JP3260331B2 - Electrode analysis monitoring device and monitoring method - Google Patents
Electrode analysis monitoring device and monitoring methodInfo
- Publication number
- JP3260331B2 JP3260331B2 JP37209298A JP37209298A JP3260331B2 JP 3260331 B2 JP3260331 B2 JP 3260331B2 JP 37209298 A JP37209298 A JP 37209298A JP 37209298 A JP37209298 A JP 37209298A JP 3260331 B2 JP3260331 B2 JP 3260331B2
- Authority
- JP
- Japan
- Prior art keywords
- light
- electrode
- reflected light
- battery
- wave number
- 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.)
- Expired - Fee Related
Links
- 238000004458 analytical method Methods 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 28
- 238000012544 monitoring process Methods 0.000 title claims description 24
- 238000012806 monitoring device Methods 0.000 title description 12
- 238000006243 chemical reaction Methods 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000011149 active material Substances 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 230000005540 biological transmission Effects 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 20
- 230000003287 optical effect Effects 0.000 claims description 15
- 230000006866 deterioration Effects 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 13
- 230000000630 rising effect Effects 0.000 claims description 12
- 238000001228 spectrum Methods 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 230000007423 decrease Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 14
- 238000001069 Raman spectroscopy Methods 0.000 description 10
- 238000001237 Raman spectrum Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000012625 in-situ measurement Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 239000013308 plastic optical fiber Substances 0.000 description 2
- 230000036647 reaction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
- Spectrometry And Color Measurement (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電池活物質流通型
電池の電極分析モニタ装置およびモニタ方法に関し、な
かでもレドックスフロー型２次電池の電極分析モニタ装
置およびモニタ方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode analysis monitoring device and a monitoring method for a battery flowing through a battery active material, and more particularly to an electrode analysis monitoring device and a monitoring method for a redox flow type secondary battery.
【０００２】[0002]
【従来の技術】大規模な電力貯蔵技術は、原子力発電、
火力発電等のベース電源を定格出力で運転しながら、オ
フピーク時に余剰となる電力を蓄え、ピーク時にこれを
放電して、ロードレベリングに役立てようという技術で
ある。このような電力貯蔵技術によれば、平均需要に見
合った適正な容量のベース電源を保有し、これを効率的
な発電量の領域で定常運転できるので、電力発電設備の
経済性を高めることができるようになる。ピーク時の需
要電力に合わせて発電設備を保有していなくてもよく、
したがって、オフピーク時に過剰な設備を大規模に減速
運転させる事態を避けることができるようになる。2. Description of the Related Art Large-scale power storage technologies include nuclear power generation,
This is a technique that, while operating a base power supply such as a thermal power generator at a rated output, stores excess power during off-peak times and discharges the power during peak times to use it for load leveling. According to such power storage technology, a base power source with an appropriate capacity corresponding to the average demand is possessed and can be operated in a steady state in the area of efficient power generation. become able to. It is not necessary to have power generation equipment according to peak demand.
Therefore, it is possible to avoid a situation in which excessive equipment is decelerated on a large scale during off-peak hours.
【０００３】さらに、需要家である工場、ビル等に、こ
のような電力貯蔵設備を設置した場合には、安価な夜間
電力を貯蔵し必要時にこれを使用することができるの
で、電気料金面でのメリットが得られるほかに、非常用
電源、瞬停防止機能等を付加することも可能となる。Further, when such an electric power storage facility is installed in a factory, a building, or the like, which is a consumer, inexpensive nighttime electric power can be stored and used when necessary, so that electricity costs can be reduced. In addition to the advantages described above, it is also possible to add an emergency power supply, a momentary power failure prevention function, and the like.
【０００４】レドックスフロー型２次電池は、このよう
な期待に応える大規模な電力貯蔵技術として開発が推進
され、実用に供されようとしている技術である。The redox flow type secondary battery is a technology that has been developed and put to practical use as a large-scale power storage technology that meets such expectations.
【０００５】図４は、レドックスフロー型２次電池の単
一電池セルの構成を示す図である。図４（ａ）は正面図
を、図４（ｂ）は断面図を、また図４（ｃ）は各構成部
分を示す。正極５は正極セルに、また負極６は負極セル
に含まれ、各セルは隔膜７によって隔てられている。正
極液は正極液入り口１から正極セルに送り込まれ、多孔
質の正極５を通り、出口３から出てゆく。また、負極液
は入り口２から負極セルに送り込まれ、同じく多孔質の
負極６を通り、出口４から排出される。充電時と放電時
とで、電解液の流れる方向を反転させる装置もあるが、
本明細書ではとくに断らないかぎり電解液は充電時と放
電時とを問わず、上記の方向に流れることとする。FIG. 4 is a diagram showing a configuration of a single battery cell of a redox flow type secondary battery. 4A is a front view, FIG. 4B is a cross-sectional view, and FIG. 4C shows each component. The positive electrode 5 is included in a positive electrode cell, and the negative electrode 6 is included in a negative electrode cell. Each cell is separated by a diaphragm 7. The cathode solution is fed into the cathode cell from the cathode solution inlet 1, passes through the porous cathode 5, and exits from the outlet 3. The negative electrode solution is fed into the negative electrode cell through the inlet 2, passes through the same porous negative electrode 6, and is discharged through the outlet 4. There is also a device that reverses the flowing direction of the electrolyte between charging and discharging,
In this specification, unless otherwise noted, the electrolyte flows in the above-described direction regardless of whether the battery is charged or discharged.
【０００６】各セルは、電極５または６を含み、隔膜
７、フレーム１１、Ｏリング９および双極板８によって
囲まれる領域に形成される。Each cell includes an electrode 5 or 6 and is formed in a region surrounded by a diaphragm 7, a frame 11, an O-ring 9 and a bipolar plate 8.
【０００７】正極液および負極液としては、バナジウム
等の金属イオンを溶解させた酸性水溶液を用いる。バナ
ジウムイオンを用いる場合、正極液はＶ4+とＶ5+とを、
負極液はＶ3+とＶ2+とを含む硫酸溶液とするのが普通で
ある。これらの正極液および負極液は、それぞれ別々の
タンクに貯蔵され、各電極を有する各電池セルへと送液
循環される。As the positive electrode solution and the negative electrode solution, an acidic aqueous solution in which metal ions such as vanadium are dissolved is used. In the case of using vanadium ions, the positive electrode solution contains V 4+ and V 5+ ,
The negative electrode solution is usually a sulfuric acid solution containing V 3+ and V 2+ . These positive electrode solution and negative electrode solution are stored in separate tanks, respectively, and circulated to each battery cell having each electrode.
【０００８】各電極で充電時に起きる反応は、正極で
は、Ｖ4+→Ｖ5+＋ｅ- （酸化反応）、また、負極では、
Ｖ3+＋ｅ- →Ｖ2+（還元反応）である。一方、放電時に
は、正極では、Ｖ5+＋ｅ- →Ｖ4+（還元反応）、また、
負極では、Ｖ2+→Ｖ3+＋ｅ- （酸化反応）の、充電時と
は逆向きの電池反応が進行する。The reaction that occurs during charging at each electrode is V 4+ → V 5+ + e − (oxidation reaction) at the positive electrode, and
V 3+ + e − → V 2+ (reduction reaction). On the other hand, at the time of discharging, at the positive electrode, V 5+ + e − → V 4+ (reduction reaction)
At the negative electrode, a battery reaction of V 2+ → V 3+ + e − (oxidation reaction) proceeds in a direction opposite to that during charging.
