JP5744600B2 - Secondary battery system - Google Patents

Secondary battery system Download PDF

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JP5744600B2
JP5744600B2 JP2011080784A JP2011080784A JP5744600B2 JP 5744600 B2 JP5744600 B2 JP 5744600B2 JP 2011080784 A JP2011080784 A JP 2011080784A JP 2011080784 A JP2011080784 A JP 2011080784A JP 5744600 B2 JP5744600 B2 JP 5744600B2
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gas
absorbent
secondary battery
absorbent material
battery system
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JP2012216413A (en
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洋平 柴田
洋平 柴田
好伸 安永
好伸 安永
渡辺　勉
勉 渡辺
稲益　徳雄
徳雄 稲益
小布施　洋
洋 小布施
真一 和田
真一 和田
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Kurita Water Industries Ltd
GS Yuasa International Ltd
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GS Yuasa International 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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  • Battery Mounting, Suspending (AREA)

Description

本発明は、異常時に内部で発生するガスの噴出を防止する機能を備えた二次電池システムに関する。   The present invention relates to a secondary battery system having a function of preventing ejection of gas generated inside during an abnormality.

二次電池は、過充電や短絡等の異常時に内部の温度が上昇し、大量のガスが発生して圧力も上昇する。そのため、二次電池の容器は安全弁を備え、所定の圧力を超えた場合に安全弁を通じて電解液から生成されるガスを安全に排出する。一方、電池内部から放出されるガスは可燃性のものや人体に有毒なものが大量に含まれているため、そのままの形で外部環境へ排出させない仕組みが必要となる。   In the secondary battery, the internal temperature rises when an abnormality such as overcharge or short circuit occurs, a large amount of gas is generated, and the pressure also rises. Therefore, the secondary battery container is provided with a safety valve, and when a predetermined pressure is exceeded, the gas generated from the electrolyte is safely discharged through the safety valve. On the other hand, since the gas emitted from the inside of the battery contains a large amount of flammable substances and toxic substances to the human body, a mechanism is required to prevent the gas from being discharged into the external environment as it is.

特許文献１は、電池の安全弁から排出される電解液とガスを分離し、電解液を電池に装着しているキャップ内に蓄えるようにして、電解液による弊害を防止することができる電池の構造について開示している。特許文献２は、酸化触媒等の触媒作用により蓄電池内で発生するガスを浄化するガス浄化部を備えたガス処理装置について開示している。特許文献３は、活性炭などのガス吸収材を封入したガス吸収素子を内部に備えた非水電解質二次電池について開示している。   Patent Document 1 discloses a battery structure in which electrolyte and gas discharged from a battery safety valve are separated and stored in a cap attached to the battery to prevent adverse effects caused by the electrolyte. Is disclosed. Patent document 2 is disclosing about the gas processing apparatus provided with the gas purification part which purify | cleans the gas which generate | occur | produces in a storage battery by catalytic action, such as an oxidation catalyst. Patent Document 3 discloses a nonaqueous electrolyte secondary battery having a gas absorption element in which a gas absorption material such as activated carbon is enclosed.

特開２００７−１２４８５号公報JP 2007-12485 A 特開２００９−２８９６５５号公報JP 2009-289655 A 特開２００３−７７５４９号公報Japanese Patent Laid-Open No. 2003-77549

しかしながら、異常時に二次電池内部から排出されるガスの種類は多岐にわたり、二酸化炭素などのほか、水素、炭化水素などの可燃性のもの、一酸化炭素などの有毒なもの、悪臭のガスなども含まれる。さらに、安全弁から排出されるのは、ガスだけでなく、高温で噴出する電解液或いはその蒸気が含まれる場合もある。ガス吸収材が電解液と接触すると、ガスの吸着サイトが埋まったり、吸収材が電解液の成分と反応することでさらに一酸化炭素等の有毒ガスを発生させるといった事象も明らかとなってきた。   However, there are a wide variety of gases discharged from the secondary battery in the event of an abnormality, including carbon dioxide, flammable substances such as hydrogen and hydrocarbons, toxic substances such as carbon monoxide, and malodorous gases. included. Further, not only the gas but also the electrolyte solution or its vapor ejected at a high temperature may be discharged from the safety valve. When the gas absorbing material comes into contact with the electrolytic solution, it has become clear that an adsorption site of the gas is filled or that the absorbing material reacts with a component of the electrolytic solution to further generate a toxic gas such as carbon monoxide.

本発明は、上記に鑑みてなされたものであり、二次電池の内部で発生するガスの吸収効率を高めることを主たる技術的課題とする。   This invention is made | formed in view of the above, and makes it a main technical subject to improve the absorption efficiency of the gas which generate | occur | produces inside a secondary battery.

本発明に係る二次電池システムは、安全弁が設けられた１個又は複数個の電池と、ガス吸収装置とを備え、前記ガス吸収装置は、カートリッジ容器と、該カートリッジ容器に形成されたガス導入部と、前記ガス導入部とは異なる部位に設けられたガス排出部とを備え、前記安全弁と前記ガス導入部とは接続され、前記ガス導入部から前記ガス排出部に到る流通経路の手前に電解液を吸収するための第１の吸収材を備え、前記第１の吸収材よりも前記ガス排出部側にガスを吸収するための第２の吸収材を備え、前記カートリッジ容器内部に、前記流通経路と、前記第１の吸収材と、前記第２の吸収材とを含むことを特徴とする。 A secondary battery system according to the present invention includes one or a plurality of batteries provided with safety valves and a gas absorption device, and the gas absorption device includes a cartridge container and a gas introduction formed in the cartridge container. And a gas discharge part provided at a site different from the gas introduction part, the safety valve and the gas introduction part are connected, and before the flow path from the gas introduction part to the gas discharge part A first absorbent material for absorbing the electrolyte solution, a second absorbent material for absorbing the gas closer to the gas discharge part than the first absorbent material, and inside the cartridge container, The distribution path, the first absorbent material, and the second absorbent material are included .

この構成により、安全弁から噴出した電解液及び一酸化炭素を含むガスは、ガス導入部から流通経路に流入後、まず、第１の吸収材で主に電解液を吸収し、その後第２の吸収材で主にガスを吸収することができる。本発明に係る二次電池システムは、第１の吸収材として電解液の成分に対して吸収効率の優れた材料を、第２の吸収材１４として一酸化炭素やその他のガスの成分に対して吸収効率に優れた材料をそれぞれ選択することが好ましい。   With this configuration, the electrolyte solution and the gas containing carbon monoxide ejected from the safety valve flow into the flow path from the gas introduction portion, and then first absorb the electrolyte solution mainly by the first absorbent, and then the second absorption. The material can mainly absorb gas. In the secondary battery system according to the present invention, a material having excellent absorption efficiency with respect to the components of the electrolytic solution is used as the first absorbent, and carbon monoxide and other gas components are used as the second absorbent 14. It is preferable to select materials each having excellent absorption efficiency.

