JP2008077945A - Flat electrochemical cell - Google Patents

Flat electrochemical cell Download PDF

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JP2008077945A
JP2008077945A JP2006254940A JP2006254940A JP2008077945A JP 2008077945 A JP2008077945 A JP 2008077945A JP 2006254940 A JP2006254940 A JP 2006254940A JP 2006254940 A JP2006254940 A JP 2006254940A JP 2008077945 A JP2008077945 A JP 2008077945A
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gas
exterior body
outer package
electrochemical cell
valve
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JP5261908B2 (en
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Takanori Yamashita
孝典 山下
Masataka Okushita
正隆 奥下
Hirohisa Akita
裕久 秋田
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Dai Nippon Printing Co Ltd
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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

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a flat electrochemical cell which sufficiently secures airtightness and steam barrier performance inside an outer package using the outer package in which a laminate consisting of a composite film is made into a bag shape or a tray shape, and prevents blowing-out of the outer package due to increase of internal pressure by releasing the gas inside and also prevents leakage of electrolyte. <P>SOLUTION: A safety valve 6 for releasing gas generated inside the outer package is installed at a part of the peripheral portion of the outer package 10, and the safety valve 6 is constructed of a valve 9 which opens when the gas pressure inside the outer package exceeds a prescribed value, a housing part 8 which houses the gas and electrolyte which have passed the valve 9, and a gas permeation part 7 which permeates only the gas. The housing part 8 is made a non-sealed region installed at a part of the outer package peripheral portion and the gas permeation part 7 is made a porous fluororesin sheet which closes an outer package aperture formed on the non-sealed region. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、外装体内部で発生したガスを外部へ逃す安全弁を備えた扁平型電気化学セルに関する。   The present invention relates to a flat electrochemical cell provided with a safety valve that allows gas generated inside an exterior body to escape to the outside.

扁平型電気化学セルとは、リチウムイオン電池、コンデンサー、キャパシタ等の、電極及び電解質を備える蓄電部を外装体内部に密封収納して構成されるものである。例えば、リチウムイオン電池は、リチウム二次電池ともいわれ、液状、ゲル状又は高分子ポリマー状の電解質を持ち、正極・負極活物質が高分子ポリマーからなるものを含むものである。このリチウムイオン電池は、充電時には正極活物質であるリチウム遷移金属酸化物中のリチウム原子（Ｌｉ）がリチウムイオン（Ｌｉ+）となって負極の炭素層間に入り込み（インターカレーション）、放電時にはリチウムイオン（Ｌｉ+）が炭素層間から離脱（デインターカレーション）して正極に移動し、元のリチウム化合物となることにより充放電反応が進行する電池である。 The flat electrochemical cell is configured by sealing and storing a power storage unit including an electrode and an electrolyte, such as a lithium ion battery, a capacitor, and a capacitor. For example, a lithium ion battery is also referred to as a lithium secondary battery, and includes a liquid, gel-like, or polymer polymer electrolyte, and a positive electrode / negative electrode active material made of a polymer polymer. In this lithium ion battery, the lithium atom (Li) in the lithium transition metal oxide, which is the positive electrode active material, is charged as lithium ion (Li + ) during charging and enters the carbon layer of the negative electrode (intercalation). This is a battery in which charge / discharge reaction proceeds when ions (Li + ) are desorbed (deintercalated) from the carbon layer and moved to the positive electrode to become the original lithium compound.

また、リチウムイオン電池の構成は、正極集電材／正極活性物質層／電解質層／負極活性物質層／負極集電材及び、これらを包装する外装体からなり、外装体として従来、金属をプレス加工し円筒状または直方体状等に容器化した金属製缶が用いられていた。   The lithium ion battery is composed of a positive electrode current collector / positive electrode active material layer / electrolyte layer / negative electrode active material layer / negative electrode current collector and an outer package that wraps them. Metallic cans that have been formed into a cylindrical shape or a rectangular parallelepiped shape have been used.

しかし、金属製缶は、容器外壁がリジッドであるため、電池自体の形状が限定されてしまい、ハード側を電池に合わせて設計する必要から形状の自由度がないため、近年、金属製缶に替わって多層フィルムが外装体として用いられる傾向にある。この外装体は、少なくとも基材層、金属箔、熱接着性樹脂層で構成され、袋状に形成し電池本体を収納するパウチタイプ、または、多層フィルムをプレス加工して凹部を形成し、該凹部に電池本体を収納するエンボスタイプに大別される。   However, since the outer wall of the container is rigid, the shape of the battery itself is limited, and there is no degree of freedom in shape because it is necessary to design the hardware side to match the battery. Instead, multilayer films tend to be used as exterior bodies. This exterior body is composed of at least a base material layer, a metal foil, and a heat-adhesive resin layer, and is formed into a bag shape to store a battery body, or a recess is formed by pressing a multilayer film, It is roughly divided into embossed types that house the battery body in the recess.