【０００９】上記したように、単一電池セルは、隔膜７
によって隔てられ、正極５および負極６を備えたものと
して構成される。高電圧を得るためには、両端に双極板
８を備えた単一電池セルを積層し電気的に直列に接続し
て、電池セルスタックと称する構造にして用いる。実際
の電池システムでは、この電池セルスタックをさらに複
数個、電気的に直列および並列に組合せて所要の出力を
得る構成が採用される。[0009] As described above, the single battery cell includes the diaphragm 7.
And a positive electrode 5 and a negative electrode 6. In order to obtain a high voltage, a single battery cell having bipolar plates 8 at both ends is stacked and electrically connected in series, and used in a structure called a battery cell stack. An actual battery system employs a configuration in which a plurality of battery cell stacks are electrically combined in series and parallel to obtain a required output.
【００１０】上記の電池反応が行われる場所である電極
の材料には、まず何よりも第一に、電極反応を活性化さ
せる役割が課せられる。電池反応が活性化されると電池
の内部抵抗が減少するので、電池反応の活性化と内部抵
抗の減少とは同じ意味に解してさしつかえない。したが
って、電池反応の活性化は電池の効率を左右する基本的
に重要な項目である。The role of activating the electrode reaction is, first and foremost, of the material of the electrode where the above-mentioned battery reaction takes place. When the battery reaction is activated, the internal resistance of the battery is reduced. Therefore, the activation of the battery reaction and the decrease of the internal resistance may be understood in the same meaning. Therefore, activation of the battery reaction is a fundamentally important item that affects the efficiency of the battery.
【００１１】電極材の役割としては、次いで、電解液送
液時の圧力低下の防止、耐酸性等が求められる。このよ
うな性能を兼ね備えた材料として、通常、多孔質の孔表
面を活性化させた層状のカーボンフェルトが使用され
る。Next, as the role of the electrode material, it is required to prevent the pressure from dropping at the time of feeding the electrolytic solution and to prevent acidity. As a material having such performance, a layered carbon felt having a porous pore surface activated is usually used.
【００１２】レドックスフロー型２次電池の実用運転に
おいては、電極の状態は内部抵抗に影響し電池効率を左
右するので、常にモニタしておき、劣化が激しくなった
場合には良好な状態の電極と直ちに取り替える必要があ
る。In a practical operation of a redox flow type secondary battery, the condition of the electrode affects the internal resistance and affects the battery efficiency. Therefore, the condition of the electrode is always monitored, and if the deterioration becomes severe, the electrode in a good state is used. Need to be replaced immediately.
【００１３】電解液のモニタ装置については、循環供給
する導管の一部に設けられた被測定部について測定を行
う、光源、光伝達用部材、受光センサおよび受光分析装
置を備えた電解液組成分析装置が開示されている（実用
新案公報平４−３６０５９号公報）。[0013] With respect to the electrolytic solution monitoring device, an electrolytic solution composition analysis system provided with a light source, a light transmitting member, a light receiving sensor, and a light receiving analyzing device for measuring a portion to be measured provided in a part of a circulating supply conduit. An apparatus is disclosed (Japanese Utility Model Publication No. Hei 4-36059).
【００１４】しかしながら、電極については、オンサイ
トでその状態をモニタする技術は開発されていない。Ｘ
線解析装置を設置して、回折Ｘ線を測定することも考え
られるが、オンサイトでのモニタ装置として用いても有
力な情報が簡便に得にくく、また、とくに重要な表面の
状態のみを選別して得ることが不可能である。However, no technique has been developed for monitoring the state of the electrode on-site. X
It is conceivable to install a X-ray analyzer to measure diffracted X-rays, but it is difficult to easily obtain powerful information even when used as an on-site monitoring device, and to select only important surface conditions. It is impossible to get.
【００１５】したがって、実際に電池を組み、電池の評
価試験を実施して、電池効率が下がっているかどうか、
換言すれば、電池の内部抵抗が上がったかどうかを知る
ことにより、初めて電極の状態を認知することが可能で
あった。また、オンサイトでモニタする方法がないため
に、電極の劣化のメカニズムについての研究も思うよう
に進まなかった。Therefore, a battery is actually assembled, and an evaluation test of the battery is performed to determine whether the battery efficiency is reduced.
In other words, it was possible to recognize the state of the electrode for the first time by knowing whether or not the internal resistance of the battery had increased. In addition, research on electrode degradation mechanisms did not proceed as expected because there was no way to monitor them onsite.
【００１６】[0016]
【発明が解決しようとする課題】本発明の目的は、オン
サイトで操業中に電極の劣化状態を知ることができる電
池活物質流通型電池の電極分析モニタ装置およびモニタ
方法を提供すること、なかでもレドックスフロー型２次
電池の電極分析モニタ装置およびモニタ方法を提供する
ことにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrode analysis monitoring apparatus and method for a battery active material flow type battery, which can determine the deterioration state of the electrode during on-site operation. An object of the present invention is to provide an electrode analysis monitoring device and a monitoring method for a redox flow type secondary battery.
【００１７】[0017]
【課題を解決するための手段】本発明の第１の局面にお
ける電極分析モニタ装置は、液体状または気体状の電池
活物質が流通する電池セルを含む電池活物質流通型電池
の電極を分析する分析モニタ装置である。この分析モニ
タ装置は、光を出射する光源と、光源から発した光を伝
送するものであり、電池活物質を含む電解液が循環流通
される電池セル内に位置する電極の表面近くまで挿入さ
れ、その照射端から電極の被測定部に光を照射する第１
光伝送部材と、被測定部から反射した反射光を、電極の
表面近くに位置するその受光端によって受光して、分光
器まで伝送する第２光伝送部材と、第２光伝送部材を伝
送されてきた反射光を分光して、照射光との波数差にお
いてその反射光のスペクトルを測定する反射光測定装置
と、反射光測定装置によって測定された、２つの反射光
ピークがそれぞれ位置する照射光との波数差１３６０ｃ
ｍ-1と１５８０ｃｍ-1とを含む波数差領域において、反
射光の基線の立上がり勾配を、その反射光中での蛍光の
強度を表わす指標として、その立ち上がり勾配を検知す
る手段とを備えている。また、本発明の第２の局面にお
ける電極分析モニタ装置は、バナジウムイオンを含む電
池活物質が流通する電池セルを含む電池活物質流通型電
池の、主要構成部材がカーボンフェルトである電極を分
析する分析モニタ装置である。この電極分析モニタ装置
は、光を出射する光源と、光源から発した光を伝送する
ものであり、電池活物質を含む電解液が循環流通される
電池セル内に位置する電極の表面近くまで挿入され、そ
の照射端から電極の被測定部に光を照射する第１光伝送
部材と、被測定部から反射した反射光を、電極の表面近
くに位置するその受光端によって受光して、分光器まで
伝送する第２光伝送部材と、第２光伝送部材を伝送され
てきた反射光を分光して、照射光との波数差においてそ
の反射光のスペクトルを測定する反射光測定装置と、照
射光との波数差１３６０ｃｍ-1での反射光のピーク強度
と、照射光との波数差１５８０ｃｍ-1での反射光のピー
ク強度との比の使用開始からの低下を、バナジウム含有
電解液との反応によって生じる、カーボンフェルトにお
ける電池反応の活性化度の使用開始からの劣化とする、
バナジウム電解液中での前記カーボンフェルトの劣化検
出手段とを備える。According to a first aspect of the present invention, there is provided an electrode analysis monitor apparatus for analyzing an electrode of a battery active material flowing type battery including a battery cell in which a liquid or gaseous battery active material flows. An analysis monitor device. This analysis monitor device is a light source that emits light, and transmits light emitted from the light source, and is inserted to near the surface of an electrode located in a battery cell in which an electrolyte solution containing a battery active material is circulated and circulated. Irradiates light from the irradiation end to the measured portion of the electrode.