また、上記二次電池システムは、安全弁が設けられた複数個の電池で構成されるとともに、各電池の安全弁が１つの集積配管に接続されていてもよい。すなわち、複数の電池からなる電池モジュールにも適用することができる。   The secondary battery system may be configured by a plurality of batteries provided with safety valves, and the safety valves of the respective batteries may be connected to one integrated pipe. That is, the present invention can be applied to a battery module including a plurality of batteries.

また、上記二次電池システムは、流通経路上であって第１の吸収材と第２の吸収材との間に酸化触媒がさらに配置されていてもよい。これにより第２の吸収材におけるガス吸収効率を一層高めることができる。   In the secondary battery system, an oxidation catalyst may be further disposed between the first absorbent material and the second absorbent material on the distribution channel. Thereby, the gas absorption efficiency in a 2nd absorber can be improved further.

また、上記二次電池システムは、前記第１の吸収材と前記第２の吸収材とを、前記流通経路に対して交差するように区画する仕切体を備え、その仕切体が少なくとも１箇所の貫通部分を有するように構成してもよい。この構成により、安全弁から噴出した電解液及び一酸化炭素を含むガスが第１の吸収材や第２の吸収材を通過する距離を長くすることができ、電解液及び一酸化炭素を含むガスと第１の吸収材や第２の吸収材との接触効率を向上させ、全体的にガス吸収効率をさらに向上させることができる。   In addition, the secondary battery system includes a partition that partitions the first absorbent material and the second absorbent material so as to intersect the flow path, and the partition body includes at least one partition. You may comprise so that it may have a penetration part. With this configuration, the distance that the gas containing the electrolytic solution and carbon monoxide ejected from the safety valve passes through the first absorbent and the second absorbent can be increased, and the gas containing the electrolytic solution and carbon monoxide; Contact efficiency with the first absorbent material and the second absorbent material can be improved, and the gas absorption efficiency can be further improved as a whole.

また、上記二次電池システムは、流通経路上であって第１の吸収材の手前及び／又は第１の吸収材と第２の吸収材との間に熱吸収材が設けられていてもよい。この構成により、安全弁から噴出した電解液及び一酸化炭素を含むガスを熱吸収材で冷却することで第１の吸収材及び第２の吸収材の吸収効率を向上させることができる。また、熱吸収材は第１の吸収材の手間又は第１の吸収材と第２の吸収材との間の両方に配置されていてもよい。   In the secondary battery system, a heat absorbing material may be provided on the distribution channel and before the first absorbent material and / or between the first absorbent material and the second absorbent material. . With this configuration, the absorption efficiency of the first absorbent material and the second absorbent material can be improved by cooling the gas containing the electrolyte solution and carbon monoxide ejected from the safety valve with the heat absorbent material. Moreover, the heat absorption material may be arrange | positioned both in the effort of the 1st absorption material, or between the 1st absorption material and the 2nd absorption material.

また、上記二次電池システムに用いられるガス吸収装置は、取付部材が設けられた密閉容器と、その密閉容器内部に、流通経路と、第１の吸収材と、第２の吸収材とを含む、取付自在にしたカートリッジとして構成することができる。 Moreover, the gas absorption apparatus used for the said secondary battery system contains the distribution channel, the 1st absorber, and the 2nd absorber in the airtight container provided with the attachment member, and the inside of the airtight container. The cartridge can be configured to be freely mounted.

本発明によれば、第１の吸収材で電解液を吸収後、電解液が除去されたガスを第２の吸収材で吸収するため、ガス吸収効率が非常に高い。   According to the present invention, after absorbing the electrolytic solution with the first absorbent, the gas from which the electrolytic solution has been removed is absorbed by the second absorbent, so that the gas absorption efficiency is very high.

第１の実施形態の二次電池システムSecondary battery system of the first embodiment カートリッジの内部構造を説明するための断面図Sectional drawing for demonstrating the internal structure of a cartridge ガス吸収率測定用の二次電池システムSecondary battery system for gas absorption rate measurement 第２の実施形態の二次電池システムSecondary battery system of second embodiment カートリッジの他の構成例Other configuration examples of cartridge

以下、本発明の実施形態について図面を参照して詳細に説明する。ただし、各実施形態はいずれも例示であり、本発明の限定的な解釈を与えるものではない。各実施形態において、同一又は同種の部材には同一の符号を用いる場合がある。
（第１の実施形態）
図１は、第１の実施形態の二次電池システムの構成を示している。矢印は、非水電解質二次電池１１の内部から噴出する電解液及びガスの流通方向を示す。図１に示すように、二次電池システム２１は、二次電池１１と、ガス吸収装置としてのカートリッジ１２とを備える。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, each embodiment is an exemplification, and does not give a limited interpretation of the present invention. In each embodiment, the same code | symbol may be used for the same or the same kind of member.
(First embodiment)
FIG. 1 shows the configuration of the secondary battery system of the first embodiment. The arrows indicate the flow direction of the electrolyte solution and gas ejected from the inside of the nonaqueous electrolyte secondary battery 11. As shown in FIG. 1, the secondary battery system 21 includes a secondary battery 11 and a cartridge 12 as a gas absorption device.

カートリッジ１２は、カートリッジ容器１２ａの底部に第１のカートリッジ弁１２ｂを、上部に第２のカートリッジ弁１２ｃを有する。これらの弁は、いずれも所定の圧力で開く圧力弁である。   The cartridge 12 has a first cartridge valve 12b at the bottom of the cartridge container 12a and a second cartridge valve 12c at the top. Each of these valves is a pressure valve that opens at a predetermined pressure.

カートリッジ１２は、第１のカートリッジ弁１２ｂと第２のカートリッジ弁１２ｃとを連通する流通経路１２ｄを有する。流通経路１２ｄ上には主に液体を吸収するための第１の吸収材１３と、主にガスを吸収するための第２の吸収材１４とを有し、それらが少なくとも１箇所の貫通部分を有する板状の仕切体１５によって区画されている。二次電池１１の安全弁４と第１のカートリッジ弁とは外部に液体や気体が漏出しないように気密性を保持した状態で取付部材３ａ、１２ｅによって接続されている。   The cartridge 12 has a flow path 12d that communicates the first cartridge valve 12b and the second cartridge valve 12c. The flow path 12d has a first absorbent material 13 for mainly absorbing liquid and a second absorbent material 14 for mainly absorbing gas, and these have at least one penetrating portion. It is divided by the plate-shaped partition 15 which has. The safety valve 4 of the secondary battery 11 and the first cartridge valve are connected to each other by the attachment members 3a and 12e in a state where airtightness is maintained so that liquid or gas does not leak outside.