図４（ａ）は、パウチタイプのリチウムイオン電池１の斜視図であり、図４（ｂ）に示すように袋状に形成された外装体５にリチウムイオン電池本体２が密封収納される。また、図５（ａ）はエンボスタイプのリチウムイオン電池１の斜視図であり、図５（ｂ）に示すようにエンボス部が形成されたトレイ５ｔとシート５ｓとから成る外装体５を用いてリチウムイオン電池本体２が密封収納される。なお、４はリチウムイオン電池本体２の正極及び負極に接続される金属端子である。   FIG. 4A is a perspective view of the pouch-type lithium ion battery 1, and the lithium ion battery main body 2 is hermetically housed in an outer package 5 formed in a bag shape as shown in FIG. 4B. FIG. 5A is a perspective view of the embossed type lithium ion battery 1, and as shown in FIG. 5B, an exterior body 5 including a tray 5t on which an embossed portion is formed and a sheet 5s is used. The lithium ion battery body 2 is hermetically stored. Reference numeral 4 denotes a metal terminal connected to the positive electrode and the negative electrode of the lithium ion battery body 2.

ここで、いずれのタイプも外装体外部から外装体内部に水蒸気が浸入した場合、電解質と前記水蒸気との反応によりフッ化水素酸が生成し、デラミネーション（剥離）の発生を引き起こす。   Here, in any type, when water vapor enters the exterior body from outside the exterior body, hydrofluoric acid is generated by the reaction between the electrolyte and the water vapor, causing delamination.

一方、外装体内部では、リチウムイオン電池の充放電により電解質と電極の間でイオンの交換がおこなわれており、この過程で少量の水素や酸素等が発生する場合がある。特に急速な充放電や過充電をした場合、ガスが発生し易く、これらのガスは充放電を繰り返すことで、徐々に外装体内部に蓄積し、内圧が上昇し続けた場合、最終的に外装体がその力に抗しきれず破裂することがある。   On the other hand, in the exterior body, ions are exchanged between the electrolyte and the electrodes by charging and discharging the lithium ion battery, and a small amount of hydrogen, oxygen, or the like may be generated in this process. In particular, when rapid charge / discharge or overcharge occurs, gas is likely to be generated, and these gases accumulate gradually inside the exterior body by repeating charge / discharge, and if the internal pressure continues to rise, the exterior The body may not resist the force and may burst.

つまり、リチウムイオン電池を構成する外装体は外装体内部の気密性を保ちながら外部からの水蒸気を遮断する水蒸気バリア性と外装体内部で発生するガスを外装体外部へ放出する機能が要求される。   That is, the exterior body constituting the lithium ion battery is required to have a water vapor barrier property that blocks water vapor from the outside while maintaining the airtightness inside the exterior body and a function of releasing the gas generated inside the exterior body to the outside of the exterior body. .

これまで、この課題を解決するため種々の提案がなされており、例えば、外装材に切り込み部を設け、該切り込み部を金属箔で塞ぎ、ガス圧の上昇により外装体の破裂を防ぐもの（特許文献１参照）や、シール部の一部に剥離強度の低い箇所を設け、ガス圧の上昇により当該箇所が剥離しガスを放出するもの（特許文献２参照）等があった。   Various proposals have been made so far to solve this problem. For example, a cut portion is provided in an exterior material, the cut portion is closed with a metal foil, and an explosion of the exterior body is prevented by increasing the gas pressure (patent There are some which are provided with a part having a low peel strength in a part of the seal part, and the part is peeled off and gas is released due to an increase in gas pressure (see Patent Document 2).

しかし、これらの発明は、ガスを放出する機能を有するが、外装体内部の密封シール性については不十分であるため、外装体内部の気密性が低下し水蒸気が浸入したり、ガスの放出とともに電解質が漏洩し周辺機器を汚す可能性があった。
特開平１１−１０２６７３号広報 特開平１１−９７０７０号広報 However, these inventions have a function of releasing gas, but the sealing and sealing properties inside the exterior body are insufficient, so that the airtightness inside the exterior body decreases and water vapor enters or gas is released. There was a possibility that electrolyte leaked and contaminated peripheral equipment.
JP 11-102673 A JP 11-97070 A

そこで、本発明は上記問題点に鑑み、多層フィルムからなる外装体を用いて、外装体内部の気密性と外装体外部の水蒸気バリア性を十分確保し、内圧の上昇による外装体の破裂を防ぎ、電解質の漏洩防止機能を有するリチウムイオン電池等の扁平型電気化学セルを提供することを目的とする。   Therefore, in view of the above problems, the present invention uses a multilayer film exterior body to sufficiently secure the airtightness inside the exterior body and the water vapor barrier property outside the exterior body, and prevent the exterior body from bursting due to an increase in internal pressure. An object of the present invention is to provide a flat electrochemical cell such as a lithium ion battery having an electrolyte leakage prevention function.

上記目的を達成するために本発明の構成は、正極と負極と、前記正極及び負極間に充填される電解質とを含む蓄電部を、最内層にシール層を有する積層体からなる外装体に封入し前記外装体の周縁部を密封シールして成る扁平型電気化学セルにおいて、前記外装体周縁部に外装体内部で発生したガスを外装体外部に逃すための安全弁を設け、前記安全弁が外装体内部のガス圧が所定値を超えたとき開く弁部と、前記弁部を通過したガス及び電解質を収容する収容部と、前記収容部からガスのみを透過するガス透過部とからなり、前記収容部は前記外装体周縁部の一部に設けられた未シール領域であり、前記ガス透過部は前記未シール領域上に形成された外装体開口部を塞ぐ高分子シートであることを特徴とする扁平型電気化学セルである。   In order to achieve the above object, the configuration of the present invention encloses a power storage unit including a positive electrode, a negative electrode, and an electrolyte filled between the positive electrode and the negative electrode in an outer package made of a laminate having a seal layer as an innermost layer. In the flat electrochemical cell formed by hermetically sealing the peripheral portion of the exterior body, a safety valve is provided at the peripheral portion of the exterior body to release the gas generated inside the exterior body to the outside of the exterior body, and the safety valve is the exterior body The storage unit includes a valve unit that opens when an internal gas pressure exceeds a predetermined value, a storage unit that stores gas and electrolyte that have passed through the valve unit, and a gas transmission unit that transmits only gas from the storage unit. The portion is an unsealed region provided in a part of the outer peripheral portion of the exterior body, and the gas permeable portion is a polymer sheet that closes the exterior body opening formed on the unsealed region. It is a flat electrochemical cell.