A light transmitting member, a second light transmitting member for receiving the reflected light reflected from the measured portion by its light receiving end located near the surface of the electrode, and transmitting the light to the spectroscope; and a second light transmitting member. A reflected light measuring device that disperses the reflected light and measures the spectrum of the reflected light at a wave number difference from the irradiated light; and the irradiated light where two reflected light peaks measured by the reflected light measuring device are respectively located. Wave number difference 1360c
means for detecting the rising gradient of the baseline of the reflected light in the wave number difference region including m -1 and 1580 cm -1 as an index representing the intensity of the fluorescence in the reflected light. . Further, the electrode analysis monitor device according to the second aspect of the present invention is a battery active material flowing type battery including a battery cell through which a battery active material containing vanadium ions flows, wherein a main constituent member is carbon felt. This is an analysis monitor device for analyzing a certain electrode. This electrode analysis monitor device transmits a light source that emits light and light emitted from the light source, and is inserted close to the surface of an electrode located in a battery cell in which an electrolyte solution containing a battery active material is circulated and circulated. A first light transmission member that irradiates light from the irradiation end to the measured portion of the electrode, and a light reflected from the measured portion is received by the light receiving end located near the surface of the electrode, and the spectroscope A second light transmitting member for transmitting the reflected light, a reflected light measuring device for dispersing the reflected light transmitted through the second light transmitting member, and measuring a spectrum of the reflected light at a wave number difference from the irradiated light; reducing the vanadium-containing and the peak intensity of the reflected light at the wave number difference 1360 cm -1, from the use of the ratio start of the peak intensity of the reflected light at the wave number difference 1580 cm -1 of the irradiation light with
Caused by the reaction with the electrolyte solution, your in carbon felt
Degradation of the degree of activation of the battery reaction from the start of use ,
Deterioration detection of the carbon felt in vanadium electrolyte
Output means .
【００１８】最も基本的な上記の発明の対象とする電池
は、レドックスフロー型２次電池、燃料電池等であり、
電池活物質は、Ｖイオン等を含んだ電解液、酸素、水
素、空気等が対象となる。The most basic objects of the present invention are redox flow type secondary batteries, fuel cells and the like.
The battery active material includes an electrolyte containing V ions and the like, oxygen, hydrogen, air, and the like.
【００１９】反射光を分光し、照射光の波数から一定波
数だけずれた波数のスペクトルを観察して、被測定部の
構成原子特有の格子振動等の情報を得る分光法はラマン
分光分析法と呼ばれる。その照射光には、通常、単色光
が用いられ、その単色光の波数との波数差によって反射
光のスペクトルを表示するのが普通である。この照射光
との波数差を、単に波数差またはラマンシフトという。A spectroscopic method for dispersing the reflected light and observing a spectrum of a wave number shifted from the wave number of the irradiation light by a certain wave number to obtain information such as lattice vibration peculiar to constituent atoms of the part to be measured is a Raman spectroscopic analysis method. Called. Normally, monochromatic light is used as the irradiation light, and the spectrum of the reflected light is usually displayed by a wave number difference from the wave number of the monochromatic light. The wave number difference from the irradiation light is simply referred to as a wave number difference or Raman shift.
【００２０】上記の本発明の基本構成により、このラマ
ン分光分析が可能となる。ラマン分光では、反射光を用
いるので、電池反応の活性箇所となる電極の表面の状態
のみを知ることができ、電極が電池反応を促進するか否
か正確に認知できるようになる。Ｘ線は透過力が強いた
めに、上記したように、従来のＸ線解析では表面のみの
状態を得ることが困難であった。The above-described basic configuration of the present invention enables this Raman spectroscopic analysis. Since the reflected light is used in Raman spectroscopy, it is possible to know only the state of the surface of the electrode, which is the active part of the battery reaction, and to accurately recognize whether or not the electrode promotes the battery reaction. As described above, it is difficult to obtain only the surface state in the conventional X-ray analysis because X-rays have a high penetrating power.
【００２１】上記の電極分析モニタ装置をレドックスフ
ロー型２次電池用に用いる場合は、電池活物質は電解液
に含まれ、電極は、その電解液が電解液経路を経て循環
流通される電池セル内に含まれており、第１光伝送部材
の照射端の部分および第２光伝送部材の受光端の部分と
はともに電池セル内に挿入され、電解液中の電極の表面
近くに位置するものとする。When the above-mentioned electrode analysis monitoring device is used for a redox flow type secondary battery, the battery active material is contained in the electrolyte, and the electrode is used as a battery cell in which the electrolyte is circulated through the electrolyte solution path. And the irradiation end portion of the first light transmission member and the light reception end portion of the second light transmission member are both inserted into the battery cell and located near the surface of the electrode in the electrolyte. And
【００２２】上記のように、第１光伝送部材の照射端の
部分および第２光伝送部材の受光端の部分とを電極の表
面近くに位置させることにより、強度の高い反射光を効
率よく受光して、精度の高いラマン分光分析が可能とな
る。また、さらに電極の使用期間が長くなり劣化が進む
と、反射光中に蛍光が含まれるようになり、２つの反射
光ピークがそれぞれ位置する波数差１３６０ｃｍ -1 と１
５８０ｃｍ -1 とを含む波数差領域において、反射光の基
線の立上がり勾配を、その反射光中での蛍光の強度を表
わす指標として、その立ち上がり勾配を検知する手段を
備える。上記の蛍光は、波数差１２００ｃｍ -1 からより
高い波数差領域にかけて強度が高くなるので、２つの反
射光ピークがそれぞれ位置する波数差１３６０ｃｍ -1 と
１５８０ｃｍ -1 とを含む波数差領域の基線を右肩上がり
にかさあげする。この蛍光は、電極材の劣化に伴って進
行する炭素原子とバナジウム原子との結合に由来するも
のと考えられている。したがって、上記の手段により、
上記の波数差の領域での基線の立ち上がり勾配により蛍
光の強度を知ることができ、電極材であるカーボンフェ
ルトのさらなる劣化の程度を認知することが可能とな
る。 As described above, since the irradiation end portion of the first optical transmission member and the light receiving end portion of the second optical transmission member are located near the surface of the electrode, reflected light having high intensity can be efficiently received. As a result, highly accurate Raman spectroscopy can be performed. In addition, the service life of the electrodes is further prolonged and deterioration proceeds.
And the reflected light contains fluorescent light.
Wavenumber differences 1360 cm -1 and 1 where the optical peaks are located
In the wave number difference region including 580 cm −1 ,
The rising slope of the line represents the intensity of the fluorescence in the reflected light.
As an index to pass, means to detect the rising slope
Prepare. The above fluorescence has a wave number difference of 1200 cm -1 or more.
Since the intensity increases over the high wave number difference region,
The wave number difference 1360 cm -1 which Shako peaks located respectively
The baseline of the wave number difference region including 1580 cm -1 rises to the right
Raise it. This fluorescence proceeds with the deterioration of the electrode material.
Originating from the bond between the carbon atom and the vanadium atom
It is believed that Therefore, by the above means,
Due to the rising slope of the baseline in the above wave number difference region,
The light intensity can be known, and the carbon
It is possible to recognize the degree of further deterioration of the
You.
