JP2001332312A - Gas measurement method and device utilizing this method - Google Patents
Gas measurement method and device utilizing this methodInfo
- Publication number
- JP2001332312A JP2001332312A JP2000148777A JP2000148777A JP2001332312A JP 2001332312 A JP2001332312 A JP 2001332312A JP 2000148777 A JP2000148777 A JP 2000148777A JP 2000148777 A JP2000148777 A JP 2000148777A JP 2001332312 A JP2001332312 A JP 2001332312A
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- JP
- Japan
- Prior art keywords
- gas
- cell
- container
- measuring
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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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- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガス量の計測とガ
ス成分の分析を行うガス測定方法およびこれを利用する
装置に関する。更に詳述すると、本発明は二次電池のセ
ル内に発生したガスのガス量およびガス成分の測定に適
したガス測定方法およびこれを利用する装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas measuring method for measuring a gas amount and analyzing a gas component, and an apparatus using the same. More specifically, the present invention relates to a gas measuring method suitable for measuring a gas amount and a gas component of a gas generated in a cell of a secondary battery, and an apparatus using the same.
【０００２】[0002]
【従来の技術】二次電池の充放電の繰り返しによる劣化
の程度を検査するために、二次電池の電解液の劣化によ
りセル内に発生したガス量とその成分を測定する技術が
知られている。このガスの測定は、アルゴンガスを封入
したグローブバッグ（容積は約５０リットル）中で使用
により劣化した二次電池を解体し、セル中のガスをアル
ゴンガス中に混入させてアルゴンガスごとガス量および
ガス成分を測定している。2. Description of the Related Art In order to inspect the degree of deterioration of a secondary battery due to repeated charge and discharge, a technique for measuring the amount of gas generated in a cell due to deterioration of an electrolyte of a secondary battery and its components is known. I have. This gas was measured by disassembling a secondary battery that had been deteriorated by use in a glove bag (volume: about 50 liters) filled with argon gas, mixing the gas in the cell with argon gas, and measuring the gas volume together with the argon gas. And gas components are measured.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上述し
たガス測定の方法では、セル内で発生したガスは微量で
ありグローブバッグ内の多量のアルゴンガスに混合して
希釈されてしまうので、ガス測定の感度が大幅に低減し
てしまい測定精度が悪くなってしまう。例えば、上述の
例のように容積約５０リットルのアルゴンガスにセルで
発生した約１ｍｌのガスを混合した場合は、希釈率が約
１／５００００になってしまい高精度な測定は期待でき
ない。However, in the gas measurement method described above, the amount of gas generated in the cell is very small and is diluted by mixing with a large amount of argon gas in the glove bag. Sensitivity is greatly reduced and measurement accuracy is degraded. For example, when about 1 ml of gas generated in the cell is mixed with about 50 liters of argon gas as in the above-described example, the dilution ratio becomes about 1 / 50,000 and high-precision measurement cannot be expected.
【０００４】希釈による精度低下を防止するために濃縮
操作を行うこともあるが、濃縮操作には多くの器具と時
間を要し、場合によっては更に測定精度の低下を招くこ
とになる。そして、このようにして希釈と濃縮を経て得
られたデータは、希釈率や濃縮率を考慮して濃度計算を
するため大きな誤差を含むことになってしまい、高精度
の測定を行うことは極めて困難である。[0004] Concentration operations are sometimes performed to prevent a decrease in accuracy due to dilution. However, the concentration operation requires a lot of equipment and time, and in some cases, further lowers the measurement accuracy. The data obtained through dilution and concentration in this manner contains a large error because the concentration is calculated in consideration of the dilution ratio and the concentration ratio, and it is extremely difficult to perform highly accurate measurement. Have difficulty.
【０００５】そこで、本発明は、二次電池のセル内に発
生したガスの測定を高精度に行うことができるガス測定
方法およびこれを利用する装置を提供することを目的と
する。Accordingly, an object of the present invention is to provide a gas measuring method capable of measuring gas generated in a cell of a secondary battery with high accuracy, and an apparatus utilizing the gas measuring method.
【０００６】[0006]
【課題を解決するための手段】かかる目的を達成するた
め、請求項１記載のガス測定方法は、既知の容積を有す
る密閉空間に二次電池のセルを収容したまま空間を真空
雰囲気にする真空工程と、セルを解体して内部のガスを
空間に噴出させる噴出工程と、空間に充填されたガスの
圧力を測定して、そのガス圧と空間の容積とからガスの
大気圧下での体積を算出するガス量測定工程と、ガスに
希釈ガスを加えてからガス成分を測定する成分測定工程
とを備えるようにしている。In order to achieve the above object, a gas measuring method according to the first aspect of the present invention is a vacuum measuring method in which a space of a secondary battery is housed in a closed space having a known volume and the space is vacuumed. The process, the cell is disassembled, and the ejection process of ejecting the gas inside the space, and the pressure of the gas filled in the space is measured, and the volume of the gas under the atmospheric pressure is determined from the gas pressure and the volume of the space. And a component measuring step of measuring a gas component after adding a diluent gas to the gas.
【０００７】したがって、セル内の発生ガスを真空雰囲
気の空間に噴出してその圧力を測定して該ガス圧に基づ
き発生ガスの大気圧下での体積を算出しているので、従
来のように発生ガスを希釈してから測定する場合に比べ
て発生ガスの体積を高精度に測定することができる。Therefore, the generated gas in the cell is ejected into the space of the vacuum atmosphere, the pressure is measured, and the volume of the generated gas under the atmospheric pressure is calculated based on the gas pressure. The volume of the generated gas can be measured with higher precision than when measuring after diluting the generated gas.
【０００８】また、発生ガスの噴出前に真空雰囲気にす
るので、配管中およびセルに付着した微量の不純ガスの
脱気・洗浄が可能になる。よって、極微量の発生ガスで
も量および成分共に高精度に測定することができるよう
になる。Further, since the vacuum atmosphere is set before the generated gas is blown out, it is possible to remove and clean a trace amount of impurity gas adhering to the piping and to the cell. Therefore, even a very small amount of generated gas can be measured with high accuracy in both the amount and the component.
【０００９】さらに、発生ガスに必要最小限の希釈ガス
を加えて試料を作製して成分を測定することができるの
で、従来のようにセル内の発生ガスを大幅に希釈してか
ら濃縮して測定する場合に比べて測定精度を大きく高め
ることができる。Further, since a sample can be prepared by adding a minimum necessary diluent gas to the generated gas and the components can be measured, the generated gas in the cell is greatly diluted and concentrated as in the prior art. The measurement accuracy can be greatly improved as compared with the case where measurement is performed.
【００１０】そして、請求項２記載の発明は、請求項１
記載のガス測定方法において、噴出工程では、セルの安
全弁に針部材を貫通させてガスを空間に解放するように
している。したがって、従来のようにグローブバッグ内
で電池解体や分析操作をするのに比べて針部材を突き刺
すだけの容易な操作によってセルからガスを噴出させる
ことができる。よって、測定作業を短時間で行うことが
できるようになる。[0010] The invention described in claim 2 is based on claim 1.