本発明は上記構成の扁平型電気化学セルにおいて、前記高分子シートが多孔質フッ素系樹脂シートであることを特徴とする。   In the flat electrochemical cell having the above-described configuration, the present invention is characterized in that the polymer sheet is a porous fluororesin sheet.

本発明は上記構成の扁平型電気化学セルにおいて、前記多孔質フッ素系樹脂シートが延伸多孔質ポリテトラフルオロエチレンシートであることを特徴とする。   In the flat electrochemical cell having the above-described configuration, the present invention is characterized in that the porous fluororesin sheet is a stretched porous polytetrafluoroethylene sheet.

本発明は上記構成の扁平型電気化学セルにおいて、前記弁部が、シールされた前記外装体の周縁部より内側に突出した形状であることを特徴とする。   In the flat electrochemical cell having the above-described configuration, the valve portion has a shape protruding inward from the peripheral edge portion of the sealed outer package.

本発明は上記構成の扁平型電気化学セルにおいて、前記弁部が、前記シール層よりも接着強度の低いシール樹脂で構成されていることを特徴とする。   In the flat electrochemical cell having the above-mentioned structure, the present invention is characterized in that the valve portion is made of a seal resin having lower adhesive strength than the seal layer.

本発明は上記構成の扁平型電気化学セルにおいて、前記シール層がポリプロピレンで構成され、且つシール樹脂がポリプロピレンとポリエチレンを含むブレンド樹脂で構成されていること特徴とする。   In the flat electrochemical cell having the above-described configuration, the sealing layer is made of polypropylene, and the sealing resin is made of a blend resin containing polypropylene and polyethylene.

本発明は上記構成の扁平型電気化学セルにおいて、前記弁部が、前記外装体周縁部の一部に設けられた未シール領域を外装体外部からクリップ材で挟持して構成されることを特徴とする。   In the flat electrochemical cell having the above-described configuration, the valve portion is configured by sandwiching an unsealed region provided in a part of the outer peripheral portion of the outer casing with a clip material from the outer side of the outer casing. And

本発明の第１の構成によると、外装体の周縁部の一部に設けられた安全弁において、外装体内部のガス圧が所定値を超えた場合、弁部が開き、一旦、ガス及び電解質を収納部に導いた後、ガス透過部より、ガスのみを外装体外部へ放出する。   According to the first configuration of the present invention, in the safety valve provided at a part of the peripheral portion of the exterior body, when the gas pressure inside the exterior body exceeds a predetermined value, the valve portion opens, and once the gas and the electrolyte are supplied. After being guided to the storage part, only the gas is discharged from the gas transmission part to the outside of the exterior body.

また、外装体内部のガス圧が所定値を超えていない場合、水蒸気がガス透過部を透過して収容部まで浸入しても、弁部が閉じているため、収納部から外装体内部への水蒸気の侵入は遮断される。   In addition, when the gas pressure inside the exterior body does not exceed a predetermined value, even if water vapor permeates the gas permeation part and enters the accommodation part, the valve part is closed, so that the storage part can enter the exterior body. Intrusion of water vapor is blocked.

このように、外装体内部と外装体外部の間に収納部を設けることで、ガス圧が一定の間は、弁部により外装体内部の気密性が確保され外部からの水蒸気の浸入を防ぐことができる。また、ガス圧が上昇し弁部が開いた後は、一旦ガス及び電解質が収納部に流入した後、ガスが透過されるため、ガス圧の急激な上昇を抑え外装体の破裂を防ぐことができる。   In this way, by providing a storage portion between the exterior body exterior and the exterior body exterior, the gas tightness inside the exterior body is ensured by the valve portion while the gas pressure is constant, and the entry of water vapor from the outside is prevented. Can do. Also, after the gas pressure rises and the valve part opens, the gas and electrolyte once flow into the storage part, and then the gas is permeated. it can.

また、前記収容部は外装体周縁部に設けた未シール領域であることから、ヒートシール時に容易に形成することができ、前記ガス透過部も外装体開口部に高分子シートを貼り付けるだけで形成することができるため、製造コストを抑えることができる。   Moreover, since the said accommodating part is an unsealed area | region provided in the outer periphery part of the exterior body, it can be easily formed at the time of heat sealing, and the gas permeable part can be formed by simply attaching a polymer sheet to the exterior body opening. Since it can form, manufacturing cost can be held down.

