JP2020016479A - Device and method for evaluating electrode and battery kit - Google Patents
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- 239000000758 substrate Substances 0.000 claims abstract description 58
- 239000004065 semiconductor Substances 0.000 claims abstract description 53
- 238000011156 evaluation Methods 0.000 claims abstract description 37
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- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 230000006399 behavior Effects 0.000 abstract 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 19
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
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- 239000007773 negative electrode material Substances 0.000 description 2
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
本発明は、二次電池の電極の評価に用いる電極評価装置、電極評価方法及び電池キットに関する。 The present invention relates to an electrode evaluation device, an electrode evaluation method, and a battery kit used for evaluating electrodes of a secondary battery.
リチウムイオン二次電池において、動作時の正極材料の構造変化を分析する方法として、in-situマイクロXAFS（X-ray absorption fine structure）手法が提案されている（例えば、非特許文献１参照。）。この手法では、正極材料に対して高強度のＸ線を照射して、原子の価数の変化を評価しており、正極材料中のリチウムイオンが、正極材料の構造とどのように結合し、さらには不可逆な反応となるかを解明するための優れた手法として知られている。 In a lithium ion secondary battery, an in-situ micro XAFS (X-ray absorption fine structure) technique has been proposed as a method of analyzing a structural change of a positive electrode material during operation (for example, see Non-Patent Document 1). . In this method, the positive electrode material is irradiated with high-intensity X-rays to evaluate the change in the valence of atoms, and how the lithium ions in the positive electrode material combine with the structure of the positive electrode material, Furthermore, it is known as an excellent method for elucidating whether or not an irreversible reaction occurs.
しかしながら、この手法では高強度のＸ線が必要となるため、SPring-8等のような放射光施設を利用する必要があり、簡便に利用できる手法ではなかった。 However, since this technique requires high-intensity X-rays, it is necessary to use a synchrotron radiation facility such as SPring-8, which is not a technique that can be easily used.
本発明者の一人は、パルスレーザー光を用いた物質検出装置であって、半導体基板の表面に物質感応膜を設けて、この半導体基板の裏面にパルスレーザー光を照射するとともに、半導体基板から発生する電磁波を検出することで、物質感応膜に接触している物質の有無を検出可能とした物質検出装置を提案している（例えば、特許文献１参照。）。 One of the present inventors is a substance detection device using pulsed laser light, in which a substance sensitive film is provided on the surface of a semiconductor substrate, and the backside of the semiconductor substrate is irradiated with the pulsed laser light and generated from the semiconductor substrate. There has been proposed a substance detection device capable of detecting the presence or absence of a substance that is in contact with a substance-sensitive film by detecting an electromagnetic wave (see, for example, Patent Document 1).
本発明者らは、上記のパルスレーザー光を用いた物質検出装置を利用することで、リチウムイオン二次電池等の二次電池における電極近傍での振る舞いを観察できないかと考えて検討を行った。 The present inventors have studied whether the use of the above-described substance detection device using pulsed laser light can observe the behavior in the vicinity of an electrode in a secondary battery such as a lithium ion secondary battery.
しかしながら、二次電池はレーザー光に対して不透明な金属製のケースでパッケージされているため、そのままではレーザー光を計測面の近傍に照射することができなかった。 However, since the secondary battery is packaged in a metal case that is opaque to laser light, the laser light could not be irradiated near the measurement surface as it is.
そこで、ケースに観察窓を設けることで観察可能となるのではないかと考え、本発明を成すに至ったものである。 Therefore, the present inventors thought that it would be possible to observe the image by providing an observation window in the case, and thus completed the present invention.
本発明の電極評価装置は、二次電池の電極にフェムト秒レーザー光を照射することで発生させた電磁波を検出して電極を評価する電極評価装置であって、電極は、フェムト秒レーザー光が透過する透明基板を備え、この透明電極には絶縁膜で被覆された半導体膜を設けている電極評価装置である。 The electrode evaluation device of the present invention is an electrode evaluation device that evaluates an electrode by detecting an electromagnetic wave generated by irradiating a femtosecond laser beam to an electrode of a secondary battery, and the electrode is a femtosecond laser beam. The electrode evaluation apparatus includes a transparent substrate that transmits light, and a semiconductor film covered with an insulating film is provided on the transparent electrode.