In the gas measurement method described above, in the ejection step, the gas is released to the space by penetrating the needle member through the safety valve of the cell. Therefore, gas can be ejected from the cell by an easy operation of piercing the needle member as compared with the conventional operation of disassembling the battery or performing an analysis operation in the glove bag. Therefore, the measurement operation can be performed in a short time.
【００１１】また、請求項３記載の発明は、請求項１ま
たは２記載のガス測定方法において、成分測定工程で
は、ガスに希釈ガスを加えた混合ガスを、予め真空雰囲
気にした試料採取容器に圧力差により移行させて、試料
採取容器内の混合ガスをガスクロマトグラフにより測定
するようにしている。According to a third aspect of the present invention, in the gas measuring method according to the first or second aspect, in the component measuring step, a mixed gas obtained by adding a diluent gas to the gas is supplied to a sample collection container which has been previously brought into a vacuum atmosphere. The pressure is shifted by the pressure difference, and the mixed gas in the sampling container is measured by a gas chromatograph.
【００１２】したがって、試料採取容器に充填された希
釈後のガスを利用してガスクロマトグラフにより成分を
分析することができるので、発生ガス成分の測定を容易
に行うことができる。Therefore, the components can be analyzed by gas chromatography using the diluted gas filled in the sample collection container, so that the generated gas components can be easily measured.
【００１３】一方、請求項４記載のガス測定装置は、二
次電池のセルを収容するセル収容容器と、セル収容容器
に収容されたセルを解体して内部のガスを噴出させる解
体手段と、ガスを収容可能な試料採取容器と、セル収容
容器と試料採取容器とを連結するガス管と、試料採取容
器およびガス管の連結部分を開閉可能な開閉弁と、ガス
管と試料採取容器とセル収容容器とを真空にできる吸引
手段と、ガス管に希釈ガスを供給可能な希釈ガス供給手
段と、ガス管内の圧力を測定する圧力計とを備えるよう
にしている。According to a fourth aspect of the present invention, there is provided a gas measuring apparatus, comprising: a cell container for accommodating cells of a secondary battery; disassembly means for disassembling the cells accommodated in the cell container to eject gas therein; A sample collection container capable of storing gas, a gas pipe connecting the cell storage container and the sample collection container, an on-off valve capable of opening and closing the connection between the sample collection container and the gas pipe, a gas pipe, a sample collection container and a cell A suction unit capable of evacuating the storage container, a dilution gas supply unit capable of supplying a dilution gas to the gas pipe, and a pressure gauge for measuring a pressure in the gas pipe are provided.
【００１４】この場合、二次電池のセルをセル収容容器
に収容してから試料採取容器の開閉弁を開いて吸引手段
を作動させる。これにより、セル収容容器および試料採
取容器とガス管とが真空にされる。そして、開閉弁を閉
じて試料採取容器を真空のまま密封する。この状態で解
体手段によりセルを解体するとセルの内部の発生ガスが
真空雰囲気に吸い出されて、セル収容容器およびガス管
内に移行して充填される。このとき、圧力計でガス管内
の圧力を測定し、そのガス圧とセル収容容器およびガス
管の容積とから発生ガスの大気圧下での体積を算出する
ことができる。In this case, after the cells of the secondary battery are stored in the cell storage container, the on-off valve of the sample collection container is opened to operate the suction means. Thereby, the cell housing container, the sample collection container, and the gas pipe are evacuated. Then, the on-off valve is closed and the sampling container is sealed in a vacuum state. When the cell is dismantled by the dismantling means in this state, the gas generated inside the cell is sucked out into a vacuum atmosphere, and is transferred to and filled in the cell container and the gas pipe. At this time, the pressure in the gas pipe is measured with a pressure gauge, and the volume of the generated gas under the atmospheric pressure can be calculated from the gas pressure and the volumes of the cell container and the gas pipe.
【００１５】そして、開閉弁を開くと共に希釈ガス供給
手段により希釈ガスを供給する。これにより、発生ガス
と希釈ガスとが混合して真空の試料採取容器に移行し
て、これら試料採取容器とガス管とセル収容容器とに充
填される。このとき、発生ガスに対する希釈ガスの混合
により、ガス成分を測定するための試料として十分なガ
ス圧を得ることができる。試料採取容器に充填された混
合ガスは、そのままガスクロマトグラフ等の成分測定手
段により測定される。Then, the on-off valve is opened and the diluent gas is supplied by the diluent gas supply means. As a result, the generated gas and the diluent gas are mixed and transferred to the vacuum sampling container, and the sample collection container, the gas pipe, and the cell storage container are filled. At this time, by mixing the dilution gas with the generated gas, a sufficient gas pressure as a sample for measuring gas components can be obtained. The mixed gas filled in the sampling container is directly measured by a component measuring means such as a gas chromatograph.
【００１６】また、請求項５記載の発明は、請求項４記
載のガス測定装置において、セル収容容器は絶縁性樹脂
から成るようにしている。したがって、二次電池がセル
収容容器内で短絡することを防止できるので、解体作業
を安全に行うことができる。According to a fifth aspect of the present invention, in the gas measuring apparatus of the fourth aspect, the cell container is made of an insulating resin. Therefore, it is possible to prevent the secondary battery from being short-circuited in the cell accommodating container, so that the dismantling operation can be performed safely.
【００１７】さらに、請求項６記載の発明は、請求項４
または５記載のガス測定装置において、解体手段はセル
の安全弁を貫通する針部材を備えるようにしている。し
たがって、従来のようにグローブバッグ内で電池解体や
分析操作等をするのに比べて簡易な機構でセルから発生
ガスを容易に噴出させることができる。よって、測定作
業を短時間で行うことができるようになる。[0017] Further, the invention according to claim 6 is based on claim 4.
In the gas measuring device described in Item 5 or 5, the disassembling means includes a needle member penetrating the safety valve of the cell. Therefore, the generated gas can be easily ejected from the cell with a simpler mechanism than in the conventional case where the battery is disassembled or analyzed in a glove bag. Therefore, the measurement operation can be performed in a short time.
【００１８】[0018]
【発明の実施の形態】以下、本発明の構成を図面に示す
実施の形態の一例に基づいて詳細に説明する。図１およ
び図２に本発明のガス測定装置１の実施形態を示す。こ
のガス測定装置１は、二次電池のセル２を収容するセル
収容容器３と、このセル２を解体して内部で発生したガ
ス（以下、発生ガスという）を噴出させる解体手段４
と、ガスを収容可能な試料採取容器５と、セル収容容器
３および試料採取容器５を連結するガス管６とを備えて
いる。ガス管６には、圧力計７と吸引手段８と希釈ガス
供給手段９とが取り付けられている。また、試料採取容
器５のガス管６を取り付けた部分には、流路を開閉可能
な開閉弁（バルブ）１０が設けられている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail based on an example of an embodiment shown in the drawings. 1 and 2 show an embodiment of a gas measuring device 1 according to the present invention. The gas measuring device 1 includes a cell container 3 for accommodating a cell 2 of a secondary battery, and a disassembling means 4 for disassembling the cell 2 and ejecting gas generated inside (hereinafter referred to as generated gas).