本発明の第２の構成によると、ガス透過部を多孔質フッ素系樹脂シートで構成することでガスのみを透過させ電解質等の液体を透過させない機能を容易に付与することができる。   According to the 2nd structure of this invention, the function which does not permeate | transmit only gas, but permeate | transmits liquids, such as an electrolyte, can be easily provided by comprising a gas permeation | transmission part with a porous fluorine resin sheet.

本発明の第３の構成によると、ガス透過部を延伸多孔質構造を持つポリテトラフルオロエチレンシートで構成することにより、優れたガス透過性を発揮し、外装体内部で発生したガスを外装体外部へ放出するとともに、撥水性に優れるため、外装体外部から浸入しようとする液体及び外装体内部から外部へ漏れだす電解質を遮断することができる。また、延伸法により前記シートの孔径及び空孔率を調整することで本発明に係るガス透過部として最適な特性を選択することができる。   According to the third configuration of the present invention, the gas permeable portion is made of a polytetrafluoroethylene sheet having a stretched porous structure, thereby exhibiting excellent gas permeability, and the gas generated inside the exterior body In addition to being released to the outside and being excellent in water repellency, it is possible to block the liquid that tries to enter from the exterior of the exterior body and the electrolyte that leaks from the interior of the exterior body to the exterior. Further, by adjusting the hole diameter and the porosity of the sheet by a stretching method, it is possible to select optimum characteristics as the gas permeable portion according to the present invention.

また、ポリテトラフルオロエチレンは耐熱性、耐薬品性、強靭性にも優れるため、高温の電解質が付着した場合にも劣化することなくガス透過性を継続的に発揮することができる。   Moreover, since polytetrafluoroethylene is excellent also in heat resistance, chemical resistance, and toughness, even when a high-temperature electrolyte adheres, it can continuously exhibit gas permeability without deterioration.

本発明の第４の構成によると、弁部を、シールされた外装体の周縁部より内側に突出した形状にすることで、外装体内部でガスが発生し内圧が上昇したとき外装体が膨張し、外装体周縁部のシール層が剥れる前にまず内側に突出した箇所が剥離する。これにより、弁部からガスと共に電解質が収納部へ流入し、ガスのみガス透過部から外装体外部へ放出される。従って、外装体の内圧は低下し、外装体周縁部における弁部以外のシール層の剥れを防ぐことができる。   According to the fourth configuration of the present invention, the valve body has a shape protruding inward from the peripheral edge of the sealed exterior body, so that the exterior body expands when gas is generated inside the exterior body and the internal pressure rises. Then, before the seal layer on the outer periphery of the exterior body is peeled off, the portion protruding inward is peeled off first. Thereby, electrolyte flows into a storage part with gas from a valve part, and only gas is discharge | released from the gas permeation | transmission part to the exterior body exterior. Accordingly, the internal pressure of the exterior body is reduced, and peeling of the seal layer other than the valve portion at the periphery of the exterior body can be prevented.

本発明の第５の構成によると、弁部をシール層よりも接着強度の低いシール樹脂で構成することにより、外装体内部でガスが発生し、内圧が上昇したとき外装体周縁部のシール層が剥れる前にまず弁部を構成するシール樹脂が剥れる。これにより、弁部が開き、ガスと共に電解質が収納部へ流入し、ガスのみガス透過部から外装体外部へ放出される。従って、外装体の内圧は低下し、外装体周縁部における弁部以外のシール層の剥れを防ぐことができる。   According to the fifth configuration of the present invention, by forming the valve portion with a seal resin having lower adhesive strength than the seal layer, gas is generated inside the exterior body, and when the internal pressure rises, the seal layer on the periphery of the exterior body Before peeling off, the sealing resin constituting the valve part is peeled off first. Thereby, the valve part is opened, the electrolyte flows into the storage part together with the gas, and only the gas is discharged from the gas permeable part to the outside of the exterior body. Accordingly, the internal pressure of the exterior body is reduced, and peeling of the seal layer other than the valve portion at the periphery of the exterior body can be prevented.

本発明の第６の構成によると、外装体最内層に設けられたシール層をポリプロピレンで構成し、弁部を構成するシール樹脂をポリプロピレンとポリエチレンを含むブレンド樹脂で構成することにより、ヒートシールする場合シール層と弁部が同程度の融点を有するため、融着させ易い。また、ポリプロピレンとポリエチレンの配合を変えることにより、シール強度を調整することができる。これにより、弁部が開く内圧の所定値も調節が可能となる。   According to the sixth configuration of the present invention, the seal layer provided in the innermost layer of the exterior body is made of polypropylene, and the seal resin constituting the valve portion is made of a blend resin containing polypropylene and polyethylene, thereby heat-sealing. In this case, since the sealing layer and the valve portion have the same melting point, they are easily fused. Also, the seal strength can be adjusted by changing the blending of polypropylene and polyethylene. Thereby, the predetermined value of the internal pressure at which the valve portion opens can also be adjusted.

本発明の第７の構成によると、外装体外部からクリップ材で挟持するのみで簡易に弁部を形成することができる。   According to the 7th structure of this invention, a valve part can be easily formed only by clamping with a clip material from the exterior body exterior.

