate extension part 8 Positive electrode active material electrode sheet 9 Negative electrode active material electrode sheet 10 Separator 11 Through-hole 12 Lithium insertion electrode plate 13 Metallic lithium 14 Lithium insertion external terminals 15, 25, 35 Electrode plate extension parts 16, 26, 36 Active material electrode sheet 17 Through-hole 18 formed in the active material electrode sheet Current collection Through holes formed in the body

Claims (9)

金属箔からなる集電体の少なくとも一方の主面に活物質を配した活物質電極シートが形成された正極電極板および負極電極板と、前記正極電極板と前記負極電極板の間に積層されたセパレータを有する電気化学素子と、前記正極電極板および前記負極電極板にそれぞれ電気的に接続された正極外部端子板および負極外部端子板と、前記電気化学素子を内蔵し、電解液を充填し、密閉する外装フィルムシートを備える電気化学デバイスであって、前記正極電極板および前記負極電極板の少なくとも一方には、前記集電体および活物質電極シートを貫通する複数の貫通孔を有し、前記活物質電極シートの貫通孔の開孔径が前記集電体の貫通孔の開孔径よりも小さいことを特徴とする電気化学デバイス。   A positive electrode plate and a negative electrode plate on which an active material electrode sheet having an active material disposed on at least one main surface of a current collector made of metal foil is formed, and a separator laminated between the positive electrode plate and the negative electrode plate A positive electrode terminal plate and a negative electrode external terminal plate electrically connected to the positive electrode plate and the negative electrode plate, respectively, and the electrochemical device, filled with an electrolyte, and sealed In the electrochemical device including the exterior film sheet, at least one of the positive electrode plate and the negative electrode plate has a plurality of through holes penetrating the current collector and the active material electrode sheet, An electrochemical device, wherein an opening diameter of a through hole of a material electrode sheet is smaller than an opening diameter of a through hole of the current collector. 前記集電体の貫通孔の内壁は、前記活物質で覆われていることを特徴とする請求項１に記載の電気化学デバイス。   The electrochemical device according to claim 1, wherein an inner wall of the through hole of the current collector is covered with the active material. 前記集電体の貫通孔の開孔径は、０．０１ｍｍ以上５ｍｍ以下であることを特徴とする請求項１または請求項２に記載の電気化学デバイス。   The electrochemical device according to claim 1 or 2, wherein an opening diameter of the through hole of the current collector is 0.01 mm or more and 5 mm or less. 前記集電体の貫通孔の開孔率は、前記集電体の面積に対して０．１％以上３０％以下であることを特徴とする請求項１乃至請求項３のいずれか一項に記載の電気化学デバイス。   The aperture ratio of the through holes of the current collector is 0.1% or more and 30% or less with respect to the area of the current collector, according to any one of claims 1 to 3. The described electrochemical device. 金属箔からなる集電体の少なくとも一方の主面に、活物質を配した活物質電極シートを形成した正極電極板および負極電極板と、前記正極電極板および前記負極電極板の間に積層するセパレータとを有する電気化学素子と、前記正極電極板および前記負極電極板にそれぞれ電気的に接続される正極外部端子板および負極外部端子板と、前記電気化学素子を内蔵し、電解液を充填し、密閉する外装フィルムシートを備える電気化学デバイスの製造方法であって、前記正極電極板および負極電極板の少なくとも一方には、前記集電体および活物質電極シートを貫通する複数の貫通孔を形成し、前記貫通孔を形成後に、前記活物質電極シートの貫通孔の開孔径が前記集電体の貫通孔の開孔径よりも小さくなるように加工することを特徴とする電気化学デバイスの製造方法。   A positive electrode plate and a negative electrode plate on which an active material electrode sheet having an active material disposed is formed on at least one main surface of a current collector made of metal foil; and a separator laminated between the positive electrode plate and the negative electrode plate; A positive electrode terminal plate and a negative electrode external terminal plate electrically connected to the positive electrode plate and the negative electrode plate, respectively, and the electrochemical device, filled with an electrolyte, and sealed A method for producing an electrochemical device comprising an exterior film sheet to be formed, wherein at least one of the positive electrode plate and the negative electrode plate is formed with a plurality of through holes penetrating the current collector and the active material electrode sheet, After forming the through hole, the electrification is characterized in that the opening diameter of the through hole of the active material electrode sheet is processed to be smaller than the opening diameter of the through hole of the current collector. A device manufacturing method. 前記集電体の貫通孔の内壁を、前記活物質で覆うことを特徴とする請求項５に記載の電気化学デバイスの製造方法。   The method for producing an electrochemical device according to claim 5, wherein an inner wall of the through hole of the current collector is covered with the active material. 前記集電体の貫通孔の開孔径を、０．０１ｍｍ以上５ｍｍ以下とすることを特徴とする請求項５または請求項６に記載の電気化学デバイスの製造方法。   The method for producing an electrochemical device according to claim 5 or 6, wherein an opening diameter of the through hole of the current collector is 0.01 mm or more and 5 mm or less. 前記集電体の貫通孔の開孔率を、前記集電体の面積に対して０．１％以上３０％以下とすることを特徴とする請求項５乃至請求項７のいずれか一項に記載の電気化学デバイスの製造方法。 The opening ratio of the through holes of the current collector is 0.1% or more and 30% or less with respect to the area of the current collector, according to any one of claims 5 to 7. The manufacturing method of the electrochemical device of description. 前記電気化学デバイスが、リチウムイオン二次電池またはハイブリッドキャパシタであることを特徴とする請求項１乃至請求項４のいずれか一項に記載の電気化学デバイス。   The electrochemical device according to any one of claims 1 to 4, wherein the electrochemical device is a lithium ion secondary battery or a hybrid capacitor.
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FR3004290A1 (en) * 2013-04-08 2014-10-10 Accumulateurs Fixes CURRENT COLLECTOR FOR ELECTROCHEMICAL ELEMENT ELECTRODE
JP2015138614A (en) * 2014-01-21 2015-07-30 日産自動車株式会社 Method for manufacturing battery electrode, battery electrode, and secondary battery
JP2017017085A (en) * 2015-06-29 2017-01-19 株式会社フジクラ Ultrasonic-welding method of electrode unit
WO2017094526A1 (en) * 2015-11-30 2017-06-08 日立マクセル株式会社 Electrode for electrochemical elements and lithium ion secondary battery
CN107818874A (en) * 2017-11-28 2018-03-20 广州驰裕网络科技有限公司 A kind of ultracapacitor and preparation method thereof
WO2018211916A1 (en) * 2017-05-18 2018-11-22 富士フイルム株式会社 Perforated metal foil, perforated metal foil manufacturing method, secondary battery negative electrode, and secondary battery positive electrode
KR20190048123A (en) * 2017-10-30 2019-05-09 한국전기연구원 Porous electrodes for energy storage devices
WO2020004453A1 (en) * 2018-06-29 2020-01-02 株式会社ワイヤード Negative electrode for lithium ion battery, lithium ion battery using said negative electrode, and method for producing lithium ion battery
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Cited By (12)