安全弁４から噴出した電解液及びガスは、ガス導入部としての第１のカートリッジ弁１２ｂからカートリッジ１２内に流入し、第１及び第２の吸収材１３、１４を通過することで無害化された後、ガス排出部としての第２のカートリッジ弁１２ｃから流出する。   The electrolyte solution and gas ejected from the safety valve 4 flowed into the cartridge 12 from the first cartridge valve 12b as the gas introduction portion, and were rendered harmless by passing through the first and second absorbents 13 and 14. Thereafter, the gas flows out from the second cartridge valve 12c as a gas discharge unit.

図２は、カートリッジの内部構造を説明するための断面図である。図中の矢印は、電解液及びガスの流通方向を示す。電解液やガスをカートリッジ内に長時間滞留させるため、第２のカートリッジ弁１２ｃの開放圧力は、第１のカートリッジ弁のそれよりも高いことが好ましい。   FIG. 2 is a cross-sectional view for explaining the internal structure of the cartridge. The arrow in a figure shows the distribution direction of electrolyte solution and gas. In order to allow the electrolytic solution or gas to stay in the cartridge for a long time, the opening pressure of the second cartridge valve 12c is preferably higher than that of the first cartridge valve.

仕切体１５は、第１の吸収材１３と第２の吸収材１４が混ざり合わないように仕切ると共に電解液やガスを通過させるための少なくとも１箇所の貫通部分を有するもの、例えば、金属メッシュ、ネット、ろ紙、フィルター、貫通孔を有する板等などでもよい。仕切体１５によって、カートリッジ１２は、第１及び第２の吸収材１３、１４による２層構造の状態を保持できる。   The partition 15 has at least one penetrating portion for partitioning the first absorbent 13 and the second absorbent 14 so that the first absorbent 13 and the second absorbent 14 are not mixed with each other, for example, a metal mesh, A net, a filter paper, a filter, a plate having a through hole, or the like may be used. With the partition 15, the cartridge 12 can maintain a two-layer structure of the first and second absorbent members 13 and 14.

ただし、第１及び第２の吸収材１３、１４の大きさや形状や保持方法を工夫して、仕切体１５を省略してもよい。例えば、第１の吸収材１３及び第２の吸収材１４がいずれもカートリッジ容器１２ａの内部に収まるように、予め塊状に形成して配置してもよく、それらを貫通孔を有する容器又は袋等にそれぞれ収納して配置してもよい。   However, the partition 15 may be omitted by devising the size and shape of the first and second absorbent members 13 and 14 and the holding method. For example, the first absorbent material 13 and the second absorbent material 14 may be previously formed and arranged in a lump shape so that both are accommodated in the cartridge container 12a, and they are containers or bags having through holes. You may store and arrange in each.

第１の吸収材１３は、活性炭又は有機系材料や無機多孔質材料を含む分子化合物を用いることが好ましく、特に活性炭を用いることが好ましい。第２の吸収材１４は、有機系材料や無機多孔質材料を含む分子化合物を用いることが好ましく、特に、無機系多孔質材料を含む分子化合物を用いることが好ましい。但し、第１の吸収材１３として、第２の吸収材と同一の吸収材を用いてもよい。また、第１及び第２の吸収材１３、１４は、いずれも複数の材料を混合して用いてもよい。複数の分子化合物の組合せにより電解液や種々のガスを効率よく吸収することができるからである。   As the first absorbent material 13, it is preferable to use activated carbon or a molecular compound including an organic material or an inorganic porous material, and it is particularly preferable to use activated carbon. The second absorbent material 14 is preferably a molecular compound including an organic material or an inorganic porous material, and particularly preferably a molecular compound including an inorganic porous material. However, the same absorbent material as the second absorbent material may be used as the first absorbent material 13. Moreover, you may use the 1st and 2nd absorbers 13 and 14 for all, mixing a some material. This is because the electrolyte solution and various gases can be efficiently absorbed by the combination of a plurality of molecular compounds.

分子化合物とは、１つの化合物の結晶の三次元網目構造の中にできる隙間に、他の化合物が入りこんでできる一種の付加化合物であり、単独で安定に存在することのできる化合物の２種類以上の化合物が水素結合やファンデルワールス力等に代表される、共有結合以外の比較的弱い相互作用によって結合した化合物である。具体的には、水和物、溶媒化物、付加化合物、包接化合物等が含まれる。このような分子化合物は、分子化合物を形成する化合物と電解液との接触反応により形成することができ、電解液を固体状の化合物に変化させることができる。
分子化合物を形成する材料としては、化合物と電解液との接触反応により、電解液をホスト化合物で包接してなる包接化合物が挙げられる。分子化合物を形成する材料のうち、電解液を包接した包接化合物を形成するホスト化合物としては、有機化合物、無機化合物及び有機・無機複合化合物よりなるものが知られており、また、有機化合物においては単分子系、多分子系、高分子系ホスト等が知られている。
分子化合物は、ガスとの接触効率や容器等に充填した場合の充填効率等を考慮すると、平均粒子径１０〜５０００［μｍ］、特に２００〜３００［μｍ］であるものが好ましく、その比表面積３０［ｍ２／ｇ］以上、特に２００［ｍ２／ｇ］以上であるものが好ましい。 A molecular compound is a kind of addition compound that can be formed by the penetration of another compound into the gaps formed in the three-dimensional network structure of a single compound crystal. Two or more types of compounds that can exist stably alone Is a compound bonded by a relatively weak interaction other than a covalent bond, such as a hydrogen bond or van der Waals force. Specifically, hydrates, solvates, addition compounds, inclusion compounds and the like are included. Such a molecular compound can be formed by a contact reaction between a compound that forms the molecular compound and an electrolytic solution, and the electrolytic solution can be changed to a solid compound.
Examples of the material forming the molecular compound include an inclusion compound formed by inclusion of an electrolytic solution with a host compound by a contact reaction between the compound and the electrolytic solution. Among the materials forming the molecular compound, as the host compound that forms the clathrate compound that clathrates the electrolyte, those composed of organic compounds, inorganic compounds, and organic / inorganic composite compounds are known. Monomolecular, multimolecular, and polymeric hosts are known.
The molecular compound preferably has an average particle diameter of 10 to 5000 [μm], particularly 200 to 300 [μm], considering the contact efficiency with gas and the filling efficiency when filled in a container, etc., and its specific surface area It is preferably 30 [m 2 / g] or more, particularly 200 [m 2 / g] or more.