【００２３】上記第１の局面の電極分析モニタ装置で
は、レドックスフロー型２次電池の電極がカーボンフェ
ルトで構成されている場合には、照射光との波数差１３
６０ｃｍ-1での前記反射光のピーク強度と、照射光との
波数差１５８０ｃｍ-1でのピーク強度との比を算出する
手段を備える電極分析モニタ装置とする。上記第２の局
面の電極分析モニタ装置は、バナジウムイオンを含む電
池活物質が流通するレドックスフロー型２次電池の電極
がカーボンフェルトで構成されている場合には、照射光
との波数差１３６０ｃｍ -1 での反射光のピーク強度と、
照射光との波数差１５８０ｃｍ -1 での反射光のピーク強
度との比の使用開始からの低下を、バナジウム含有電解
液との反応によって生じる、カーボンフェルトにおける
電池反応の活性化度の使用開始からの劣化とする、バナ
ジウム電解液中でのカーボンフェルトの劣化検出手段と
を備える。 In the electrode analysis monitoring device according to the first aspect, when the electrode of the redox flow type secondary battery is made of carbon felt, the wave number difference from the irradiation light is 13%.
And the peak intensity of the reflected light at 60cm -1, and the electrode analytical monitoring device comprising means for calculating a ratio of the peak intensity at a wavenumber difference 1580 cm -1 of the illumination light. The second station above
The surface electrode analysis and monitoring device uses an electrode containing vanadium ions.
Electrodes of redox flow type secondary battery through which pond active material flows
When is composed of carbon felt, the irradiation light
The peak intensity of the reflected light at a wave number difference of 1360 cm -1 and
Peak intensity of reflected light at 1580 cm -1 wave number difference from irradiation light
The decrease in the ratio from the start of use to the vanadium-containing electrolysis
In carbon felt caused by reaction with liquid
Degradation of the degree of activation of the battery reaction from the start of use
Means for detecting deterioration of carbon felt in electrolyte electrolyte
Is provided.
【００２４】波数差１３６０ｃｍ-1および１５８０ｃｍ
-1でのピーク強度の比を算出する手段を備えることによ
り、電池反応の活性化に寄与する物質を構成する炭素原
子と活性化に寄与するところの少ない物質を構成する炭
素原子との比を知り、電極の状態を定量的に認知するこ
とが可能となる。Wave number differences 1360 cm -1 and 1580 cm
By providing a means for calculating the ratio of the peak intensities at -1 , the ratio between the carbon atoms constituting the substance contributing to the activation of the battery reaction and the carbon atoms constituting the substance contributing little to the activation can be calculated. It is possible to know and quantitatively recognize the state of the electrode.
【００２５】[0025]
【００２６】[0026]
【００２７】[0027]
【００２８】上記の第１および第２の電極分析モニタ装
置は、つぎの本発明における最も基本的な第１および第
２の電極分析モニタ方法に用いられる装置である。その
第１の局面における電極分析モニタ方法とは、液体状ま
たは気体状の電池活物質が流通する電池セルを含む電池
活物質流通型電池の電極をモニタするモニタ方法であっ
て、光源から発した光を、電池活物質を含む電解液が循
環流通される電池セル内に位置する電極の表面近くまで
光伝送部材によって伝送し、その光伝送部材の照射端か
ら被測定部に照射し、その被測定部から反射した反射光
を、その電極の表面近くから、上記光伝送部材とは別に
設けた光伝送部材の受光端によって受光して、分光器ま
で伝送して分光し、その反射光のスペクトルを照射光と
の波数差において測定し、２つの反射光ピークがそれぞ
れ位置する照射光との波数差１３６０ｃｍ-1と１５８０
ｃｍ-1とを含む波数差領域において、反射光の基線の立
上がり勾配を、反射光中の蛍光の強度の指標とし、その
立ち上がり勾配の増大につれ、電極が劣化していること
を認知する。また、第２の局面における電極分析モニタ
方法とは、液体状または気体状の電池活物質が流通する
電池セルを含む電池活物質流通型電池の、主要構成部材
がカーボンフェルトである電極をモニタするモニタ方法
である。この電極分析モニタ方法は、光源から発した光
を、電池活物質を含む電解液が循環流通される電池セル
内に位置する電極の表面近くまで光伝送部材によって伝
送し、その光伝送部材の照射端から被測定部に照射し、
その被測定部から反射した反射光を、電極の表面近くか
ら上記の光伝送部材とは別に設けた光伝送部材の受光端
によって受光して、分光器まで伝送して分光し、その反
射光のスペクトルを照射光との波数差において測定し、
照射光との波数差１３６０ｃｍ-1での反射光のピーク強
度と、照射光との波数差１５８０ｃｍ-1での反射光のピ
ーク強度との比の使用開始からの低下を、電解液との反
応によって生じるカーボンフェルトにおける電池反応の
活性化度の使用開始からの劣化と評価して、その電解液
中でのカーボンフェルトにおける電池反応の活性化度の
劣化状態を検出する。The above-described first and second electrode analysis monitoring devices are devices used in the following most basic first and second electrode analysis monitoring methods of the present invention. The electrode analysis monitoring method according to the first aspect is a monitoring method for monitoring an electrode of a battery active material flowing type battery including a battery cell in which a liquid or gaseous battery active material flows, emitted from a light source. The light is transmitted by the light transmission member to near the surface of the electrode located in the battery cell in which the electrolyte containing the battery active material is circulated and circulated, and is irradiated from the irradiation end of the light transmission member to the portion to be measured. The reflected light reflected from the measuring unit is received from near the surface of the electrode by the light receiving end of the light transmitting member provided separately from the light transmitting member, and transmitted to a spectroscope to be spectrally separated. Is measured at the wave number difference from the irradiation light, and the wave number differences from the irradiation light at which the two reflected light peaks are respectively located are 1360 cm −1 and 1580
In the wave number difference region including cm −1 , the rising gradient of the baseline of the reflected light is used as an index of the intensity of the fluorescence in the reflected light, and it is recognized that the electrode is deteriorated as the rising gradient increases. Further, the electrode analysis monitoring method according to the second aspect is to monitor an electrode whose main constituent member is carbon felt in a battery active material flowing type battery including a battery cell in which a liquid or gaseous battery active material flows. This is a monitoring method. This electrode analysis monitoring method transmits light emitted from a light source to near the surface of an electrode located in a battery cell in which an electrolyte solution containing a battery active material is circulated and circulated, and irradiates the light transmission member. Irradiate the part to be measured from the end,
The reflected light reflected from the part to be measured is received from near the surface of the electrode by the light receiving end of the light transmitting member provided separately from the above light transmitting member, transmitted to a spectroscope to be split, and the reflected light is reflected. Measure the spectrum at the wave number difference from the irradiation light,
The decrease in the ratio between the peak intensity of the reflected light at a wave number difference of 1360 cm −1 from the irradiation light and the peak intensity of the reflected light at a wave number difference of 1580 cm −1 from the start of use is determined by the reaction with the electrolyte.
Of cell reaction in carbon felt caused by reaction
Assessing that the degree of activation has deteriorated since the start of use
Of the degree of activation of the battery reaction in carbon felt in air
Deterioration state is detected .
【００２９】上記本発明の第１および第２の局面におけ
る電極分析モニタ方法により、電極についてラマン分光
分析が可能となり、電極を構成している材料の表面の電
池反応箇所密度等の情報を得ることができるようにな
る。また、本発明の第１の局面における電極分析モニタ
方法では、電極の使用期間が長くなり、劣化がさらに進
んだ場合に、２つの反射光ピークがそれぞれ位置する照
射光との波数差１３６０ｃｍ -1 と波数差１５８０ｃｍ -1
とを含む波数差領域において、反射光の基線の立ち上が
り勾配を、反射光中の蛍光の強度の指標とし、その立ち
上がり勾配の増加につれ、電極が非常に劣化しているこ
とを認知することができる。電極の使用を連続長期間と
せざるをえない場合、ピーク強度比による方法とこの蛍
光の強度によって電極の状態を認知する方法とを併用す
ることにより、より正確に電極をモニタすることが可能
となる。 In the first and second aspects of the present invention,
According to the electrode analysis monitoring method, Raman spectroscopy can be performed on the electrode, and information such as the density of a battery reaction site on the surface of the material constituting the electrode can be obtained. Further, the electrode analysis monitor according to the first aspect of the present invention.