以下、本発明の実施形態について扁平型電気化学セルの一種であるリチウムイオン電池を用いて図面を参照しながら説明する。本発明では外装体内部に蓄積されたガスを放出する安全弁を設け外装体の破裂を未然に防止するとともに、外部からの水蒸気の浸入を有効に防ぎ、電解質の飛散を防止する扁平型電気化学セルを提供しようとするものである。また、扁平型電気化学セルは、その蓄電部を包装する外装体のタイプにより、パウチタイプと、エンボスタイプとがあり、本発明はいずれのタイプにも適用することができる。なお、図１〜図３ではエンボスタイプを例に挙げて説明しており、従来例の図４、図５と共通する部分には同一の符号を付して説明を省略する。   Hereinafter, embodiments of the present invention will be described with reference to the drawings using a lithium ion battery which is a kind of flat electrochemical cell. In the present invention, a flat electrochemical cell is provided which has a safety valve for releasing the gas accumulated in the exterior body to prevent the exterior body from being ruptured, effectively prevents the intrusion of water vapor from the outside, and prevents the scattering of the electrolyte. Is to provide. The flat electrochemical cell includes a pouch type and an embossed type depending on the type of the outer package that wraps the power storage unit, and the present invention can be applied to any type. 1 to 3, the embossed type is described as an example, and portions common to FIGS. 4 and 5 of the conventional example are denoted by the same reference numerals and description thereof is omitted.

図１（ａ）、（ｂ）、（ｃ）はそれぞれ本発明に係るリチウムイオン電池１の概略斜視図、概略断面図、概略正面図である。安全弁６は金属端子４が配置される辺と対向する辺に設けられており、安全弁６は弁部９、収納部８、ガス透過部７により構成されている。   1A, 1B, and 1C are a schematic perspective view, a schematic cross-sectional view, and a schematic front view, respectively, of a lithium ion battery 1 according to the present invention. The safety valve 6 is provided on a side opposite to the side where the metal terminal 4 is disposed, and the safety valve 6 includes a valve part 9, a storage part 8, and a gas permeation part 7.

外装体５内部と接するシール周縁部５ａに設けられた弁部９は、ガス内部の圧力が所定値に達するまで外装体内部を閉弁し気密性を確保している。このとき、ガス透過部７から収納部８に透過した水蒸気を遮断するために一定の水蒸気バリア性も有している。一方、内圧が所定値を超えたとき弁部９は開きガスの通気口を形成し、内圧の力で外装体内部のガスとともに電解質が収納部８側へ流入する。   The valve portion 9 provided on the seal peripheral portion 5a in contact with the inside of the exterior body 5 closes the interior of the exterior body until the pressure inside the gas reaches a predetermined value, thereby ensuring airtightness. At this time, it also has a certain water vapor barrier property in order to block the water vapor transmitted from the gas permeable part 7 to the storage part 8. On the other hand, when the internal pressure exceeds a predetermined value, the valve portion 9 opens and forms a gas vent, and the electrolyte flows into the storage portion 8 side together with the gas inside the exterior body due to the internal pressure.

ガス透過部７は、収納部８に流入した電解質を遮断し外部への漏洩を防ぐとともに、ガスを外装体外部へ放出する。したがって、ガス透過部７を構成する高分子シートは有機溶媒等の電解質が付着しても劣化しない耐薬品性、過充電等により高温に過熱されても熱劣化しない耐熱性、及び過度な折り曲げ時にも使用可能な強靭性等が必要とされるとともに、ガス透過性及び電解質を遮断する撥水性が必要となる。なお、この高分子シートについては後で詳しく説明する。   The gas permeation unit 7 blocks the electrolyte flowing into the storage unit 8 to prevent leakage to the outside, and discharges the gas to the outside of the exterior body. Therefore, the polymer sheet constituting the gas permeable portion 7 has chemical resistance that does not deteriorate even when an electrolyte such as an organic solvent adheres, heat resistance that does not deteriorate even when heated to a high temperature due to overcharging, and excessive bending. In addition, usable toughness and the like are required, as well as gas permeability and water repellency that blocks the electrolyte. The polymer sheet will be described in detail later.

図２は本発明に係るリチウムイオン電池１を分解して示す斜視図であり、本発明に係るリチウムイオン電池１に用いられる外装体は図５に示した従来例のエンボスタイプの外装体５とは異なり、外装体周縁部５ａの一辺に所定の領域を有するトレイ５ｔとそれに対応する大きさのシート５ｓを用いてリチウムイオン電池本体２を収納する。また、シート５ｓには開口部７ｂが設けられ、高分子シート７ａで塞ぐことでガス透過部７が形成される。このとき、高分子シート７ａ自身が粘着性を有する必要はなく中央部付近が開口する粘着シート７ｃにより高分子シート７ａを上方から被覆することで高分子シート７ａの機能を低下させることなく開口部７ｂを塞ぐことができる。なお、高分子シート７ａはシート５ｓの上面から貼り付ける場合に限らずシート５ｓの下面から貼り付けてもよい。   FIG. 2 is an exploded perspective view of the lithium ion battery 1 according to the present invention. The exterior body used in the lithium ion battery 1 according to the present invention is the embossed exterior body 5 of the conventional example shown in FIG. In contrast, the lithium ion battery main body 2 is accommodated using a tray 5t having a predetermined area on one side of the outer periphery 5a and a sheet 5s having a size corresponding to the tray 5t. Moreover, the opening part 7b is provided in the sheet | seat 5s, and the gas permeation | transmission part 7 is formed by plugging with the polymer sheet 7a. At this time, the polymer sheet 7a itself does not need to have adhesiveness, and the opening portion without covering the function of the polymer sheet 7a can be obtained by covering the polymer sheet 7a from above with the adhesive sheet 7c having an opening near the center. 7b can be blocked. The polymer sheet 7a is not limited to being attached from the upper surface of the sheet 5s, and may be attached from the lower surface of the sheet 5s.