第１及び第２の吸収材１３、１４に用いることができる分子化合物としては、例えば、α−シクロデキストリン、β−シクロデキストリン、γ−シクロデキストリン等のシクロデキストリン類、カリックスアレン類、尿素、デオキシコール酸、コール酸、１，１，６，６−テトラフェニルヘキサ−２，４−ジイン−１，６−ジオール等のアセチレンアルコール類、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン等のビスフェノール類、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン等のテトラキスフェノール類、ビス−β−ナフトール等のナフトール類、ジフェン酸ビス（ジシクロヘキシルアミド）等のカルボン酸アミド類、２，５−ジ−ｔ−ブチルヒドロキノン等のヒドロキノン類、キチン、キトサン、多孔質シリカ、金属ポーラス構造体、ケイ酸カルシウム、ケイ酸マグネシウム、メタケイ酸アルミン酸マグネシウム、活性アルミナ、アパタイト、多孔質ガラス、ケイ酸マグネシウム、ケイ酸アルミニウム、多孔質有機金属化合物、カーボンブラック、ナノカーボン、ゼオライト、酸化チタン、酸化マグネシウム等が好適である。ただし、第１の吸収材１３は主に吸収対象である電解液に応じて選択し、第２の吸収材１４は主に吸収対象とするガスに応じて選択することが好ましい。   Examples of molecular compounds that can be used for the first and second absorbent materials 13 and 14 include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, calixarenes, urea, and deoxy. Cholic acid, cholic acid, acetylene alcohols such as 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol, and bisphenols such as 1,1-bis (4-hydroxyphenyl) cyclohexane , Tetrakisphenols such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, naphthols such as bis-β-naphthol, carboxylic acid amides such as bis (dicyclohexylamide) diphenate, Hydroquinones such as 5-di-t-butylhydroquinone, chitin, chitosan, porous shii Mosquito, metal porous structure, calcium silicate, magnesium silicate, magnesium aluminate metasilicate, activated alumina, apatite, porous glass, magnesium silicate, aluminum silicate, porous organometallic compound, carbon black, nanocarbon, Zeolite, titanium oxide, magnesium oxide and the like are suitable. However, it is preferable that the first absorbent material 13 is mainly selected according to the electrolytic solution to be absorbed, and the second absorbent material 14 is mainly selected according to the gas to be absorbed.

−実施例−
図３はガス吸収率測定用の二次電池システムを示している。このシステムにより、以下の１５種類のカートリッジを用いて、非水電解質二次電池の安全弁から噴出した一酸化炭素（ＣＯ）及び二酸化炭素（ＣＯ２）の吸収率をそれぞれ調べた。まず、実験で用いた二次電池システムの基本構成について説明する。 -Example-
FIG. 3 shows a secondary battery system for gas absorption rate measurement. Using this system, the absorption rates of carbon monoxide (CO) and carbon dioxide (CO 2 ) ejected from the safety valve of the nonaqueous electrolyte secondary battery were examined using the following 15 types of cartridges. First, the basic configuration of the secondary battery system used in the experiment will be described.

二次電池システム２１ａは、二次電池１１と、カートリッジ２２からなる。カートリッジ２２は、ガス導入部としての１つの流入口２２ｂとガス排出部としての複数の流出口２２ｃを備え、流入口２２ｂ及び流出口２２ｃの近傍にはろ紙２０ａ、２０ｂが設けられている。また、カートリッジ内部にも第１及び第２の吸収材１３，１４を仕切るための仕切体としてろ紙２５が設けられている。   The secondary battery system 21 a includes the secondary battery 11 and the cartridge 22. The cartridge 22 includes a single inlet 22b as a gas inlet and a plurality of outlets 22c as a gas outlet, and filter papers 20a and 20b are provided in the vicinity of the inlet 22b and the outlet 22c. A filter paper 25 is also provided inside the cartridge as a partition for partitioning the first and second absorbents 13 and 14.

二次電池１１は、定格容量０．５［Ａｈ］のリチウムイオン二次電池であり、電解液としてエチレンカーボネート、ジメチルカーボネート及びエチルメチルカーボネートを混合した混合溶媒に電解質塩を溶解させた非水電解質を含む。   The secondary battery 11 is a lithium ion secondary battery having a rated capacity of 0.5 [Ah], and is a non-aqueous electrolyte in which an electrolyte salt is dissolved in a mixed solvent in which ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate are mixed as an electrolytic solution. including.

カートリッジ２２は、第１の吸収材１３及び第２の吸収材１４の組合せにより、実施例１〜実施例７として（１）〜（７）、比較例１〜比較例８として（８）〜（１５）の１５種類を用いた。   The cartridge 22 is a combination of the first absorbent material 13 and the second absorbent material 14 (1) to (7) as Examples 1 to 7 and (8) to (8) as Comparative Examples 1 to 8. 15) of 15) was used.