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Publication number Priority date Publication date Assignee Title
FR3004290A1 (en) * 2013-04-08 2014-10-10 Accumulateurs Fixes CURRENT COLLECTOR FOR ELECTROCHEMICAL ELEMENT ELECTRODE
JP2015138614A (en) * 2014-01-21 2015-07-30 日産自動車株式会社 Method for manufacturing battery electrode, battery electrode, and secondary battery
JP2017017085A (en) * 2015-06-29 2017-01-19 株式会社フジクラ Ultrasonic-welding method of electrode unit
WO2017094526A1 (en) * 2015-11-30 2017-06-08 日立マクセル株式会社 Electrode for electrochemical elements and lithium ion secondary battery
WO2018211916A1 (en) * 2017-05-18 2018-11-22 富士フイルム株式会社 Perforated metal foil, perforated metal foil manufacturing method, secondary battery negative electrode, and secondary battery positive electrode
CN110637385A (en) * 2017-05-18 2019-12-31 富士胶片株式会社 Perforated metal foil, method for producing perforated metal foil, negative electrode for secondary battery, and positive electrode for secondary battery
JPWO2018211916A1 (en) * 2017-05-18 2020-03-12 富士フイルム株式会社 Perforated metal foil, method for producing perforated metal foil, negative electrode for secondary battery and positive electrode for secondary battery
KR20190048123A (en) * 2017-10-30 2019-05-09 한국전기연구원 Porous electrodes for energy storage devices
KR102348796B1 (en) * 2017-10-30 2022-01-06 한국전기연구원 Porous electrodes for energy storage devices
CN107818874A (en) * 2017-11-28 2018-03-20 广州驰裕网络科技有限公司 A kind of ultracapacitor and preparation method thereof
WO2020004453A1 (en) * 2018-06-29 2020-01-02 株式会社ワイヤード Negative electrode for lithium ion battery, lithium ion battery using said negative electrode, and method for producing lithium ion battery
WO2024057727A1 (en) * 2022-09-16 2024-03-21 株式会社Ｇｓユアサ Electricity storage element

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