収納部８は、外装体周縁部５ａをヒートシールする際、未シール領域を設けることで形成される。ここで、収納部８はリチウムイオン電池１全体の大きさを考慮する必要はあるが、弁部９からガス透過部７への通路として設けるのではなく、弁部９から流入するガス及び電解質を一旦収納するため、できるだけ大きく設けることが望ましい。つまり、収納部８が一定の容量を有する場合、外装体内部のガス圧が急激に上昇したときでも、収納部８を経由することである程度ガス圧の上昇を緩め外装体の破裂を防ぐことができる。   The storage portion 8 is formed by providing an unsealed region when the outer peripheral edge portion 5a is heat sealed. Here, although it is necessary to consider the size of the lithium ion battery 1 as a whole, the storage unit 8 is not provided as a passage from the valve unit 9 to the gas permeation unit 7, but the gas and electrolyte flowing from the valve unit 9 are provided. In order to store it once, it is desirable to provide it as large as possible. That is, when the storage unit 8 has a certain capacity, even when the gas pressure inside the exterior body suddenly increases, the increase in gas pressure is moderated to some extent by the storage unit 8 to prevent the exterior body from bursting. it can.

弁部９は、外装体５に上下に挟持された状態でシールされており、内圧が所定値に達するまでは、外装体内部は高い機密性を保ち、外部からの水蒸気の浸入に対しても高いバリア性を有する。   The valve portion 9 is sealed in a state of being sandwiched by the exterior body 5 up and down, and the interior of the exterior body keeps high confidentiality until the internal pressure reaches a predetermined value, and also against the intrusion of water vapor from the outside. High barrier properties.

弁部９を構成する基材としてポリプロピレン（以下ＰＰと略す）とポリエチレン（以下ＰＥと略す）のブレンド樹脂が好適に用いられる。ＰＰはＰＥをブレンドすることにより純粋なＰＰと比較してシール強度を下げることができる。したがって、外装体のヒートシール層にＰＰ層を用い、弁部９を設けたい箇所に上記ブレンド樹脂を用いることで、外装体の内圧が上昇し外装体上面と外装体下面を引き剥がす圧力がかかったとき、このブレンド樹脂のシール部分を優先的に剥離させることができる。   A blend resin of polypropylene (hereinafter abbreviated as PP) and polyethylene (hereinafter abbreviated as PE) is preferably used as the base material constituting the valve portion 9. PP can lower the seal strength compared to pure PP by blending PE. Therefore, by using a PP layer for the heat seal layer of the exterior body and using the blended resin at a location where the valve portion 9 is to be provided, the internal pressure of the exterior body rises and pressure is applied to peel off the exterior body upper surface and the exterior body lower surface. When this occurs, the seal portion of this blend resin can be peeled off preferentially.

これにより、他の外装体周縁部５ａが剥離する前に弁部９からガスを収納部８へ流入し、ガス透過部７からガスを外部へ放出することができる。   Thereby, before other exterior body peripheral part 5a peels, gas can flow in into the accommodating part 8 from the valve part 9, and gas can be discharge | released outside from the gas permeation | transmission part 7. FIG.

しかし、弁部９と外装体５のシール強度が低過ぎる場合、外装体５内部の気密性が確保されず外部からの蒸気の浸入を招き易い。また、弁部９のシール強度が高過ぎる場合、外装体内部の圧力が相当高くなった状態で弁部９が凝集破壊され、その衝撃でガス透過部７を破壊する可能性がある。したがって弁部９には、ＰＰとＰＥの構成比率を調整し好適な強度のブレンド樹脂を用いる必要がある。また、弁部９は内圧が上昇したときに外装体周縁部５ａのシール部より先に剥離させるため図１（ｃ）に示すようにシールされた外装体周縁部５ａよりも先端を外装体内側に突出した形状とすることが好ましい。   However, when the sealing strength between the valve portion 9 and the outer casing 5 is too low, the airtightness inside the outer casing 5 is not ensured, and the invasion of vapor from the outside tends to occur. Moreover, when the sealing strength of the valve part 9 is too high, the valve part 9 may be aggregated and destroyed in a state where the pressure inside the exterior body becomes considerably high, and the gas permeable part 7 may be destroyed by the impact. Therefore, it is necessary to use a blend resin having a suitable strength by adjusting the constituent ratio of PP and PE for the valve portion 9. Further, since the valve portion 9 is peeled off before the seal portion of the outer periphery portion 5a when the internal pressure is increased, the tip of the valve portion 9 is more inside than the sealed outer periphery portion 5a as shown in FIG. It is preferable to have a shape protruding in