In this method, the service life of the electrode is prolonged and the deterioration is further accelerated.
The reflected light is located at each of the two reflected light peaks.
Wave number difference of 1360 cm -1 and wave number difference of 1580 cm -1
The rise of the baseline of the reflected light in the wave number difference region including
The gradient is used as an indicator of the intensity of the fluorescence in the reflected light,
The electrode is very deteriorated as the ascending gradient increases.
Can be recognized. Use electrodes for long periods of time
If it is inevitable, the method based on the peak intensity ratio and this method
Using the method of recognizing the state of the electrode based on the light intensity
Enables more accurate electrode monitoring
Becomes
【００３０】上記第１および第２の局面の電極分析モニ
タ方法では、レドックスフロー型２次電池の電極の主要
構成材料がカーボンフェルトである場合、照射光との波
数差１３６０ｃｍ-1での反射光のピーク強度と、波数差
１５８０ｃｍ-1での反射光のピーク強度との比を算出
し、そのピーク強度比が低下するにつれ、電極が劣化し
ていることを認知することができる。本発明が対象とす
るレドックスフロー型２次電池の電極は、カーボンフェ
ルトで構成されている。この場合、上記ラマンシフトに
おける波数差１３６０ｃｍ -1 での反射光のピークは、グ
ラファイトの格子状態の崩れた炭素原子に由来するピー
クであり、電池反応活性箇所密度に対応する成分であ
る。一方、波数差１５８０ｃｍ -1 でのピークは、グラフ
ァイト格子を構成する活性化に寄与することの少ない箇
所密度に対応する成分である。カーボンフェルトを電極
に使用した使用開始時には、波数差１３６０ｃｍ -1 での
反射光のピークは大きく、使用期間が長くなり劣化が進
行するにつれ、低下する。これに対して、波数差１５８
０ｃｍ -1 でのピークは、使用期間が長くなり劣化するに
つれ増大してくる。 The electrode analysis monitor according to the first and second aspects.
In the method, when the main constituent material of the electrode of the redox flow type secondary battery is carbon felt, the peak intensity of the reflected light at a wave number difference of 1360 cm -1 from the irradiation light and the wave number difference
The ratio to the peak intensity of the reflected light at 1580 cm -1 is calculated, and it can be recognized that the electrode has deteriorated as the peak intensity ratio decreases. The present invention is directed to
The electrode of a redox flow type secondary battery is
It is composed of defaults. In this case, the Raman shift
The peak of the reflected light at a wave number difference of 1360 cm -1
The peaks originating from the broken carbon atoms of the graphite
Component that corresponds to the density
You. On the other hand, the peak at a wave number difference of 1580 cm -1
Clauses that do not contribute much to the activation that constitutes the wite lattice
This is a component corresponding to the density. Carbon felt electrode
To use at the start, which was used in the, in the wave number difference 1360cm -1
The peak of the reflected light is large, and the use period is prolonged and the deterioration proceeds.
It goes down as you go. On the other hand, the wave number difference 158
The peak at 0 cm -1 has a longer service life and deteriorates.
It will increase.
【００３１】電池反応の活性化に寄与する、格子状態の
崩れた炭素原子に由来する波数差１３６０ｃｍ-1でのピ
ークと、活性化に寄与することの少ないグラファイト格
子を構成する炭素原子に由来する波数差１５６０ｃｍ-1
でのピークとの比を用いることにより、カーボンフェル
トの劣化状態を知ることが可能となる。A peak at a wave number difference of 1360 cm -1 derived from carbon atoms having a distorted lattice state, which contributes to activation of a battery reaction, and a carbon atom constituting a graphite lattice, which hardly contributes to activation. Wave number difference 1560cm -1
By using the ratio to the peak at the above, it is possible to know the deterioration state of the carbon felt.
【００３２】[0032]
【００３３】[0033]
【００３４】[0034]
【発明の実施の形態】図１は、本発明の電極分析モニタ
装置の構成を示す図である。図１（ｂ）は、図１（ａ）
に示した光伝送部材の照射端と受光端の部分および電極
の拡大図である。光源としてハロゲンランプ５０が設け
られ、単色光を照射光として用いている。光源５０から
出た光は、チョッパおよびカプラを経て光伝送部材５１
に導入され、光伝送部材５１によって被測定部まで導か
れる。光伝送部材５１および５２としては、プラスチッ
ク光ファイバが用いられている。FIG. 1 is a diagram showing a configuration of an electrode analysis monitoring device according to the present invention. FIG. 1 (b) is the same as FIG.
FIG. 3 is an enlarged view of an irradiation end and a light reception end of the optical transmission member shown in FIG. A halogen lamp 50 is provided as a light source, and monochromatic light is used as irradiation light. The light emitted from the light source 50 passes through a chopper and a coupler,
And guided by the optical transmission member 51 to the portion to be measured. Plastic optical fibers are used as the light transmission members 51 and 52.
【００３５】この光ファイバ５１の先端部である照射端
から出射した光は、電極５、６の表面に照射され、反射
を受ける。反射光は、光ファイバ５２に導入され、この
中を伝送されて、分光器５３に導かれる。この分光器５
３によって得られる反射光のスペクトルを得るために、
処理装置（パソコン）によって波長駆動しながら、光電
子倍増管（ＰＭＴ:Photo-Multiplying Tube ）によって
増幅する。本発明の記載における「反射光測定装置」と
は、上記の分光器５３、光電子倍増管５４および処理装
置５５を備えた装置をさす。The light emitted from the irradiation end, which is the tip of the optical fiber 51, is applied to the surfaces of the electrodes 5, 6 and is reflected. The reflected light is introduced into the optical fiber 52, transmitted through the optical fiber 52, and guided to the spectroscope 53. This spectroscope 5
3 to obtain the spectrum of the reflected light obtained by
Amplification is performed by a photomultiplier tube (PMT) while the wavelength is driven by a processing device (personal computer). The “reflected light measuring device” in the description of the present invention refers to a device provided with the above-described spectroscope 53, photomultiplier tube 54, and processing device 55.
【００３６】これらの装置の接続部においては光を平行
光線にするために、または焦点に集光するために、とう
ぜんレンズ系が用いられている。たとえば、光源から発
した光は、レンズにより平行光線とされて光ファイバ５
１の一端に入射される。図１においては、このような接
続部のレンズ系は一々示されていないが、それらのレン
ズ系が配置されていることは前提とされている。At the connection of these devices, a lens system is almost always used to collimate the light or focus it at the focal point. For example, light emitted from a light source is converted into a parallel light by a lens, and
1 at one end. FIG. 1 does not show each lens system of such a connection portion, but it is assumed that these lens systems are arranged.
【００３７】なお、当然のことであるが、外部の光によ
る影響を避けるために、この装置は全体または部分的に
外部の光から遮断されている。As a matter of course, this device is wholly or partially shielded from external light in order to avoid the influence of external light.