And a sample collection container 5 capable of storing gas, and a gas pipe 6 connecting the cell storage container 3 and the sample collection container 5. A pressure gauge 7, a suction means 8, and a dilution gas supply means 9 are attached to the gas pipe 6. An opening / closing valve (valve) 10 that can open and close the flow path is provided in a portion of the sample collection container 5 to which the gas pipe 6 is attached.
【００１９】このガス測定装置１では、二次電池のセル
２をセル収容容器３に収容してから試料採取容器５の開
閉弁１０を開いて吸引手段８を作動させる。これによ
り、セル収容容器３および試料採取容器５とガス管６と
が真空にされる。試料採取容器５が真空になってから開
閉弁１０を閉じる。そして、解体手段４によりセル２を
解体するとセル２の発生ガスが吸い出されて、セル収容
容器３およびガス管６に移行して充填される。このと
き、圧力計７でガス管６のガス圧を測定し、そのガス圧
とセル収容容器３およびガス管６の容積とから発生ガス
の大気圧下での体積を算出することができる。このた
め、発生ガスに希釈ガスを混合する必要が無いので、発
生ガスの大気圧下での体積を高精度に算出することがで
きる。In the gas measuring device 1, the cell 2 of the secondary battery is housed in the cell housing 3 and then the opening / closing valve 10 of the sample collecting container 5 is opened to operate the suction means 8. Thereby, the cell storage container 3, the sample collection container 5, and the gas pipe 6 are evacuated. After the sampling container 5 is evacuated, the on-off valve 10 is closed. Then, when the cell 2 is disassembled by the disassembly means 4, the gas generated from the cell 2 is sucked out and transferred to the cell container 3 and the gas pipe 6 to be filled. At this time, the gas pressure of the gas pipe 6 is measured by the pressure gauge 7, and the volume of the generated gas under the atmospheric pressure can be calculated from the gas pressure and the volumes of the cell container 3 and the gas pipe 6. For this reason, there is no need to mix the dilution gas with the generated gas, so that the volume of the generated gas under atmospheric pressure can be calculated with high accuracy.
【００２０】また、開閉弁１０を開いて希釈ガス供給手
段９により希釈ガスを供給する。これにより、発生ガス
と希釈ガスとが混合して試料採取容器５に移行して充填
される。試料採取容器５に充填された混合ガスは、その
ままガスクロマトグラフ等の成分測定手段により測定さ
れる。このため、最小限の希釈ガスを混合して成分測定
を行うことができるので、成分測定を高精度に行うこと
ができる。Further, the on-off valve 10 is opened, and the dilution gas is supplied by the dilution gas supply means 9. As a result, the generated gas and the dilution gas are mixed and transferred to the sampling container 5 to be filled. The mixed gas filled in the sampling container 5 is directly measured by a component measuring means such as a gas chromatograph. For this reason, since the component measurement can be performed by mixing the minimum dilution gas, the component measurement can be performed with high accuracy.
【００２１】セル収容容器３はデルリン等の絶縁性樹脂
から成る。このため、二次電池がセル収容容器３により
短絡することを防止できるので、解体作業を安全に行う
ことができる。そして、セル収容容器３は収容されるセ
ル２より僅かに大きい収容空間を有している。このよう
に収容空間を収容されるセル２より僅かに大きい程度に
抑えているので、気密性を高めることができる。また、
セル収容容器３の内部にはセル２に密着して支持する突
部１１が形成されている。このため、セル２のぐらつき
を防止して安全に解体を行うことができる。The cell container 3 is made of an insulating resin such as Delrin. For this reason, it is possible to prevent the secondary battery from being short-circuited by the cell storage container 3, so that the dismantling operation can be performed safely. The cell storage container 3 has a storage space slightly larger than the cell 2 to be stored. As described above, the accommodation space is suppressed to a level slightly larger than the accommodated cell 2, so that the airtightness can be improved. Also,
A protrusion 11 is formed inside the cell container 3 so as to closely contact and support the cell 2. For this reason, the disassembly can be performed safely by preventing the cell 2 from wobbling.
【００２２】解体手段４はセル２の安全弁を貫通する針
部材１２を備えている。この針部材１２が安全弁に突き
刺さることによりセル２の内外が連通されるので、発生
ガスが真空雰囲気に噴き出される。このため、簡単な機
構でセル２から発生ガスを容易に移行させることができ
る。The disassembling means 4 has a needle member 12 penetrating the safety valve of the cell 2. When the needle member 12 pierces the safety valve, the inside and outside of the cell 2 are communicated with each other, so that the generated gas is blown out into a vacuum atmosphere. Therefore, the generated gas can be easily transferred from the cell 2 with a simple mechanism.
【００２３】針部材１２は例えば直径４ｍｍで、セル収
容容器３の内部に出没可能に設けられている。また、針
部材１２はねじ部１３ａを有するハンドル１３が一体化
されて、ハンドル１３の回転により針部材１２の先端が
セル収容容器３の内部に出没するように設けられてい
る。さらに、セル収容容器３の針部材１２が貫通する孔
１４には、ガス管６に連通するガス路１５が形成されて
いる。また、針部材１２とセル収容容器３との間にはＯ
リング１６が設けられており、これらの間の気密性を高
めている。The needle member 12 has a diameter of, for example, 4 mm, and is provided so as to be able to protrude and retract inside the cell container 3. The needle member 12 is provided such that a handle 13 having a screw portion 13 a is integrated with the needle member 12 so that the tip of the needle member 12 protrudes and retracts inside the cell container 3 by rotation of the handle 13. Further, a gas passage 15 communicating with the gas pipe 6 is formed in a hole 14 of the cell container 3 through which the needle member 12 penetrates. O between the needle member 12 and the cell container 3
A ring 16 is provided to increase the airtightness between them.
【００２４】そして、セル２の安全弁の周囲はＯリング
１７により囲われてセル収容容器３の内壁に密着されて
いる。このため、針部材１２をセル２に突き刺して内部
の発生ガスが漏れ出たときに、該発生ガスがセル２の外
面に沿って拡散してしまうことを防止できる。さらに、
Ｏリング１７は針部材１２を中心に二重に設けられてい
る。よって、気密性を更に高くすることができる。The periphery of the safety valve of the cell 2 is surrounded by an O-ring 17 and is in close contact with the inner wall of the cell container 3. For this reason, when the generated gas inside leaks out by piercing the needle member 12 into the cell 2, it is possible to prevent the generated gas from diffusing along the outer surface of the cell 2. further,
The O-ring 17 is provided doubly around the needle member 12. Therefore, the airtightness can be further improved.
【００２５】圧力計７としては、計量用圧力計１８と希
釈用圧力計１９とがそれぞれガス管６に取り付けられて
いる。計量用圧力計１８は、０〜３００Ｔｏｒｒ（０〜
約４０ｋＰａ、０〜約０．３９気圧）程度の圧力を測定
可能なものとして、また希釈用圧力計１９は、０〜２０
００Ｔｏｒｒ（０〜約２６６．６ｋＰａ、０〜約２．６
３気圧、）程度の圧力を測定可能なものとしている。こ
のように圧力計７を気圧ごとに分けているので、それぞ
れの範囲での測定精度を高めることができる。本実施形
態では圧力計７を計量用圧力計１８と希釈用圧力計１９
とに分けているが、これには限られず一つの圧力計のみ
を使用するようにしても良い。As the pressure gauge 7, a measurement pressure gauge 18 and a dilution pressure gauge 19 are respectively attached to the gas pipe 6. The measuring pressure gauge 18 is 0 to 300 Torr (0 to 300 Torr).