（１）実施例１（＃２０２）
第１の吸収材１３として活性炭を２０［ｍｌ］、第２の吸収材１４として分子化合物＃２０２を１０［ｍｌ］用いた。ただし、分子化合物＃２０２は、Ｓｉ：Ａｌ：Ａｇ：Ｏ＝８．１：１：１：１８．３のモル比で構成される無機多孔質材料である。
（２）実施例２（＃２０３）
第１の吸収材１３として活性炭を２０［ｍｌ］、第２の吸収材１４として分子化合物＃２０３を１０［ｍｌ］用いた。ただし、分子化合物＃２０３は、Ｓｉ：Ａｌ：Ｃｕ：Ｏ＝４０：１：１：８０のモル比で構成される無機多孔質材料である。
（３）実施例３（＃２０４）
第１の吸収材１３として活性炭を２０［ｍｌ］、第２の吸収材１４として分子化合物＃２０４を１０［ｍｌ］用いた。ただし、分子化合物＃２０４は、Ｓｉ：Ａｌ：Ｃａ：Ｏ＝４．６：２：１：１３．２のモル比で構成される無機多孔質材料である。
（４）実施例４（＃２０７）
第１の吸収材１３として活性炭を２０［ｍｌ］、第２の吸収材１４として分子化合物＃２０７を１０［ｍｌ］用いた。ただし、分子化合物＃２０７は、Ｓｉ：Ａｌ：Ｃａ：Ｏ＝２：２：１：８のモル比で構成される無機多孔質材料である。
（５）実施例５（＃２０８）
第１の吸収材１３として活性炭を２０［ｍｌ］、第２の吸収材１４として分子化合物＃２０８を１０［ｍｌ］用いた。ただし、分子化合物＃２０８は、Ｓｉ：Ａｌ：Ｎａ：Ｏ＝２．３：１：１：６．６のモル比で構成される無機多孔質材料である。
（６）実施例６（＃２１５）
第１の吸収材１３として活性炭を２０［ｍｌ］、第２の吸収材１４として分子化合物＃２１５を１０［ｍｌ］用いた。ただし、分子化合物＃２１５は、Ｓｉ：Ａｌ：Ｌｉ：Ｏ＝１．３：１：１：４．１のモル比で構成される無機多孔質材料である。
（７）実施例７（＃２０７）
第１の吸収材１３として活性炭を１０［ｍｌ］、第２の吸収材１４として分子化合物＃２０７を１０［ｍｌ］用いた。ただし、分子化合物＃２０７は、Ｓｉ：Ａｌ：Ｃａ：Ｏ＝２：２：１：８のモル比で構成される無機多孔質材料である。 (1) Example 1 (# 202)
Activated carbon 20 [ml] was used as the first absorbent 13 and molecular compound # 202 10 [ml] was used as the second absorbent 14. However, the molecular compound # 202 is an inorganic porous material configured with a molar ratio of Si: Al: Ag: O = 8.1: 1: 1: 18.3.
(2) Example 2 (# 203)
Activated carbon 20 [ml] was used as the first absorbent 13 and molecular compound # 203 10 [ml] was used as the second absorbent 14. However, molecular compound # 203 is an inorganic porous material comprised by the molar ratio of Si: Al: Cu: O = 40: 1: 1: 80.
(3) Example 3 (# 204)
Activated carbon 20 [ml] was used as the first absorbent 13 and molecular compound # 204 10 [ml] was used as the second absorbent 14. However, molecular compound # 204 is an inorganic porous material comprised by the molar ratio of Si: Al: Ca: O = 4.6: 2: 1: 13.2.
(4) Example 4 (# 207)
Activated carbon 20 [ml] was used as the first absorbent 13 and molecular compound # 207 10 [ml] was used as the second absorbent 14. However, molecular compound # 207 is an inorganic porous material comprised by the molar ratio of Si: Al: Ca: O = 2: 2: 1: 8.
(5) Example 5 (# 208)
Activated carbon 20 [ml] was used as the first absorbent 13 and molecular compound # 208 10 [ml] was used as the second absorbent 14. However, the molecular compound # 208 is an inorganic porous material configured with a molar ratio of Si: Al: Na: O = 2.3: 1: 1: 6.6.
(6) Example 6 (# 215)
Activated carbon 20 [ml] was used as the first absorbent 13 and molecular compound # 215 10 [ml] was used as the second absorbent 14. However, molecular compound # 215 is an inorganic porous material comprised by the molar ratio of Si: Al: Li: O = 1.3: 1: 1: 4.1.
(7) Example 7 (# 207)
Activated carbon 10 [ml] was used as the first absorbent 13 and molecular compound # 207 10 [ml] was used as the second absorbent 14. However, molecular compound # 207 is an inorganic porous material comprised by the molar ratio of Si: Al: Ca: O = 2: 2: 1: 8.

（８）比較例１（ブランク）
第１の吸収材１３及び第２の吸収材１４は、いずれも吸収材無しとした。
（９）比較例２
第１の吸収材１３として活性炭を２０［ｍｌ］用いた。第２の吸収材１４は吸収材無しとした。
（１０）比較例３
第１の吸収材１３として上記分子化合物＃２０２を２０［ｍｌ］用いた。第２の吸収材１４は吸収材無しとした。
（１１）比較例４
第１の吸収材１３として上記分子化合物＃２０３を２０［ｍｌ］用いた。第２の吸収材１４は吸収材無しとした。
（１２）比較例５
第１の吸収材１３として上記分子化合物＃２０４を２０［ｍｌ］用いた。第２の吸収材１４は吸収材無しとした。
（１３）比較例６
第１の吸収材１３として上記分子化合物＃２０７を２０［ｍｌ］用いた。第２の吸収材１４は吸収材無しとした。
（１４）比較例７
第１の吸収材１３として上記分子化合物＃２０８を２０［ｍｌ］用いた。第２の吸収材１４は吸収材無しとした。
（１５）比較例８
第１の吸収材１３として上記分子化合物＃２１５を２０［ｍｌ］用いた。第２の吸収材１４は吸収材無しとした。 (8) Comparative example 1 (blank)
The first absorbent material 13 and the second absorbent material 14 were both free of absorbent material.
(9) Comparative Example 2
As the first absorbent 13, 20 [ml] of activated carbon was used. The second absorbent material 14 was free of absorbent material.
(10) Comparative Example 3
As the first absorbent 13, 20 [ml] of the molecular compound # 202 was used. The second absorbent material 14 was free of absorbent material.
(11) Comparative Example 4
As the first absorbent material 13, 20 [ml] of the molecular compound # 203 was used. The second absorbent material 14 was free of absorbent material.
(12) Comparative Example 5
As the first absorbent 13, 20 [ml] of the molecular compound # 204 was used. The second absorbent material 14 was free of absorbent material.
(13) Comparative Example 6
As the first absorbent 13, 20 [ml] of the molecular compound # 207 was used. The second absorbent material 14 was free of absorbent material.
(14) Comparative Example 7
As the first absorbent 13, 20 [ml] of the molecular compound # 208 was used. The second absorbent material 14 was free of absorbent material.
(15) Comparative Example 8
As the first absorbent 13, 20 [ml] of the molecular compound # 215 was used. The second absorbent material 14 was free of absorbent material.

次に、試験方法について説明する。まず、上記リチウムイオン二次電池の充放電を１サイクル実施した。具体的には、上記リチウムイオン二次電池を、温度２５［℃］において、電流０．２［ＣｍＡ］（約５時間率）、電圧３．６［Ｖ］、８時間の定電流及び定電圧で充電し、電流０．２［ＣｍＡ］（約５時間率）、終止電圧２．０［Ｖ］の定電流で放電した。その後、そのリチウムイオン二次電池に上記（１）〜（１５）の１５種類のカートリッジをそれぞれ接続して過充電試験を実施した。この過充電試験では、電流５［ＣｍＡ］（約１／５時間率）、電圧５０［Ｖ］、２時間の定電流及び定電圧で充電した。   Next, the test method will be described. First, the lithium ion secondary battery was charged and discharged for one cycle. Specifically, the above lithium ion secondary battery was measured at a temperature of 25 [° C.], a current of 0.2 [CmA] (approximately 5 hours rate), a voltage of 3.6 [V], a constant current of 8 hours and a constant voltage. And discharged at a constant current of 0.2 [CmA] (approximately 5 hours rate) and a final voltage of 2.0 [V]. Thereafter, the lithium ion secondary battery was connected to each of the 15 types of cartridges (1) to (15), and an overcharge test was performed. In this overcharge test, the battery was charged with a current of 5 [CmA] (about 1/5 hour rate), a voltage of 50 [V], a constant current and a constant voltage of 2 hours.