【００３８】図２は、図１に示す分析モニタによって得
られたラマンスペクトルを示す図である。図２（ａ）の
ラマンスペクトルには、波数差１３６０ｃｍ-1と１５８
０ｃｍ-1とに、特徴的な２つのピークが現れている。図
２（ａ）中の上段のラマンスペクトルは、電極を使用開
始するときに採取したラマンスペクトルであり、下段
は、一定期間充放電を繰り返したものについて採取した
ラマンスペクトルである。波数差１３６０ｃｍ-1のピー
クをＤバンド、また１５８０ｃｍ-1のピークをＧバンド
と呼ぶ場合がある。FIG. 2 is a diagram showing a Raman spectrum obtained by the analysis monitor shown in FIG. The Raman spectrum of FIG. 2A shows that the wave number difference is 1360 cm -1 and 158
At 0 cm -1 , two characteristic peaks appear. The upper Raman spectrum in FIG. 2A is a Raman spectrum collected when the electrode is started to be used, and the lower Raman spectrum is a Raman spectrum collected after repeated charging and discharging for a certain period. The peak of wavenumber difference 1360 cm -1 there is a case D band and the peak of 1580 cm -1 called the G band.
【００３９】同図において１３６０ｃｍ-1に現れるピー
クは、未組織炭素成分に由来するピークであり、このピ
ーク強度をＩA と記す。未組織炭素成分とは、黒鉛の結
晶構造が崩れた組織であり、反応活性箇所密度の高い黒
鉛成分である。したがって、このＩA が高いものほど、
電池反応が活発に行なわれ、内部抵抗は低いものにな
る。The peak appearing at 1360 cm -1 in the figure is a peak derived from unorganized carbon component, referred to the peak intensity and I A. The unstructured carbon component is a structure in which the crystal structure of graphite is broken, and is a graphite component having a high reaction active site density. Accordingly, as those the I A is high,
The battery reaction is active and the internal resistance is low.
【００４０】一方、波数差１５８０ｃｍ-1に現れるピー
クは、黒鉛成分に由来するピークであり、この強度をＩ
B と記す。このＩB が大きいものほど、反応活性箇所密
度が低いために、電池反応が活性化されることは少な
い。On the other hand, the peak appearing at a wave number difference of 1580 cm -1 is a peak derived from the graphite component.
Write B. As those greater this I B, because of the low reaction activity points density, you are less likely that cell reaction is activated.
【００４１】図２（ｂ）に、ピーク強度比（ＩA ／
ＩB ）の値と、電池の内部抵抗（Ω・ ｃｍ2 ）を示す。
図２（ｂ）によれば、ピーク強度比（ＩA ／ＩB ）は、
充放電が進むにつれて、１．２１から０．３５まで低下
する。このとき電池の内部抵抗は１．６Ω・ ｃｍ2 から
１．９Ω・ ｃｍ2 まで上昇していることが判明した。す
なわち、従来においては、電池を組み、内部抵抗測定装
置によりはじめて知ることができた内部抵抗を、電池に
組まれるか否かに関係なく、ラマン分光分析を行うこと
により簡便に知ることができるようになった。当然のこ
とであるが、本レドックスフロー型２次電池において
は、電池の状態で操業中にオンサイトで内部抵抗を知る
ことことの工学的意義は非常に大きく、本発明はこのよ
うな測定を可能としたために重要視されるものである。FIG. 2B shows the peak intensity ratio (I A /
Shows the value of I B), the internal resistance of the batteries (Ω · cm 2).
According to FIG. 2 (b), the peak intensity ratio (I A / I B) is
As the charging and discharging progress, it decreases from 1.21 to 0.35. At this time, it was found that the internal resistance of the battery increased from 1.6 Ω · cm 2 to 1.9 Ω · cm 2 . That is, in the related art, the internal resistance that can be obtained for the first time by using an internal resistance measuring device by assembling a battery can be easily known by performing Raman spectroscopic analysis regardless of whether or not the battery is assembled. Became. Naturally, in the present redox flow type secondary battery, knowing the internal resistance on-site during operation in the state of the battery has a great engineering significance, and the present invention makes such measurements. It is important to make it possible.
【００４２】上記したように、ピーク強度比（ＩA ／Ｉ
B ）を操業中にオンサイトで知ることにより、電極の状
態、すなわち電池の内部抵抗を知ることができ、電極の
取り替え時期を誤ることがなくなる。この結果、電池効
率の低い状態で運転する期間がなくなり、効率良く充放
電することが可能となる。As described above, the peak intensity ratio (I A / I
By knowing B ) on-site during operation, it is possible to know the state of the electrodes, that is, the internal resistance of the battery, so that the electrode replacement time is not mistaken. As a result, there is no longer a period of operation in a state where the battery efficiency is low, and charging and discharging can be performed efficiently.
【００４３】図３は、上記の使用状態からさらに充放電
反応を続けた電極のラマンスペクトルである。図３にお
いて、特徴的なことは、２つの反射光ピークがそれぞれ
位置する波数差１３６０ｃｍ-1と１５８０ｃｍ-1とを含
む波数差領域において、反射光の基線の立上がり勾配が
生じている。FIG. 3 is a Raman spectrum of an electrode that has been subjected to a charge / discharge reaction further from the above-mentioned use state. 3, the characteristic that, in the wave number difference region including the wave number difference 1360 cm -1 and 1580 cm -1 which two reflected light peak is located respectively, the rising slope of the baseline of the reflected light is generated.
【００４４】この蛍光は、電極の使用に伴って各種原子
の結合が進行し、それら結合状態にある原子から発せら
れるものであり、とくに炭素原子の蛍光（フォトルミネ
ッセンス ＰＬ:Photo-luminescence ）に由来するもの
である。The fluorescence is emitted from the atoms in the bonding state of various atoms as the electrodes are used, and the fluorescence is emitted from the carbon atoms (photoluminescence PL: Photo-luminescence). Is what you do.
【００４５】先に述べたように、蛍光は波数差１２００
ｃｍ-1以上の波数差域で右肩上がりに強度を高めるの
で、波数差１３６０ｃｍ-1と１５８０ｃｍ-1とを含む波
数差領域の基線は、その蛍光の強度分だけ右肩上がりに
かさあげされる。このような基線の立上がりは、図２
（ａ）には観測されていないことから、蛍光は電極の使
用が一定期間以上進行して、はじめて発生することがわ
かる。As described above, the fluorescence has a wave number difference of 1200.
Since increasing the strength soaring in cm -1 or more wavenumber difference range, baseline wavenumber difference region including the wave number difference 1360 cm -1 and 1580 cm -1 it is raised to soaring by strength portion of the fluorescent You. The rise of such a baseline is shown in FIG.
Since it is not observed in (a), it is understood that the fluorescence is generated only after the use of the electrode has progressed for a certain period or more.
【００４６】上記の波数差域の右肩上がりの基線は、直
線で近似され、この直線をＰＬ線と呼ぶ。このＰＬ線が
明確に認められる図３の状態において、電池の内部抵抗
は２．１Ω・ ｃｍ2 と、図２（ａ）中の下段のラマンス
ペクトルの状態よりもさらに高くなっていた。The base line rising to the right in the wave number difference region is approximated by a straight line, and this straight line is called a PL line. In the state of FIG. 3 where the PL line is clearly recognized, the internal resistance of the battery was 2.1 Ω · cm 2 , which was even higher than the state of the Raman spectrum in the lower part of FIG. 2A.
【００４７】上記により、反射光の２つのピーク強度比
および蛍光の強度を知ることにより、簡便に操業中にオ
ンサイトで、電極が電池反応を促進する状態にあるか否
かを認知することが可能であることが判明した。これら
の結果は、本発明が、レドックスフロー型２次電池の円
滑な運転に役立つ有力な技術として期待されることを示
している。As described above, by knowing the ratio of the two peak intensities of the reflected light and the intensity of the fluorescence, it is possible to easily recognize whether the electrode is in a state of accelerating the battery reaction on-site during operation. It turned out to be possible. These results indicate that the present invention is expected to be a powerful technique that can be used for smooth operation of a redox flow secondary battery.