A pressure of about 40 kPa, 0 to about 0.39 atm) can be measured.
00 Torr (0 to about 266.6 kPa, 0 to about 2.6
A pressure of about 3 atm) can be measured. Since the pressure gauge 7 is divided for each atmospheric pressure, the measurement accuracy in each range can be improved. In this embodiment, the pressure gauge 7 is replaced by a measurement pressure gauge 18 and a dilution pressure gauge 19.
However, the present invention is not limited to this, and only one pressure gauge may be used.
【００２６】試料採取容器５は、ガスクロマトグラフ等
の成分測定に使用する試料を採取するための容器であ
る。The sample collection container 5 is a container for collecting a sample used for measuring components such as a gas chromatograph.
【００２７】吸引手段８はガス管６を真空にするもので
あり、例えば真空ポンプやオイルレスポンプを使用する
ことができる。ここでの真空とは、完全な真空には限ら
れず約７０Ｐａ（約０．５Ｔｏｒｒ）以下の状態を意味
する。例えば７０Ｐａとした場合は、３０〜４０分ごと
で真空雰囲気を生成できるので、ガス測定のサイクルを
早めることができる。また、真空の圧力をもっと低くす
れば測定の精度を更に高めることができる。図１中符号
２８は、密封系のガスの解放を図るリークバルブを示
す。The suction means 8 is for making the gas pipe 6 vacuum, and for example, a vacuum pump or an oilless pump can be used. The vacuum here is not limited to a complete vacuum, but means a state of about 70 Pa (about 0.5 Torr) or less. For example, when the pressure is set to 70 Pa, a vacuum atmosphere can be generated every 30 to 40 minutes, so that the gas measurement cycle can be accelerated. Further, if the vacuum pressure is further reduced, the accuracy of the measurement can be further increased. Reference numeral 28 in FIG. 1 denotes a leak valve for releasing gas in a sealed system.
【００２８】希釈ガス供給手段９としては、アルゴンガ
スあるいはヘリウムガス、その他の標準ガス等の希釈ガ
スをガス管６内に吐出するボンベやポンプ等を使用する
ことができる。As the dilution gas supply means 9, a cylinder or a pump for discharging a dilution gas such as an argon gas, a helium gas, or another standard gas into the gas pipe 6 can be used.
【００２９】本実施形態では、セル収容容器３と各圧力
計１８，１９と試料採取容器５と吸引手段８と希釈ガス
供給手段９との他に検量タンク２７がガス管６に連結さ
れて、密封系が形成されている。そして、各要素とガス
管６との間には、それぞれバルブ２１〜２５が設けられ
ている。また、吸引手段８および希釈ガス供給手段９
と、セル収容容器３・各圧力計７・試料採取容器５・検
量タンク２７との間には、流量調整バルブ２６が設けら
れている。検量タンク２７は既知の容積を有するもの
で、例えば公共事業者検定の容器を用いる。In this embodiment, a calibration tank 27 is connected to the gas pipe 6 in addition to the cell container 3, each of the pressure gauges 18, 19, the sample container 5, the suction means 8, and the dilution gas supply means 9. A sealing system is formed. Valves 21 to 25 are provided between each element and the gas pipe 6. Further, the suction means 8 and the dilution gas supply means 9
A flow control valve 26 is provided between the cell storage container 3, each pressure gauge 7, the sample collection container 5, and the calibration tank 27. The calibration tank 27 has a known volume, and uses, for example, a container for public enterprise verification.
【００３０】ところで、発生ガスの測定に先立ってガス
測定装置１の密封系の各部の容積を測定しておく必要が
ある。この測定は、ある量のガスを被測定部分のみに封
入してガス圧を計測してから該ガスを被測定部分と検量
タンク２７に移行して再びガス圧を計測し、ガス圧と容
積の積を一定と仮定して被測定部の容積を算出して行う
ようにしている。Before measuring the generated gas, it is necessary to measure the volume of each part of the sealed system of the gas measuring device 1. In this measurement, a certain amount of gas is sealed only in the portion to be measured, the gas pressure is measured, the gas is transferred to the portion to be measured and the calibration tank 27, and the gas pressure is measured again. Assuming that the product is constant, the volume of the part to be measured is calculated and performed.
【００３１】まず、ガス管６の主要部、即ち各バルブ１
０，２０〜２６の間の管路の容量Ｖ１を測定する際は、
検量タンク２７として容量Ｖ０＝１０ｍｌを取り付け
る。そして、吸引手段８と検量タンク２７と計量用圧力
計１８との各バルブ２３，２５，２１と流量調整バルブ
２６とを開にして他のバルブ１０，２２，２４，２５は
全て閉じる。吸引手段８を起動させ、配管系を真空にす
る。次いで、流量調整バルブ２６と検量タンク２７のバ
ルブ２５を閉にし、吸引手段８を止める。この時の圧力
値Ｐ０を計量用圧力計１８で読み取る。そして、流量調
整バルブ２６を徐々に開き、計量用圧力計１８による値
が例えば４０ｋＰａ程度に上がったら流量調整バルブ２
６を閉じる。この時の圧力値Ｐ１を計量用圧力計１８で
読み取る。また、検量タンク２７のバルブ２５を開き、
この時の圧力値Ｐ２を計量用圧力計１８で読み取る。First, the main part of the gas pipe 6, that is, each valve 1
When measuring the capacity V1 of the pipeline between 0, 20 and 26,
A capacity V0 = 10 ml is attached as the calibration tank 27. Then, the valves 23, 25, 21 of the suction means 8, the calibration tank 27, and the measuring pressure gauge 18 and the flow control valve 26 are opened, and the other valves 10, 22, 24, 25 are all closed. The suction means 8 is activated, and the piping system is evacuated. Next, the flow control valve 26 and the valve 25 of the calibration tank 27 are closed, and the suction means 8 is stopped. The pressure value P0 at this time is read by the measuring pressure gauge 18. Then, the flow control valve 26 is gradually opened, and when the value measured by the measuring pressure gauge 18 rises to, for example, about 40 kPa, the flow control valve 2 is opened.
Close 6. The pressure value P1 at this time is read by the measuring pressure gauge 18. Also, open the valve 25 of the calibration tank 27,
The pressure value P2 at this time is read by the measuring pressure gauge 18.
【００３２】これらの測定値から数式１によってガス管
６の主要部の容量Ｖ１を算出することができる。From these measured values, the capacity V1 of the main part of the gas pipe 6 can be calculated by equation (1).