過充電試験によってリチウムイオン二次電池１１の安全弁４から噴出したガス及び電解液をカートリッジ２２の流入口２２ｂからカートリッジの内部に流入させ、流出口２２ｃから流出するガスをアルミバッグに回収し、ガスクロマトグラフィー（ＧＣ）分析装置（HP5890、HEWLETT PACKRD社製）を用いて一酸化炭素及び二酸化炭素の量をそれぞれ測定した。なお、測定条件として、カラム１及び２にはPorapakQ（ポーラスポリマー）を、カラム３には40/60 Molecular Sieve 13X1（合成ゼオライト）を、キャリアガスにはＡｒを用いた。また、注入口（Inlet）及び検出器（TCD）の温度は２００［℃］とした。以上の試験を実施して得られた結果は、以下の表１に示す通りである。ここで、比較例１（ブランク）に対する吸収率は、一酸化炭素及び二酸化炭素のそれぞれに対して以下の式１により算出している。
比較例１（ブランク）に対する吸収率＝（Ｘ−Ｙ）／Ｘ×１００ （式１）
ただし、Ｘは比較例１（ブランク）の対象ガスの測定量を、Ｙは対象とするカートリッジを用いた場合の対象ガスの測定量である。このことから、表中の−（マイナス）は、対象ガスの量が増大したことを示すものと考えられる。 Gas and electrolyte discharged from the safety valve 4 of the lithium ion secondary battery 11 in the overcharge test are caused to flow into the cartridge from the inlet 22b of the cartridge 22, and the gas flowing out from the outlet 22c is collected in an aluminum bag. The amounts of carbon monoxide and carbon dioxide were measured using a chromatographic (GC) analyzer (HP5890, manufactured by HEWLETT PACKRD). As measurement conditions, Porapak Q (porous polymer) was used for columns 1 and 2, 40/60 Molecular Sieve 13X1 (synthetic zeolite) was used for column 3, and Ar was used for the carrier gas. The temperature of the inlet (Inlet) and the detector (TCD) was 200 [° C.]. The results obtained by carrying out the above tests are as shown in Table 1 below. Here, the absorptance with respect to the comparative example 1 (blank) is computed by the following formula | equation 1 with respect to each of carbon monoxide and a carbon dioxide.
Absorption rate with respect to Comparative Example 1 (blank) = (X−Y) / X × 100 (Formula 1)
However, X is the measured amount of the target gas of Comparative Example 1 (blank), and Y is the measured amount of the target gas when the target cartridge is used. From this, it is considered that-(minus) in the table indicates that the amount of the target gas has increased.

Figure 0005744600
Figure 0005744600

表１より以下の点が確認された。
（１）活性炭のみの場合、比較例１（ブランク）に比べて一酸化炭素の量が増加し、二酸化炭素の量が１０％程度減少した。
（２）分子化合物＃２０７、分子化合物＃２０８、分子化合物＃２１５をそれぞれ単独で用いても比較例１（ブランク）に比べて一酸化炭素の量が増加した。
（３）分子化合物＃２０８及び分子化合物＃２１５は、いずれも比較例１（ブランク）に比べて二酸化炭素の量が大きく増加した。
（４）第１の吸収材として活性炭を用い、かつ、第２の吸収材として分子化合物＃２０７、＃２０８、＃２１５をそれぞれ用いた場合には、比較例１（ブランク）に比べて一酸化炭素の量が約２０％以上減少し二酸化炭素の量が５０％以上減少した。 From Table 1, the following points were confirmed.
(1) In the case of only activated carbon, the amount of carbon monoxide increased and the amount of carbon dioxide decreased by about 10% compared to Comparative Example 1 (blank).
(2) Even when each of molecular compound # 207, molecular compound # 208, and molecular compound # 215 was used alone, the amount of carbon monoxide increased as compared with Comparative Example 1 (blank).
(3) In both molecular compound # 208 and molecular compound # 215, the amount of carbon dioxide was greatly increased as compared with Comparative Example 1 (blank).
(4) When activated carbon is used as the first absorbent and molecular compounds # 207, # 208, and # 215 are used as the second absorbent, respectively, compared with Comparative Example 1 (blank), monoxide is oxidized. The amount of carbon decreased by about 20% or more, and the amount of carbon dioxide decreased by 50% or more.

よって、表１の実施例４〜６と比較例２、比較例６〜８の結果を考慮すると、単純に活性炭と分子化合物＃２０７、分子化合物＃２０８、分子化合物＃２１５のいずれかとを組合せても実施例４〜６ほどの吸収率を期待できないことが確認された。   Therefore, in consideration of the results of Examples 4 to 6, Comparative Example 2, and Comparative Examples 6 to 8 in Table 1, simply combining activated carbon with any one of Molecular Compound # 207, Molecular Compound # 208, and Molecular Compound # 215. It was also confirmed that the absorptivity as high as in Examples 4 to 6 could not be expected.

実施例４〜６、比較例２、６〜８において、過充電試験前後の第１の吸収材及び第２の吸収材の重量を測定すると、第１の吸収材の重量は増加し、第２の吸収材の重量はほとんど増加しなかった。具体的には、第２の吸収材の重量は、過充電試験前後で第１の吸収材の重量の増加に対して８分の１程度以下の増加と小さい。これは、第１の吸収材が主に電解液を吸収しているのに対して、第２の吸収材は電解液をほとんど吸収していないためと考えられる。
次に、分子化合物＃２０７による一酸化炭素及び二酸化炭素の吸収率に着目すると、いずれも実施例４＞実施例７＞比較例６という関係が成立する。すなわち、分子化合物の量が同じでも、下層の活性炭量を増すことで電解液成分を除去するほど、分子化合物＃２０７のガス吸収性能が向上すること、分子化合物がなければ一酸化炭素も二酸化炭素も吸収されないばかりか却って一酸化炭素及び二酸化炭素を放出することが分かる。 In Examples 4 to 6 and Comparative Examples 2 and 6 to 8, when the weights of the first absorbent material and the second absorbent material before and after the overcharge test were measured, the weight of the first absorbent material increased. The weight of the absorbent material was hardly increased. Specifically, the weight of the second absorbent material is as small as about 1/8 or less of the increase in the weight of the first absorbent material before and after the overcharge test. This is probably because the first absorbent material mainly absorbs the electrolytic solution, whereas the second absorbent material hardly absorbs the electrolytic solution.
Next, when attention is paid to the absorption rate of carbon monoxide and carbon dioxide by the molecular compound # 207, the relationship of Example 4> Example 7> Comparative Example 6 is established. That is, even if the amount of the molecular compound is the same, the gas absorption performance of the molecular compound # 207 improves as the electrolyte component is removed by increasing the amount of the activated carbon in the lower layer. In addition to being not absorbed, carbon monoxide and carbon dioxide are released.