【００４８】今回開示された実施の形態は、あくまで例
示であって、上記の実施の形態に限定されるものではな
い。本発明の範囲は、実施の形態についての説明ではな
く、特許請求の範囲の記載によって直接的に示され、さ
らに、特許請求の範囲と均等の意味および範囲内でのす
べての変更が含まれるものである。The embodiment disclosed this time is merely an example, and is not limited to the above embodiment. The scope of the present invention is directly shown by the description of the claims, not the description of the embodiments, and further includes the meaning equivalent to the claims and all changes within the scope. It is.
【００４９】[0049]
【発明の効果】本発明の電極分析モニタ装置およびモニ
タ方法によれば、電池反応が集中して進行する電極表面
のみの情報を有する反射光をラマン分光分析するため
に、電池反応を促進するか否かの状態を、正確にモニタ
することが可能となる。According to the electrode analysis monitoring apparatus and the monitoring method of the present invention, the Raman spectroscopic analysis of the reflected light having information only on the electrode surface where the battery reaction progresses in a concentrated manner is required to promote the battery reaction. It is possible to accurately monitor the status of whether or not.
【図１】本発明の電極分析モニタ装置の構成図である。FIG. 1 is a configuration diagram of an electrode analysis monitor device of the present invention.
【図２】電極であるカーボンフェルトのラマンスペクト
ルを示す図である。FIG. 2 is a diagram showing a Raman spectrum of carbon felt as an electrode.
【図３】電極であるカーボンフェルトのラマンスペクト
ル中の基線の立ち上がり、すなわちＰＬ線を示す図であ
る。FIG. 3 is a diagram showing a rising of a base line in a Raman spectrum of carbon felt as an electrode, that is, a PL line.
【図４】レドックスフロー型２次電池の構成を示す図で
ある。FIG. 4 is a diagram showing a configuration of a redox flow type secondary battery.
１ 正極液入口 ２ 負極液入口 ３ 正極液出口 ４ 負極液出口 ５ 正極 ６ 負極 ７ 隔膜 ８ 集電板または双極板 ９ Ｏリング １０ 電解液の流れる方向 １１ フレーム ５０ 光源 ５１ 第１光伝送部材（プラスチック光ファイバ） ５２ 第２光伝送部材（プラスチック光ファイバ） ５３ 分光器 ５４ 光電子倍増管（ＰＭＴ） ５５ 処理装置（パソコン） DESCRIPTION OF SYMBOLS 1 Cathode solution inlet 2 Negative solution inlet 3 Positive solution outlet 4 Negative solution outlet 5 Positive electrode 6 Negative electrode 7 Separator 8 Current collector or bipolar plate 9 O-ring 10 Flow direction of electrolyte 11 Frame 50 Light source 51 First optical transmission member (plastic) Optical fiber) 52 Second optical transmission member (plastic optical fiber) 53 Spectroscope 54 Photomultiplier tube (PMT) 55 Processing unit (PC)
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−99849（ＪＰ，Ａ) 特開 昭61−70443（ＪＰ，Ａ) 特開 平３−257352（ＪＰ，Ａ) 特開 平２−267873（ＪＰ，Ａ) 特開 昭63−102167（ＪＰ，Ａ) 高村勉，電極表面現象のその場測定, 日本金属学会会報 第15巻第１号 （1976），日本，23−33 大沢雅俊，金属電極表面化学種の変調 ラマン分光法によるｉｎ−ｓｉｔｕ測 定，日本金属学会秋期大会シンポジウム 講演予稿（1979．10），日本，106−107 (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 21/00 - 21/74 ＪＩＣＳＴファイル（ＪＯＩＳ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-99849 (JP, A) JP-A-61-70443 (JP, A) JP-A-3-257352 (JP, A) JP-A-2- 267873 (JP, A) JP-A-63-102167 (JP, A) Tsutomu Takamura, In-situ measurement of electrode surface phenomena, Bulletin of the Japan Institute of Metals, Vol. 15, No. 1 (1976), Japan, 23-33 Masatoshi Osawa, Modulation of surface chemical species of metal electrode In-situ measurement by Raman spectroscopy, Symposium of the Fall Meeting of the Japan Institute of Metals (1979.10), Japan, 106-107 (58) Fields investigated (Int. Cl. 7 , DB) Name) G01N 21/00-21/74 JICST file (JOIS)
Claims (6)
する電池セルを含む電池活物質流通型電池の電極を分析
する分析モニタ装置であって、 光を出射する光源と、 前記光源から発した光を伝送するものであり、前記電池
活物質を含む電解液が循環流通される電池セル内に位置
する電極の表面近くまで挿入され、その照射端から前記
電極の被測定部に光を照射する第１光伝送部材と、 前記被測定部から反射した反射光を、前記電極の表面近
くに位置するその受光端によって受光して、分光器まで
伝送する第２伝送部材と、 前記第２伝送部材を伝送されてきた前記反射光を分光し
て、照射光との波数差においてその反射光のスペクトル
を測定する反射光測定装置と、 前記反射光測定装置によって測定された、２つの反射光
ピークがそれぞれ位置する照射光との波数差１３６０ｃ
ｍ-1と１５８０ｃｍ-1とを含む波数差領域において、反
射光の基線の立上がり勾配を、その反射光中での蛍光の
強度を表わす指標として、その立ち上がり勾配を検知す
る手段とを備える、電極分析モニタ装置。1. An analysis monitor device for analyzing an electrode of a battery active material flow type battery including a battery cell through which a liquid or gaseous battery active material flows, comprising: a light source for emitting light; The electrolyte containing the battery active material is inserted into the vicinity of the surface of the electrode located in the battery cell in which the battery active material is circulated, and light is irradiated from the irradiation end to the measured portion of the electrode. A first light transmitting member, a second light transmitting member for receiving reflected light reflected from the portion to be measured by a light receiving end located near a surface of the electrode, and transmitting the light to a spectroscope; A reflected light measuring device that disperses the reflected light transmitted through the member and measures the spectrum of the reflected light at a wave number difference from the irradiation light; and two reflected light peaks measured by the reflected light measuring device. Is ranked The wave number difference between the irradiation light to 1360c
a means for detecting the rising gradient of the baseline of the reflected light in the wave number difference region including m -1 and 1580 cm -1 as an index representing the intensity of the fluorescence in the reflected light. Analysis monitor device.
の前記反射光のピーク強度と、前記照射光との波数差１
５８０ｃｍ-1での前記反射光のピーク強度との比を算出
する手段を備える、請求項１に記載の電極分析モニタ装
置。2. A peak intensity of the reflected light at a wave number difference of 1360 cm −1 from the irradiation light and a wave number difference of 1 from the irradiation light.
2. The electrode analysis monitor device according to claim 1, further comprising means for calculating a ratio of the reflected light to a peak intensity at 580 cm -1 .