【数１】（Ｐ１−Ｐ０）×Ｖ１＝（Ｐ２−Ｐ０）×（Ｖ
０＋Ｖ１） ∴Ｖ１＝（（Ｐ２−Ｐ０）／（Ｐ１−Ｐ０））×Ｖ０ 次に、セル収容容器３の容量、即ちバルブ２０よりセル
収容容器３側の空間の容量Ｖ２を測定する際は、検量タ
ンク２７として容量Ｖ０＝２５ｍｌを取り付ける。そし
て、吸引手段８とセル収容容器３と検量タンク２７と計
量用圧力計１８との各バルブ２３，２０，２５，２１と
流量調整バルブ２６とを開にして他のバルブ１０，２
２，２４は全て閉じる。吸引手段８を起動させ、配管系
を真空にする。そして、流量調整バルブ２６と検量タン
ク２７のバルブ２５を閉にして、吸引手段８を止める。
この時の圧力値Ｐ０を計量用圧力計１８で読み取る。流
量調整バルブ２６を徐々に開き、計量用圧力計１８によ
る値が例えば４０ｋＰａ程度に上がったら流量調整バル
ブ２６を閉じる。この時の圧力値Ｐ１を計量用圧力計１
８で読み取る。さらに、検量タンク２７のバルブ２５を
開き、この時の圧力値Ｐ２を計量用圧力計１８で読み取
る。(P1-P0) × V1 = (P2-P0) × (V
0 + V1) ∴V1 = ((P2−P0) / (P1−P0)) × V0 Next, when measuring the capacity of the cell storage container 3, that is, the capacity V2 of the space on the cell storage container 3 side from the valve 20, A capacity V0 = 25 ml is attached as the calibration tank 27. Then, the valves 23, 20, 25, 21 of the suction means 8, the cell container 3, the calibration tank 27, and the measuring pressure gauge 18 and the flow control valve 26 are opened, and the other valves 10, 2 are opened.
2, 24 are all closed. The suction means 8 is activated, and the piping system is evacuated. Then, the flow control valve 26 and the valve 25 of the calibration tank 27 are closed, and the suction means 8 is stopped.
The pressure value P0 at this time is read by the measuring pressure gauge 18. The flow control valve 26 is gradually opened, and when the value measured by the measuring pressure gauge 18 rises to, for example, about 40 kPa, the flow control valve 26 is closed. The pressure value P1 at this time is measured by a pressure gauge 1 for measurement.
Read at 8. Further, the valve 25 of the calibration tank 27 is opened, and the pressure value P2 at this time is read by the measuring pressure gauge 18.
【００３３】これらの測定値から数式２によってセル収
容容器３の容量Ｖ２を算出することができる。From these measured values, the capacity V2 of the cell container 3 can be calculated by equation (2).
【数２】（Ｐ１−Ｐ０）×（Ｖ１＋Ｖ２）＝（Ｐ２−Ｐ
０）×（Ｖ０＋Ｖ１＋Ｖ２） ∴Ｖ２＝（（Ｐ２−Ｐ０）／（Ｐ１−Ｐ２））×Ｖ０−
Ｖ１ 次に、試料採取容器５の容量、即ち開閉弁１０より試料
採取容器５側の空間の容量Ｖ３を測定する際は、検量タ
ンク２７として容量Ｖ０＝２５ｍｌを取り付ける。そし
て、吸引手段８と試料採取容器５と検量タンク２７と計
量用圧力計１８との各バルブ２３，１０，２５，２１と
流量調整バルブ２６とを開にして他のバルブ２０，２
２，２４は全て閉じる。吸引手段８を起動させ、配管系
を真空にする。そして、流量調整バルブ２６と検量タン
ク２７のバルブ２５とを閉にして、吸引手段８を止め
る。この時の圧力値Ｐ０を計量用圧力計１８で読み取
る。流量調整バルブ２６を徐々に開き、計量用圧力計１
８による値が例えば４０ｋＰａ程度に上がったら流量調
整バルブ２６を閉じる。この時の圧力値Ｐ１を計量用圧
力計１８で読み取る。さらに、検量タンク２７のバルブ
２５を開き、この時の圧力値Ｐ２を計量用圧力計１８で
読み取る。(P1-P0) × (V1 + V2) = (P2-P
0) × (V0 + V1 + V2) ∴V2 = ((P2-P0) / (P1-P2)) × V0−
V1 Next, when measuring the capacity of the sample collection container 5, that is, the capacity V3 of the space on the sample collection container 5 side from the on-off valve 10, a capacity V0 = 25 ml is attached as the calibration tank 27. Then, the valves 23, 10, 25, 21 of the suction means 8, the sample collection container 5, the calibration tank 27, and the measuring pressure gauge 18 and the flow control valve 26 are opened, and the other valves 20, 2 are opened.
2, 24 are all closed. The suction means 8 is activated, and the piping system is evacuated. Then, the flow control valve 26 and the valve 25 of the calibration tank 27 are closed, and the suction means 8 is stopped. The pressure value P0 at this time is read by the measuring pressure gauge 18. Open the flow control valve 26 gradually and press the measuring pressure gauge 1
When the value of 8 rises to, for example, about 40 kPa, the flow control valve 26 is closed. The pressure value P1 at this time is read by the measuring pressure gauge 18. Further, the valve 25 of the calibration tank 27 is opened, and the pressure value P2 at this time is read by the measuring pressure gauge 18.
【００３４】これらの測定値から数式３によって試料採
取容器５の容量Ｖ３を算出することができる。From these measured values, the capacity V3 of the sample collection container 5 can be calculated by Expression 3.
【数３】（Ｐ１−Ｐ０）×（Ｖ１＋Ｖ３）＝（Ｐ２−Ｐ
０）×（Ｖ０＋Ｖ１＋Ｖ３） ∴Ｖ３＝（（Ｐ２−Ｐ０）／（Ｐ１−Ｐ２））×Ｖ０−
Ｖ１ 次に、希釈用圧力計１９の接続管、即ちバルブ２２より
希釈用圧力計１９側の空間の容量Ｖ４を測定する際は、
吸引手段８と計量用圧力計１８と希釈用圧力計１９との
各バルブ２３，２１，２２と流量調整バルブ２６とを開
にして他のバルブ１０，２０，２４，２５は全て閉じ
る。吸引手段８を起動させ、配管系を真空にする。そし
て、流量調整バルブ２６と希釈用圧力計１９のバルブ２
２とを閉にして、吸引手段８を止める。この時の圧力値
Ｐ０を計量用圧力計１８で読み取る。流量調整バルブ２
６を徐々に開き、計量用圧力計１８による値が例えば４
０ｋＰａ程度に上がったら流量調整バルブ２６を閉じ
る。この時の圧力値Ｐ１を計量用圧力計１８で読み取
る。さらに、希釈用圧力計１９のバルブ２２を開き、こ
の時の圧力値Ｐ２を計量用圧力計１８で読み取る。(P1-P0) × (V1 + V3) = (P2-P
0) × (V0 + V1 + V3) ∴V3 = ((P2-P0) / (P1-P2)) × V0−
V1 Next, when measuring the capacity V4 of the connection pipe of the dilution pressure gauge 19, that is, the space V4 on the dilution pressure gauge 19 side from the valve 22,
The valves 23, 21 and 22 of the suction means 8, the measuring pressure gauge 18 and the dilution pressure gauge 19, and the flow control valve 26 are opened, and the other valves 10, 20, 24 and 25 are all closed. The suction means 8 is activated, and the piping system is evacuated. Then, the flow control valve 26 and the valve 2 of the dilution pressure gauge 19 are used.