以上のことから、カートリッジの内部において、流入口から近い順に、主に電解液を吸収するための第１の吸収材、主にガスを吸収するための第２の吸収材を設けることにより、安全弁から噴出した電解液及びガスを効率よく吸収できることが確認された。   From the above, by providing the first absorbent material for mainly absorbing the electrolytic solution and the second absorbent material for mainly absorbing the gas in the order closer to the inflow port, the safety valve is provided inside the cartridge. It was confirmed that the electrolyte solution and gas ejected from the gas can be efficiently absorbed.

（第２の実施形態）
第１の実施形態で示した二次電池システムは、二次電池を複数並べて用いる形態（以下、このような形態を「モジュール」という。）において、二次電池の各安全弁とカートリッジとを集積配管により接続する構成にも適用できる。 (Second Embodiment)
In the secondary battery system shown in the first embodiment, in a form in which a plurality of secondary batteries are used side by side (hereinafter, such a form is referred to as a “module”), each safety valve and cartridge of the secondary battery are integrated. It is applicable also to the structure connected by.

図４は、第２の実施形態の二次電池システムの構成を示している。個々の二次電池及びカートリッジはいずれも図１に示すものと同様である。図４に示すカートリッジは任意の場所に配置してもよい。図４に示すように、二次電池システム３１は、複数の二次電池２１を並置してなるモジュール２３と、１つのガス吸収装置３２と、１つの集積配管２４とを備える。   FIG. 4 shows the configuration of the secondary battery system of the second embodiment. Each of the secondary batteries and cartridges are the same as those shown in FIG. The cartridge shown in FIG. 4 may be arranged at an arbitrary place. As shown in FIG. 4, the secondary battery system 31 includes a module 23 in which a plurality of secondary batteries 21 are juxtaposed, one gas absorption device 32, and one integrated pipe 24.

集積配管２４は、二次電池２１の安全弁の数と同数の分配部２４ａと、その複数の分配部を１つに集積する本体部２４ｂとを有する。集積配管２４の一端２４は各二次電池２１の安全弁４にそれぞれ接続され、他端はガス吸収装置３２に接続される。   The integrated pipe 24 has the same number of distribution parts 24a as the number of safety valves of the secondary battery 21, and a main body part 24b that integrates the plurality of distribution parts into one. One end 24 of the integrated pipe 24 is connected to the safety valve 4 of each secondary battery 21, and the other end is connected to the gas absorption device 32.

第２の実施形態の二次電池システムは、複数の二次電池から噴出した電解液及びガスを集中配管２４によってまとめてガス吸収装置３２によって吸収することができる。このような構成によると、高温の電解液が集中配管を通過する際に冷却され、ガスの発生量が小さくなる利点もある。そのため、第２の実施形態によればガス吸収効率が一層向上する。   In the secondary battery system of the second embodiment, the electrolyte solution and the gas ejected from the plurality of secondary batteries can be collected together by the concentrated pipe 24 and absorbed by the gas absorption device 32. According to such a configuration, there is an advantage that a high-temperature electrolyte is cooled when passing through the concentrated pipe, and the amount of gas generated is reduced. Therefore, according to the second embodiment, the gas absorption efficiency is further improved.

（第３の実施形態）
図５（ａ）及び図５（ｂ）は、カートリッジの他の構成例を示している。図中の矢印は、電解液やガスの流通方向を示している。 (Third embodiment)
FIG. 5A and FIG. 5B show another configuration example of the cartridge. The arrows in the figure indicate the flow direction of the electrolyte and gas.

図５（ａ）に示すカートリッジ４２は、カートリッジ容器４２ａが、２つの仕切体１５、１８によって、第１のカートリッジ弁４２ｂから第２のカートリッジ弁４２ｃに通じるガスの流通経路４２ｄが３つの領域に区画されており、第１の吸収材１３と第２の吸収材１４との間に酸化触媒１６が充填されている。仕切体１８は、仕切体１５と同様なものを用いることができる。さらに、第２のカートリッジ弁４２ｃの手前に脱臭フィルター１９が設けられている。   In the cartridge 42 shown in FIG. 5A, the cartridge container 42a is divided into three regions by the two partition bodies 15 and 18 so that the gas flow path 42d leading from the first cartridge valve 42b to the second cartridge valve 42c is divided into three regions. An oxidation catalyst 16 is filled between the first absorbent material 13 and the second absorbent material 14. The partition 18 can be the same as the partition 15. Further, a deodorizing filter 19 is provided in front of the second cartridge valve 42c.

酸化触媒１６は、電解液、ガス、第１の吸収材１３、第２の吸収材１４やカートリッジの使用態様等に応じて様々なものを用いることができ、例えば、活性アルミナ、多孔質シリカ、アルミノケイ酸塩、ゼオライト、活性炭等の各種担体にＰｄＸ２（Ｘはハロゲン原子）及びＣｕＸ２を担持させた不均一触媒、金属ポーラス構造体、過マンガン酸カリウム等の過マンガン酸塩、パラジウム化合物、ロジウム化合物、ジルコニウム化合物、白金化合物等が好適である。 As the oxidation catalyst 16, various materials can be used depending on the electrolytic solution, the gas, the first absorbent material 13, the second absorbent material 14, the usage mode of the cartridge, and the like. For example, activated alumina, porous silica, Heterogeneous catalyst in which PdX 2 (X is a halogen atom) and CuX 2 are supported on various carriers such as aluminosilicate, zeolite, activated carbon, metal porous structure, permanganate such as potassium permanganate, palladium compound, Rhodium compounds, zirconium compounds, platinum compounds and the like are suitable.

酸化触媒１６によって第１の吸収材１３を通過したガスが酸化され、第２の吸収材１４によるガスの吸収効率がさらに向上する。また、この二次電池システムは、酸化触媒１６を用いることにより第１の吸収材１３及び第２の吸収材１４に用いる材料の選択余地を広げることができる。   The gas that has passed through the first absorbent 13 is oxidized by the oxidation catalyst 16, and the gas absorption efficiency by the second absorbent 14 is further improved. Further, in the secondary battery system, the use of the oxidation catalyst 16 can widen the choice of materials used for the first absorbent material 13 and the second absorbent material 14.