通する電池セルを含む電池活物質流通型電池の、主要構
成部材がカーボンフェルトである電極を分析する分析モ
ニタ装置であって、 光を出射する光源と、 前記光源から発した光を伝送するものであり、前記電池
活物質を含む電解液が循環流通される電池セル内に位置
する電極の表面近くまで挿入され、その照射端から前記
電極の被測定部に光を照射する第１光伝送部材と、 前記被測定部から反射した反射光を、前記電極の表面近
くに位置するその受光端によって受光して、分光器まで
伝送する第２伝送部材と、 前記第２伝送部材を伝送されてきた前記反射光を分光し
て、照射光との波数差においてその反射光のスペクトル
を測定する反射光測定装置と、 前記照射光との波数差１３６０ｃｍ-1での前記反射光の
ピーク強度と、前記照射光との波数差１５８０ｃｍ-1で
の前記反射光のピーク強度との比の使用開始からの低下
を、前記バナジウム含有電解液との反応によって生じ
る、前記カーボンフェルトにおける電池反応の活性化度
の使用開始からの劣化とする、バナジウム電解液中での
前記カーボンフェルトの劣化検出手段とを備える、電極
分析モニタ装置。3. An analysis monitor device for analyzing an electrode whose main constituent member is carbon felt in a battery active material flowing type battery including a battery cell through which a battery active material containing vanadium ions flows, and emits light. A light source, which transmits light emitted from the light source, is inserted to near the surface of the electrode located in the battery cell in which the electrolyte containing the battery active material is circulated and circulated, from the irradiation end of the electrode A first optical transmission member that irradiates light to the measured part; and a second transmission that receives reflected light reflected from the measured part by its light receiving end located near the surface of the electrode and transmits the light to the spectroscope. A member; a reflected light measuring device that disperses the reflected light transmitted through the second transmission member and measures a spectrum of the reflected light at a wave number difference from the irradiation light; and a wave number difference 1360 from the irradiation light. and the peak intensity of the reflected light at m -1, a drop from the use of the ratio start of the peak intensity of the reflected light at the wave number difference 1580 cm -1 of the illumination light, the reaction with the vanadium-containing electrolyte Caused by
In the vanadium electrolyte, the degree of activation of the battery reaction in the carbon felt is considered to be deteriorated from the start of use .
An electrode analysis monitor device comprising: the carbon felt deterioration detection means .
する電池セルを含む電池活物質流通型電池の電極をモニ
タするモニタ方法であって、 光源から発した光を、前記電池活物質を含む電解液が循
環流通される電池セル内に位置する電極の表面近くまで
光伝送部材によって伝送し、その光伝送部材の照射端か
ら被測定部に照射し、その被測定部から反射した反射光
を、前記電極の表面近くから前記光伝送部材とは別に設
けた光伝送部材の受光端によって受光して、分光器まで
伝送して分光し、その反射光のスペクトルを照射光との
波数差において測定し、 ２つの反射光ピークがそれぞれ位置する照射光との波数
差１３６０ｃｍ-1と１５８０ｃｍ-1とを含む波数差領域
において、反射光の基線の立上がり勾配を、反射光中の
蛍光の強度の指標とし、その立ち上がり勾配の増大につ
れ、電極が劣化していることを認知する、電極分析モニ
タ方法。4. A monitoring method for monitoring an electrode of a battery active material flowing type battery including a battery cell through which a liquid or gaseous battery active material flows, wherein light emitted from a light source is transmitted to the battery active material. The transmitted electrolyte is transmitted by an optical transmission member to near the surface of the electrode located in the battery cell in which the circulating electrolyte is circulated, and the illuminated end of the optical transmission member irradiates the measured portion and the reflected light reflected from the measured portion Is received from near the surface of the electrode by a light receiving end of an optical transmission member provided separately from the optical transmission member, transmitted to a spectroscope to be separated, and the spectrum of the reflected light is represented by the wave number difference from the irradiation light. measured in the wave number difference region including the wave number difference 1360 cm -1 and 1580 cm -1 of the illumination light two reflected light peak is located respectively, the rising slope of the baseline of the reflected light, the intensity of fluorescence in the reflected light Indicators and , As the increase in the rising slope, recognizes that the electrode is degraded, the electrode analytical monitoring method.
の前記反射光のピーク強度と、前記照射光との波数差１
５８０ｃｍ-1での前記反射光のピーク強度との比を算出
し、そのピーク強度比が低下するにつれ、電極が劣化し
ていることを認知する、請求項４に記載の電極分析モニ
タ方法。5. A peak intensity of the reflected light at a wave number difference of 1360 cm −1 from the irradiation light and a wave number difference of 1 from the irradiation light.
5. The electrode analysis monitoring method according to claim 4, wherein a ratio with respect to the peak intensity of the reflected light at 580 cm -1 is calculated, and it is recognized that the electrode is deteriorated as the peak intensity ratio decreases.
する電池セルを含む電池活物質流通型電池の、主要構成
部材がカーボンフェルトである電極をモニタするモニタ
方法であって、 光源から発した光を、前記電池活物質を含む電解液が循
環流通される電池セル内に位置する電極の表面近くまで
光伝送部材によって伝送し、その光伝送部材の照射端か
ら被測定部に照射し、その被測定部から反射した反射光
を、前記電極の表面近くから前記光伝送部材とは別に設
けた光伝送部材の受光端によって受光して、分光器まで
伝送して分光し、その反射光のスペクトルを照射光との
波数差において測定し、 前記照射光との波数差１３６０ｃｍ-1での前記反射光の
ピーク強度と、前記照射光との波数差１５８０ｃｍ-1で
の前記反射光のピーク強度との比の使用開始からの低下
を、前記電解液との反応によって生じる前記カーボンフ
ェルトにおける電池反応の活性化度の使用開始からの劣
化と評価して、その電解液中での前記カーボンフェルト
における電池反応の活性化度の劣化状態を検出する、電
極分析モニタ方法。6. A monitoring method for monitoring an electrode whose main constituent member is carbon felt in a battery active material flowing type battery including a battery cell through which a liquid or gaseous battery active material flows, comprising: The transmitted light is transmitted by an optical transmission member to near the surface of an electrode located in a battery cell in which an electrolyte solution containing the battery active material is circulated and radiated to an object to be measured from an irradiation end of the optical transmission member. The reflected light reflected from the measured portion is received by a light receiving end of an optical transmission member provided separately from the surface of the electrode from near the surface of the electrode, transmitted to a spectroscope to be separated, and separated. spectra were measured in the wave number difference between the irradiation light, the peak intensity of the reflected light at the wave number difference 1360 cm -1 of the illumination light, the peak intensity of the reflected light at the wave number difference 1580 cm -1 of the illumination light And the ratio A decrease from start of use, to evaluate the deterioration of the start of use of the active degree of the battery reaction in the carbon felt produced by the reaction between the electrolyte, the carbon felt at the electrolyte
An electrode analysis monitoring method for detecting a deterioration state of the degree of activation of a battery reaction in the method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37209298A JP3260331B2 (en) | 1998-12-28 | 1998-12-28 | Electrode analysis monitoring device and monitoring method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37209298A JP3260331B2 (en) | 1998-12-28 | 1998-12-28 | Electrode analysis monitoring device and monitoring method |
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| Publication Number | Publication Date |
|---|---|
| JP2000193593A JP2000193593A (en) | 2000-07-14 |
| JP3260331B2 true JP3260331B2 (en) | 2002-02-25 |
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ID=18499841
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP37209298A Expired - Fee Related JP3260331B2 (en) | 1998-12-28 | 1998-12-28 | Electrode analysis monitoring device and monitoring method |
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| JP (1) | JP3260331B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7855005B2 (en) * | 2007-02-12 | 2010-12-21 | Deeya Energy, Inc. | Apparatus and methods of determination of state of charge in a redox flow battery |
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1998
- 1998-12-28 JP JP37209298A patent/JP3260331B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 大沢雅俊，金属電極表面化学種の変調ラマン分光法によるｉｎ−ｓｉｔｕ測定，日本金属学会秋期大会シンポジウム講演予稿（１９７９．１０），日本，１０６−１０７ |
| 高村勉，電極表面現象のその場測定，日本金属学会会報 第１５巻第１号（１９７６），日本，２３−３３ |
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