2 is closed, and the suction means 8 is stopped. The pressure value P0 at this time is read by the measuring pressure gauge 18. Flow control valve 2
6 is gradually opened, and the value obtained by the measuring pressure gauge 18 is, for example, 4
When the pressure rises to about 0 kPa, the flow control valve 26 is closed. The pressure value P1 at this time is read by the measuring pressure gauge 18. Further, the valve 22 of the diluting pressure gauge 19 is opened, and the pressure value P2 at this time is read by the measuring pressure gauge 18.
【００３５】これらの測定値から数式４によって希釈用
圧力計１９の接続管の容量Ｖ４を算出することができ
る。From these measured values, the capacity V4 of the connecting pipe of the diluting pressure gauge 19 can be calculated by the equation (4).
【数４】（Ｐ１−Ｐ０）×Ｖ１＝（Ｐ２−Ｐ０）×（Ｖ
１＋Ｖ４） ∴Ｖ４＝（（Ｐ１−Ｐ２）／（Ｐ２−Ｐ０））×Ｖ１ 以上によりガス測定装置１の密封系の各部の容積を算出
できたので、以後は検量タンク２７を設ける必要は無
い。(P1-P0) × V1 = (P2-P0) × (V
1 + V4) ∴V4 = ((P1−P2) / (P2−P0)) × V1 From the above, the volume of each part of the sealed system of the gas measuring device 1 can be calculated, so that there is no need to provide the calibration tank 27 thereafter.
【００３６】上述したガス測定装置１を利用して二次電
池のセル２内で発生したガスの測定を行う手順を以下に
説明する。A procedure for measuring the gas generated in the cell 2 of the secondary battery using the above-described gas measuring device 1 will be described below.
【００３７】セル収容容器３にセル２を入れてガス管６
に連結する。希釈ガス供給手段９のバルブ２４を閉じ
て、他のバルブ１０，２０〜２３，２５，２６を開く。
そして、吸引手段８を作動させて、系の全体を約７０Ｐ
ａ以下に減圧する。さらに、セル収容容器３と計量用圧
力計１８のバルブ２０，２１を除いて各バルブ１０，２
２，２３，２５，２６を閉じる。The cell 2 is placed in the cell container 3 and the gas pipe 6
Connect to The valve 24 of the dilution gas supply means 9 is closed, and the other valves 10, 20 to 23, 25, 26 are opened.
Then, the suction means 8 is operated to reduce the entire system to about 70P.
Reduce the pressure to a or less. Further, except for the cell container 3 and the valves 20 and 21 of the measuring pressure gauge 18, each of the valves 10, 2
Close 2,23,25,26.
【００３８】そして、セル収容容器３のハンドル１３を
回転させて針部材１２により電池ベント部分に孔を空け
る。これにより、電池内の発生ガスが真空雰囲気に噴き
出して、ガス管６内に充填される。さらに、この発生ガ
スの圧力を計量用圧力計１８で読み取る。Then, the handle 13 of the cell container 3 is rotated to make a hole in the battery vent with the needle member 12. As a result, the generated gas in the battery blows out into the vacuum atmosphere and fills the gas pipe 6. Further, the pressure of the generated gas is read by the measuring pressure gauge 18.
【００３９】ここで、ガス管６およびセル収容容器３の
容積は既知であるので、その容積値と計量用圧力計１８
での測定値とに基づいて発生ガスの大気圧での容積を算
出する。Here, since the volumes of the gas pipe 6 and the cell container 3 are known, the volume value and the pressure gauge 18 for measurement are used.
The volume of the generated gas at atmospheric pressure is calculated on the basis of the measurement value obtained in step (1).
【００４０】次に、セル収容容器３と計量用圧力計１８
の各バルブ２０，２１を閉めて、試料採取容器５と希釈
用圧力計１９の各バルブ１０，２２を開ける。ここで、
試料採取容器５は既に真空雰囲気にされていることか
ら、発生ガスが試料採取容器５に移行される。さらに、
希釈ガス供給手段９のバルブ２４と流量調整バルブ２６
を開けて、内圧約１０６．７ｋＰａ（約８００Ｔｏｒ
ｒ）になるまで希釈ガスを加える。この時の圧力を希釈
用圧力計１９で読み取る。希釈した後のガス圧と試料採
取容器５の容積とから希釈率が求められる。そして、試
料採取容器５に移行されたガスの成分は、ガスクロマト
グラフィやガスクロマトグラフィ／質量分析計などで測
定する。Next, the cell container 3 and the measuring pressure gauge 18
Are closed, and the valves 10 and 22 of the sample collection container 5 and the diluting pressure gauge 19 are opened. here,
Since the sampling container 5 is already in a vacuum atmosphere, the generated gas is transferred to the sampling container 5. further,
Valve 24 and flow control valve 26 of dilution gas supply means 9
, And the internal pressure is about 106.7 kPa (about 800 Torr).
Add diluent gas until r). The pressure at this time is read by the diluting pressure gauge 19. The dilution ratio is determined from the gas pressure after dilution and the volume of the sampling container 5. The components of the gas transferred to the sampling container 5 are measured by gas chromatography, gas chromatography / mass spectrometer, or the like.
【００４１】その後、セル収容容器３のバルブ２０を除
く全てのバルブを開き真空にすることにより、系全体の
洗浄を行い次の試験に向けて準備することができる。Thereafter, all valves except the valve 20 of the cell container 3 are opened and evacuated, whereby the entire system can be washed and prepared for the next test.
【００４２】また、１回の試験終了後にセル収容容器３
の各部分を分解して、容器内の汚れ（電解液などの付
着）をアルコールやアセトンで洗浄・乾燥する。乾燥
後、セル収容容器３を再組立てする。After one test, the cell container 3
Is disassembled, and the dirt (adhesion of the electrolytic solution, etc.) in the container is washed and dried with alcohol or acetone. After drying, the cell container 3 is reassembled.
【００４３】本実施形態によれば、ガス管６を使用して
いるのでセル収容容器３と計量用圧力計１８との間の容
積を小さく抑えることができる。このため、従来行って
きたグローブバッグ内での電池解体や分析操作等に比
べ、測定における感度の向上（数千〜万倍以上）と測定
精度の向上を図ることができる。また、従来のグローブ
バッグ使用の場合に比べて、安全で数段の作業性・操作
性の容易化と時間短縮も図ることができる。According to this embodiment, since the gas pipe 6 is used, the volume between the cell container 3 and the measuring pressure gauge 18 can be reduced. For this reason, compared with the conventional battery disassembly and analysis operation in a glove bag, the sensitivity in measurement can be improved (several thousands to 10,000 times or more) and the measurement accuracy can be improved. In addition, compared to the case of using a conventional glove bag, it is possible to achieve safer and easier operability and operability in several steps and shorten the time.