また、弁部９は上記以外にもクリップ材９ａを用いて外装体外部から挟持して形成する方法もある。図３（ａ）、（ｂ）、（ｃ）はクリップ材９ａを用いて弁部９を形成した場合におけるリチウムイオン電池１の概略断面図又は概略正面図である。外装体周縁部５ａの一部に未シール領域を設けクリップ材９ａで上下から挟持し押圧することで弁部は閉じた状態となり、外装体内部の電解質及びガスが収納部８へ流入しない。これにより外装体内部の気密性を一定に保つことができる。また、外装体内部のガスにより外装体が膨張しクリップ材９ａが外れたとき弁部９は開放され、電解質及びガスが収納部８へ流入する。このように、クリップ材９ａの押圧を調整することで内圧の上昇に対する弁部の開閉をある程度調整することができる。   In addition to the above, the valve portion 9 may be formed by being clamped from outside the exterior body using the clip material 9a. FIGS. 3A, 3B, and 3C are schematic sectional views or schematic front views of the lithium ion battery 1 when the valve portion 9 is formed using the clip material 9a. An unsealed region is provided in a part of the outer periphery 5a of the exterior body, and the valve portion is closed by pressing and holding the clip material 9a from above and below, so that the electrolyte and gas inside the exterior body do not flow into the storage portion 8. Thereby, the airtightness inside an exterior body can be kept constant. Further, when the exterior body expands due to the gas inside the exterior body and the clip material 9 a is detached, the valve portion 9 is opened, and the electrolyte and gas flow into the storage portion 8. Thus, the opening and closing of the valve portion with respect to the increase in internal pressure can be adjusted to some extent by adjusting the pressing of the clip material 9a.

また、クリップ材９ａと外装体外部が当接する箇所に樹脂部を設け緩衝材とすることにより、外装体内部の密封性をより安定させることができるとともに、図３（ｃ）に示すようにクリップ材９ａと当接する部分近傍を折り曲げることにより外装体内部の密封性を高めることもできる。   In addition, by providing a resin portion at a location where the clip material 9a and the exterior of the exterior body come into contact with each other to provide a cushioning material, the sealing performance inside the exterior body can be further stabilized, and the clip as shown in FIG. It is also possible to improve the sealing performance inside the exterior body by bending the vicinity of the portion in contact with the material 9a.

なお、上記ブレンド樹脂を用いた弁部や外装体内側に突出した形状からなる弁部とクリップ材９ａを組み合わせて構成することも可能である。   In addition, it is also possible to comprise combining the valve part using the said blend resin, the valve part which consists of the shape protruded inside the exterior body, and the clip material 9a.

次にガス透過部７を構成する高分子シート７ａについて説明する。高分子シート７ａは延伸多孔質構造を有するポリテトラフルオロエチレン（以下ＰＴＦＥと略す）で構成されている。ＰＴＦＥ自体は炭素とフッ素のみで構成され、フッ素原子と炭素原子間の結合力が極めて強く、分極率及び分子間力が小さいため、一般のプラスチックに比べて、耐熱性、耐薬品性、強靭性に極めて優れている。   Next, the polymer sheet 7a constituting the gas permeable part 7 will be described. The polymer sheet 7a is made of polytetrafluoroethylene (hereinafter abbreviated as PTFE) having a stretched porous structure. PTFE itself is composed of only carbon and fluorine, and has a very strong bonding force between fluorine atoms and carbon atoms, and a low polarizability and intermolecular force. Therefore, compared to ordinary plastics, heat resistance, chemical resistance, and toughness It is extremely excellent.

これにより、過充電等により外装体内部のガス圧が上昇するとともに、電解質が高温化した場合でも、ガス透過部７における樹脂シートは熱劣化することがなく、電解質等の有機溶媒に対しても安定性を有する。   As a result, the gas pressure inside the exterior body increases due to overcharge and the like, and even when the electrolyte is heated to a high temperature, the resin sheet in the gas permeable portion 7 does not thermally deteriorate, and the organic sheet such as the electrolyte does not deteriorate. Has stability.

また、ＰＴＦＥは多孔質構造を有しているため、ガスのみを透過させ、電解質等の液体を遮断することができる。このとき、ＰＴＦＥは延伸法により空孔率及び孔径の制御を自在に行なうことができるため、この空孔率及び孔径を制御することで、本発明に係るガス透過部に用いる高分子シート７ａとして最適な特性を選択することできる。   Moreover, since PTFE has a porous structure, only gas can permeate | transmit and liquids, such as an electrolyte, can be interrupted | blocked. At this time, since PTFE can freely control the porosity and the hole diameter by the stretching method, the polymer sheet 7a used for the gas permeable portion according to the present invention can be controlled by controlling the porosity and the hole diameter. Optimal characteristics can be selected.

なお、多孔質膜の空孔率が上昇すると撥水性が低下し、ガス透過性が上昇する。また、孔径は、小さいほど撥水率が上昇し、ガス透過が低下する。   Note that when the porosity of the porous film increases, the water repellency decreases and the gas permeability increases. Further, the smaller the hole diameter, the higher the water repellency and the lower the gas permeation.

また、本発明は上述した各実施形態に限定されるものではなく、種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。   The present invention is not limited to the above-described embodiments, and various modifications are possible. Embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the present invention. Included in the technical scope.

本発明は、エネルギー貯蔵用や電気自動車用の電源として好適な、耐久性、安全性の高いリチウムイオン電池に利用することができる。   INDUSTRIAL APPLICABILITY The present invention can be used for a durable and safe lithium ion battery suitable as a power source for energy storage and electric vehicles.