第３の実施形態の二次電池システムは、酸化触媒１６の代わりに、又は、さらに区画を設けて熱吸収材１７を設けても良い。熱吸収材１７は、熱容量が大きく伝熱性の高いもの、例えば、金属ビーズ等を用いることができる。熱吸収材１７には高温の電解液の蒸気を含むガスを冷却させる効果があるため、第２の吸収材１４による電解液やガスの吸収効率をさらに向上させることができる。この場合、熱吸収材１７は、第１の吸収材の前に配置することが好ましい。   In the secondary battery system according to the third embodiment, the heat absorbing material 17 may be provided instead of the oxidation catalyst 16 or by further providing a partition. As the heat absorbing material 17, a material having a large heat capacity and high heat conductivity, for example, metal beads can be used. Since the heat absorption material 17 has an effect of cooling the gas containing the vapor of the high-temperature electrolyte solution, the absorption efficiency of the electrolyte solution and gas by the second absorption material 14 can be further improved. In this case, it is preferable to arrange the heat absorbing material 17 before the first absorbing material.

図５（ｂ）に示すカートリッジ４２のように、仕切体１５の両端付近と仕切体１８の中央部付近に貫通部１５ａ、１８ａを有する板を設けてもよい。このようにすると、電解液やガスの流通経路が複雑になり、電解液やガスの滞留時間が長くなるため、電解液やガスの吸収効率をさらに向上させることができる。   As in the cartridge 42 shown in FIG. 5B, a plate having penetrating portions 15 a and 18 a may be provided near both ends of the partition 15 and near the center of the partition 18. If it does in this way, since the circulation route of electrolyte solution and gas will become complicated and the residence time of electrolyte solution and gas will become long, the absorption efficiency of electrolyte solution and gas can further be improved.

４ 安全弁
１１ 二次電池
１２、２２、４２ カートリッジ
１２ａ、２２ａ、４２ａ カートリッジ容器
１２ｂ、４２ｂ 第１のカートリッジ弁
１２ｃ、４２ｃ 第２のカートリッジ弁
１２ｄ、２２ｄ、４２ｄ 流通経路
１３ 第１の吸収材
１４ 第２の吸収材
１５、１８ 仕切体
１５ａ、１８ａ 貫通部
１６ 酸化触媒
１７ 熱吸収材
１９ 脱臭フィルター
２０、２５ ろ紙
２１、３１ 二次電池システム
２１ａ ガス吸収率測定用の二次電池システム
２２ｂ 流入口
２２ｃ 流出口
２３ モジュール
２４ 集積配管
３２ ガス吸収装置 4 Safety valve 11 Secondary battery 12, 22, 42 Cartridge 12a, 22a, 42a Cartridge container 12b, 42b First cartridge valve 12c, 42c Second cartridge valve 12d, 22d, 42d Flow path 13 First absorbent 14 First Absorbent material 15, 18 Partition 15 a, 18 a Penetration part 16 Oxidation catalyst 17 Heat absorber 19 Deodorizing filter 20, 25 Filter paper 21, 31 Secondary battery system 21 a Secondary battery system 22 b for measuring gas absorption rate Inlet 22 c Outlet 23 Module 24 Integrated piping 32 Gas absorber

Claims (7)

安全弁が設けられた１個又は複数個の電池と、ガス吸収装置とを備え、前記ガス吸収装置は、カートリッジ容器と、該カートリッジ容器に形成されたガス導入部と、前記ガス導入部とは異なる部位に設けられたガス排出部とを備え、前記安全弁と前記ガス導入部とは接続され、前記ガス導入部から前記ガス排出部に到る流通経路の手前に電解液を吸収するための第１の吸収材を備え、前記第１の吸収材よりも前記ガス排出部側にガスを吸収するための第２の吸収材を備え、前記カートリッジ容器内部に、前記流通経路と、前記第１の吸収材と、前記第２の吸収材とを含む二次電池システム。 One or a plurality of batteries provided with safety valves and a gas absorption device are provided, and the gas absorption device is different from a cartridge container, a gas introduction part formed in the cartridge container, and the gas introduction part. A gas discharge part provided at the site, the safety valve and the gas introduction part are connected, and a first for absorbing the electrolyte before the flow path from the gas introduction part to the gas discharge part And a second absorbent for absorbing the gas closer to the gas discharge part than the first absorbent , and the distribution path and the first absorption in the cartridge container. A secondary battery system including a material and the second absorbent material . 複数個の電池を備え、各電池の安全弁が１つの集積配管に接続された請求項１記載の二次電池システム。   The secondary battery system according to claim 1, further comprising a plurality of batteries, wherein a safety valve of each battery is connected to one integrated pipe. 前記流通経路上であって前記第１の吸収材と前記第２の吸収材との間に酸化触媒がさらに設けられた請求項１又は請求項２記載の二次電池システム。   The secondary battery system according to claim 1, wherein an oxidation catalyst is further provided between the first absorbent material and the second absorbent material on the distribution path. 前記第１の吸収材と前記第２の吸収材とを、前記流通経路に対して交差するように区画する仕切体を備え、その仕切体が少なくとも１箇所の貫通部分を有するように構成された請求項１乃至請求項３のいずれか１項に記載の二次電池システム。   A partition body that partitions the first absorbent material and the second absorbent material so as to intersect with the flow path, and the partition body is configured to have at least one penetrating portion. The secondary battery system according to any one of claims 1 to 3. 前記流通経路上であって前記第１の吸収材の手前及び／又は前記第１の吸収材と前記第２の吸収材との間に熱吸収材が設けられた請求項１乃至請求項４のいずれか１項に記載の二次電池システム。   5. The heat absorbing material according to claim 1, wherein a heat absorbing material is provided on the distribution path and before the first absorbing material and / or between the first absorbing material and the second absorbing material. The secondary battery system according to any one of claims. 前記第１の吸収材及び前記第２の吸収材の少なくとも一方は、分子化合物を含むことを特徴とする請求項１乃至請求項５のいずれか１項に記載の二次電池システム。   6. The secondary battery system according to claim 1, wherein at least one of the first absorbent material and the second absorbent material contains a molecular compound. 密閉された前記カートリッジ容器に取付部材が設けられた、請求項１に記載の二次電池システム。 The secondary battery system according to claim 1 , wherein a mounting member is provided in the sealed cartridge container .
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