【００４４】なお、上述の実施形態は本発明の好適な実
施の一例ではあるがこれに限定されるものではなく本発
明の要旨を逸脱しない範囲において種々変形実施可能で
ある。例えば本実施形態では解体手段４において針部材
１２がセル２に突き刺さって発生ガスが噴出するように
しているが、これには限られず他の解体方法を採用して
も良い。例えば、電動式カッターを利用することにより
解体して発生ガスが噴出するようにしても良い。この場
合も、セル収容容器３内でセル２を安全に解体すること
ができる。The above embodiment is an example of a preferred embodiment of the present invention, but the present invention is not limited to this, and various modifications can be made without departing from the spirit of the present invention. For example, in the present embodiment, the needle member 12 pierces the cell 2 in the disassembly means 4 so that the generated gas is ejected, but the present invention is not limited to this, and another disassembly method may be employed. For example, the generated gas may be ejected by disassembly by using an electric cutter. Also in this case, the cell 2 can be safely disassembled in the cell container 3.
【００４５】また、本実施形態ではセル収容容器３を絶
縁性樹脂から成るものにしているが、これには限られず
例えば導電性の容器であってもセル２に接触する部分の
みを絶縁性材料により絶縁するようにしても良い。この
場合も二次電池がセル収容容器３内で短絡することを防
止できるので、解体作業を安全に行うことができる。In the present embodiment, the cell container 3 is made of an insulating resin. However, the present invention is not limited to this. For example, even in the case of a conductive container, only the portion in contact with the cell 2 is made of an insulating material. May be used for insulation. Also in this case, since the secondary battery can be prevented from being short-circuited in the cell container 3, the disassembly operation can be performed safely.
【００４６】さらに、本実施形態では検量タンク２７を
用いてガス測定装置１の密封系の各部の容積を算出して
いるが、これには限られずガス測定装置１の各部の容積
が予め分かっていれば検量タンク２７を設けなくても良
い。Further, in this embodiment, the volume of each part of the closed system of the gas measuring device 1 is calculated using the calibration tank 27. However, the present invention is not limited to this, and the volume of each part of the gas measuring device 1 is known in advance. If so, the calibration tank 27 may not be provided.
【００４７】ところで、本実施形態では密封系の各要素
をガス管６で接続しているが、これには限られず例えば
セル収容容器３の側面に圧力計や吸引手段８等の各要素
を直接取り付けたものとしても良い。この場合もガス測
定を安全かつ高精度に行うことができる。In the present embodiment, the components of the sealed system are connected by the gas pipe 6, but the invention is not limited to this. For example, the components such as the pressure gauge and the suction means 8 are directly connected to the side of the cell container 3. It may be attached. Also in this case, gas measurement can be performed safely and with high accuracy.
【００４８】[0048]
【実施例】図１に示すガス測定装置１の各部分の容積を
算出した。その結果、ガス管６の主要部の容量Ｖ１＝１
１．８８ｍｌ、セル収容容器３の容量Ｖ２＝２９．８１
ｍｌ、試料採取容器５の容量Ｖ３＝５２．２１ｍｌ、希
釈用圧力計１９の接続管の容量Ｖ４＝２．６６ｍｌとな
った。EXAMPLE The volume of each part of the gas measuring device 1 shown in FIG. 1 was calculated. As a result, the capacity V1 = 1 of the main part of the gas pipe 6
1.88 ml, capacity V2 of cell container 3 = 29.81
ml, the capacity V3 of the sampling container 5 = 52.21 ml, and the capacity V4 of the connecting pipe of the diluting pressure gauge 19 = 2.66 ml.
【００４９】そして、このガス測定装置１を利用して、
実際の試験電池内のガス量およびガス成分を求めた。こ
こでは、二次電池を充放電サイクルしたものを複数パタ
ーン用意し、電池内に発生したガス量とその成分を測定
した。その結果を表１に示す。同図から明らかなよう
に、発生したガスの量および成分を高精度に検出するこ
とができた。また、ガス測定装置１におけるガス量測定
の精度は０．０１ｍｌであった。よって、二次電池のガ
ス量測定と成分分析とが安全かつ短時間でできることが
判明した。Then, using this gas measuring device 1,
The gas amount and gas components in the actual test battery were determined. Here, a plurality of patterns of the secondary battery that were subjected to charge / discharge cycles were prepared, and the amount of gas generated in the battery and its components were measured. Table 1 shows the results. As is clear from the figure, the amount and composition of the generated gas could be detected with high accuracy. The accuracy of the gas amount measurement in the gas measuring device 1 was 0.01 ml. Therefore, it was found that the gas amount measurement and the component analysis of the secondary battery can be performed safely and in a short time.
【表１】 [Table 1]
【００５０】[0050]
【発明の効果】以上の説明より明らかなように、請求項
１記載のガス測定方法によれば、セル内の発生ガスを真
空雰囲気の空間に噴出してその圧力を測定して該ガス圧
に基づき発生ガスの大気圧下での体積を算出しているの
で、発生ガスの体積を高精度に測定することができる。
また、発生ガスの噴出前に真空雰囲気にするので、配管
中およびセルに付着した微量の不純ガスの脱気・洗浄が
可能になる。よって、極微量の発生ガスでも量および成
分共に高精度に測定することができるようになる。さら
に、発生ガスに必要最小限の希釈ガスを加えて試料を作
製して成分を測定することができるので、測定精度を大
きく高めることができる。As is apparent from the above description, according to the gas measuring method of the present invention, the generated gas in the cell is ejected into the space of the vacuum atmosphere, the pressure is measured, and the gas pressure is measured. Since the volume of the generated gas under the atmospheric pressure is calculated based on this, the volume of the generated gas can be measured with high accuracy.
In addition, since a vacuum atmosphere is set before the generated gas is blown out, it is possible to remove and clean a trace amount of impurity gas adhering to the piping and the cell. Therefore, even a very small amount of generated gas can be measured with high accuracy in both the amount and the component. Furthermore, since the sample can be prepared by adding a necessary minimum dilution gas to the generated gas and the components can be measured, the measurement accuracy can be greatly improved.
【００５１】よって、二次電池の劣化機構を解明する上
で必要な電池解体試験を安全に、かつ短時間・高感度・
高精度で行うことが可能となる。Therefore, the battery disassembly test necessary for elucidating the deterioration mechanism of the secondary battery can be performed safely, in a short time, with high sensitivity,
It can be performed with high accuracy.
【００５２】そして、請求項２記載のガス測定方法によ
れば、針部材を突き刺すだけの容易な操作によってセル
からガスを噴出させることができる。よって、測定作業
の作業性が良くなり容易に短時間で行うことができるよ
うになる。According to the gas measuring method of the second aspect, gas can be ejected from the cell by an easy operation of piercing the needle member. Therefore, the workability of the measurement work is improved, and the work can be easily performed in a short time.
【００５３】また、請求項３記載のガス測定方法によれ
ば、試料採取容器に充填された希釈後のガスを利用して
ガスクロマトグラフにより成分を分析することができる
ので、発生ガス成分の測定を容易に行うことができる。According to the gas measuring method of the third aspect, the components can be analyzed by gas chromatography using the diluted gas filled in the sampling container, so that the generated gas components can be measured. It can be done easily.