は、本発明に係るリチウムイオン電池の概略斜視図、概略断面図、概略平面図である。These are the schematic perspective view, schematic sectional drawing, and schematic plan view of the lithium ion battery which concern on this invention. は、本発明に係るリチウムイオン電池を分解した概略斜視図である。FIG. 2 is an exploded perspective view schematically illustrating a lithium ion battery according to the present invention. は、本発明に係るリチウムイオン電池の概略断面図、概略平面図である。These are the schematic sectional drawing of the lithium ion battery which concerns on this invention, and a schematic plan view. は、従来のリチウムイオン電池（パウチタイプ）の斜視図及び分解斜視図である。These are the perspective view and exploded perspective view of the conventional lithium ion battery (pouch type). は、従来のリチウムイオン電池（エンボスタイプタイプ）の斜視図及び分解斜視図である。These are a perspective view and an exploded perspective view of a conventional lithium ion battery (embossed type).

符号の説明Explanation of symbols

１ リチウムイオン電池
２ リチウムイオン電池本体
４ 金属端子
５ 外装体
５ａ 外装体周縁部
５ｔ トレイ
５ｓ シート
６ 安全弁
７ ガス透過部
７ａ 高分子シート
７ｂ 開口部
７ｃ 粘着シート
８ 収納部
９ 弁部
９ａ クリップ材 DESCRIPTION OF SYMBOLS 1 Lithium ion battery 2 Lithium ion battery main body 4 Metal terminal 5 Exterior body 5a Outer body peripheral part 5t Tray 5s Sheet 6 Safety valve 7 Gas permeation part 7a Polymer sheet 7b Opening part 7c Adhesive sheet 8 Storage part 9 Valve part 9a Clip material

Claims (7)

正極と負極と、前記正極及び負極間に充填される電解質とを含む蓄電部を、最内層にシール層を有する積層体からなる外装体に封入し前記外装体の周縁部を密封シールしてなる扁平型電気化学セルにおいて、
前記外装体周縁部に外装体内部で発生したガスを外装体外部に逃すための安全弁を設け、
前記安全弁が
外装体内部のガス圧が所定値を超えたとき開く弁部と、
前記弁部を通過したガス及び電解質を収容する収容部と、
前記収容部からガスのみを透過するガス透過部とからなり、
前記収容部は前記外装体周縁部の一部に設けられた未シール領域であり、
前記ガス透過部は前記未シール領域上に形成された外装体開口部を塞ぐ高分子シートであることを特徴とする扁平型電気化学セル。 A power storage unit including a positive electrode, a negative electrode, and an electrolyte filled between the positive electrode and the negative electrode is sealed in an outer package made of a laminate having a seal layer as an innermost layer, and a peripheral portion of the outer package is hermetically sealed. In flat electrochemical cells,
Provided a safety valve for letting out the gas generated inside the exterior body outside the exterior body periphery,
A valve portion that opens when the gas pressure inside the exterior body exceeds a predetermined value,
An accommodating portion for accommodating the gas and electrolyte that have passed through the valve portion;
A gas permeation part that allows only gas to permeate from the housing part,
The accommodating portion is an unsealed region provided in a part of the outer periphery of the exterior body,
The flat electrochemical cell according to claim 1, wherein the gas permeable part is a polymer sheet that closes an opening of the outer package formed on the unsealed region. 前記高分子シートが多孔質フッ素系樹脂シートであることを特徴とする請求項１に記載の扁平型電気化学セル。   The flat electrochemical cell according to claim 1, wherein the polymer sheet is a porous fluororesin sheet. 前記多孔質フッ素系樹脂シートが延伸多孔質ポリテトラフルオロエチレンシートであることを特徴とする請求項２に記載の扁平型電気化学セル。   The flat electrochemical cell according to claim 2, wherein the porous fluororesin sheet is a stretched porous polytetrafluoroethylene sheet. 前記弁部が、シールされた前記外装体の周縁部より内側に突出した形状であることを特徴とする請求項１及至請求項３のいずれか１に記載の扁平型電気化学セル。   The flat electrochemical cell according to any one of claims 1 to 3, wherein the valve portion has a shape protruding inward from a peripheral edge portion of the sealed exterior body. 前記弁部が、前記シール層よりも接着強度の低いシール樹脂で構成されていることを特徴とする請求項１及至請求項４のいずれか１に記載の扁平型電気化学セル。   The flat electrochemical cell according to any one of claims 1 to 4, wherein the valve portion is made of a seal resin having lower adhesive strength than the seal layer. 前記シール層がポリプロピレンで構成され、且つ前記シール樹脂がポリプロピレンとポリエチレンを含むブレンド樹脂で構成されていること特徴とする請求項５に記載の扁平型電気化学セル。   6. The flat electrochemical cell according to claim 5, wherein the seal layer is made of polypropylene, and the seal resin is made of a blend resin containing polypropylene and polyethylene. 前記弁部が、前記外装体周縁部の一部に設けられた未シール領域を外装体外部からクリップ材で挟持して構成されることを特徴とする請求項１及至請求項３のいずれか１に記載の扁平型電気化学セル。   The said valve | bulb part is comprised by clamping the unsealed area | region provided in a part of said exterior body peripheral part with the clip material from the exterior body exterior, Any one of Claim 1 to 3 characterized by the above-mentioned. A flat electrochemical cell according to 1.
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