【００５４】一方、請求項４記載のガス測定装置によれ
ば、極微量の発生ガスでも量および成分共に高精度に測
定することができるので、二次電池の劣化機構を解明す
る上で必要な電池解体試験を安全に、かつ短時間・高感
度・高精度で行うことが可能となる。On the other hand, according to the gas measuring apparatus of the present invention, even a very small amount of generated gas can be measured with high accuracy in both the amount and the component, so that it is necessary to elucidate the deterioration mechanism of the secondary battery. The battery disassembly test can be performed safely and in a short time, with high sensitivity and high accuracy.
【００５５】また、請求項５記載のガス測定装置によれ
ば、二次電池がセル収容容器内で短絡することを防止で
きるので、解体作業を安全に行うことができる。Further, according to the gas measuring device of the fifth aspect, it is possible to prevent the secondary battery from being short-circuited in the cell container, so that the disassembling operation can be performed safely.
【００５６】さらに、請求項６記載のガス測定装置によ
れば、簡易な機構でセルから発生ガスを容易に噴出させ
ることができる。よって、測定作業を短時間で行うこと
ができるようになる。Further, according to the gas measuring device of the sixth aspect, the generated gas can be easily ejected from the cell by a simple mechanism. Therefore, the measurement operation can be performed in a short time.
【図１】本発明のガス測定装置の構成を示すブロック図
である。FIG. 1 is a block diagram illustrating a configuration of a gas measurement device according to the present invention.
【図２】セル収容容器を示す概略の縦断面側面図であ
る。FIG. 2 is a schematic longitudinal sectional side view showing a cell container.
１ ガス測定装置 ２ セル ３ セル収容容器 ４ 解体手段 ５ 試料採取容器 ６ ガス管 ７ 圧力計 ８ 吸引手段 ９ 希釈ガス供給手段 １０ 開閉弁 １２ 針部材 DESCRIPTION OF SYMBOLS 1 Gas measuring device 2 Cell 3 Cell storage container 4 Disassembly means 5 Sampling container 6 Gas pipe 7 Pressure gauge 8 Suction means 9 Diluent gas supply means 10 On-off valve 12 Needle member
───────────────────────────────────────────────────── フロントページの続き (72)発明者 竹井 勝仁 東京都狛江市岩戸北２−11−１ 財団法人 電力中央研究所 狛江研究所内 (72)発明者 小林 陽 東京都狛江市岩戸北２−11−１ 財団法人 電力中央研究所 狛江研究所内 (72)発明者 岩堀 徹 東京都狛江市岩戸北２−11−１ 財団法人 電力中央研究所 狛江研究所内 Ｆターム(参考） 5H030 AA00 AS20 FF31 ──────────────────────────────────────────────────続 き Continued on the front page (72) Katsuhito Takei 2-11-1 Iwatokita, Komae-shi, Tokyo Inside the Komae Research Center, Central Research Institute of Electric Power Industry (72) Inventor You Yo 2-11-11, Iwatokita, Komae-shi, Tokyo -1 Central Research Institute of Electric Power Industry Komae Research Institute (72) Inventor Toru Iwahori 2-11-1 Iwatokita, Komae City, Tokyo F-term in Komae Research Center Central Electric Power Research Institute 5H030 AA00 AS20 FF31
Claims (6)
のセルを収容したまま前記空間を真空雰囲気にする真空
工程と、前記セルを解体して内部のガスを前記空間に噴
出させる噴出工程と、前記空間に充填された前記ガスの
圧力を測定して、そのガス圧と前記空間の容積とから前
記ガスの大気圧下での体積を算出するガス量測定工程
と、前記ガスに希釈ガスを加えてからガス成分を測定す
る成分測定工程とを備えることを特徴とするガス測定方
法。1. A vacuum step in which a space of a secondary battery is housed in a sealed space having a known volume and a vacuum atmosphere is created in the space, and a jetting step in which the cells are disassembled and gas inside is jetted into the space. And a gas amount measuring step of measuring the pressure of the gas filled in the space, and calculating the volume of the gas under the atmospheric pressure from the gas pressure and the volume of the space; and And a component measuring step of measuring a gas component after adding the gas.
針部材を貫通させて前記ガスを前記空間に解放すること
を特徴とする請求項１記載のガス測定方法。2. The gas measuring method according to claim 1, wherein in the jetting step, the gas is released into the space by passing a needle member through a safety valve of the cell.
希釈ガスを加えた混合ガスを、予め真空雰囲気にした試
料採取容器に圧力差により移行させて、前記試料採取容
器内の前記混合ガスをガスクロマトグラフにより測定す
ることを特徴とする請求項１または２記載のガス測定方
法。3. In the component measuring step, a mixed gas obtained by adding the diluent gas to the gas is transferred by a pressure difference to a sample collection container previously set in a vacuum atmosphere, and the mixed gas in the sample collection container is transferred. 3. The gas measuring method according to claim 1, wherein the gas is measured by a gas chromatograph.
と、前記セル収容容器に収容された前記セルを解体して
内部のガスを噴出させる解体手段と、前記ガスを収容可
能な試料採取容器と、前記セル収容容器と前記試料採取
容器とを連結するガス管と、前記試料採取容器および前
記ガス管の連結部分を開閉可能な開閉弁と、前記ガス管
と試料採取容器とセル収容容器とを真空にできる吸引手
段と、前記ガス管に希釈ガスを供給可能な希釈ガス供給
手段と、前記ガス管内の圧力を測定する圧力計とを備え
ることを特徴とするガス測定装置。4. A cell accommodating container for accommodating cells of a secondary battery, disassembly means for disassembling the cells accommodated in the cell accommodating container and ejecting an internal gas, and sampling capable of accommodating the gas. A container, a gas pipe connecting the cell storage container and the sample collection container, an on-off valve capable of opening and closing a connection portion between the sample collection container and the gas pipe, the gas pipe, the sample collection container, and the cell storage container A gas measuring device, comprising: a suction means capable of supplying a vacuum to the gas pipe; a dilution gas supply means capable of supplying a dilution gas to the gas pipe; and a pressure gauge for measuring a pressure in the gas pipe.
ことを特徴とする請求項４記載のガス測定装置。5. The gas measuring device according to claim 4, wherein said cell container is made of an insulating resin.
通する針部材を備えることを特徴とする請求項４または
５記載のガス測定装置。6. The gas measuring apparatus according to claim 4, wherein the disassembling means includes a needle member penetrating a safety valve of the cell.
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|---|---|---|---|
| JP2000148777A JP3963340B2 (en) | 2000-05-19 | 2000-05-19 | Gas measuring method and apparatus using the same |
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|---|---|---|---|
| JP2000148777A JP3963340B2 (en) | 2000-05-19 | 2000-05-19 | Gas measuring method and apparatus using the same |
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| JP2001332312A true JP2001332312A (en) | 2001-11-30 |
| JP3963340B2 JP3963340B2 (en) | 2007-08-22 |
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|---|---|---|---|
| JP2000148777A Expired - Fee Related JP3963340B2 (en) | 2000-05-19 | 2000-05-19 | Gas measuring method and apparatus using the same |
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