さらに、本発明の電極評価装置では、以下の点にも特徴を有するものである。
（１）透明基板は、電極を構成する金属製のケースに設けた開口部分に装着してこの開口を閉塞するとともに、内側面に半導体膜と絶縁膜を形成していること。
（２）絶縁膜が形成された透明基板の内側面を金属膜で被覆して集電極とし、この集電極をケースに電気的に接続していること。
（３）半導体膜は平板状の透明基板の一方の平面上に形成し、この半導体膜の上面に絶縁膜を形成するとともに、透明基板の側面に絶縁性の樹脂を塗布して前記半導体膜を絶縁被覆していること。
Further, the electrode evaluation apparatus of the present invention has the following features.
(1) The transparent substrate is mounted on an opening provided in a metal case constituting an electrode to close the opening, and a semiconductor film and an insulating film are formed on the inner surface.
(2) The inner surface of the transparent substrate on which the insulating film is formed is covered with a metal film to form a collecting electrode, and the collecting electrode is electrically connected to the case.
(3) A semiconductor film is formed on one flat surface of a flat transparent substrate, an insulating film is formed on the upper surface of the semiconductor film, and an insulating resin is applied on side surfaces of the transparent substrate to form the semiconductor film. Insulation coating.
また、本発明の電極評価方法では、二次電池の電極にフェムト秒レーザー光を照射することで発生させた電磁波を検出して電極を評価する電極評価方法であって、電極にはフェムト秒レーザー光を透過させる透明基板を設けるとともに、この透明基板の内側面には半導体層を設け、この半導体層を絶縁膜で被覆するとともに集電極となる金属膜で被覆しているものである。 Further, the electrode evaluation method of the present invention is an electrode evaluation method for detecting an electromagnetic wave generated by irradiating a femtosecond laser beam to an electrode of a secondary battery and evaluating the electrode, wherein the electrode has a femtosecond laser. A transparent substrate that transmits light is provided, a semiconductor layer is provided on the inner surface of the transparent substrate, and the semiconductor layer is covered with an insulating film and covered with a metal film serving as a collecting electrode.
また、本発明の電池キットでは、嵌合させることで一体化される第１のケースと第２のケースとを有するボタン電池型の電池キットにおいて、第１のケースには、電極部分に開口を設けるとともに、この開口を透明基板で閉塞し、この透明基板の内側面には、絶縁膜で被覆された半導体膜と、絶縁膜を被覆するとともに第１のケースと電気的に接続する金属膜を設けているものである。 Further, in the battery kit of the present invention, in a button battery type battery kit having a first case and a second case which are integrated by being fitted together, the first case has an opening in an electrode portion. At the same time, the opening is closed with a transparent substrate, and a semiconductor film covered with an insulating film and a metal film that covers the insulating film and is electrically connected to the first case are formed on the inner surface of the transparent substrate. It is provided.
さらに、本発明の電池キットでは、半導体膜は平板状の透明基板の一方の平面上に形成し、この半導体膜の上面に絶縁膜を形成するとともに、透明基板の側面に絶縁性の樹脂を塗布して半導体膜を絶縁被覆していることにも特徴を有するものである。 Further, in the battery kit of the present invention, the semiconductor film is formed on one flat surface of the flat transparent substrate, an insulating film is formed on the upper surface of the semiconductor film, and an insulating resin is applied on the side surface of the transparent substrate. It is also characterized in that the semiconductor film is insulated and coated.
本発明によれば、電池内の電極材料のインピーダンスや電位の変化をin-site解析でき、特に、フェムト秒レーザー光を用いていることから電池内の電極材料の一粒子ごとに解析することができ、電池内で生じている反応を詳細に評価することができる。 According to the present invention, changes in the impedance and potential of the electrode material in the battery can be analyzed in-site, and in particular, since femtosecond laser light is used, analysis can be performed for each particle of the electrode material in the battery. The reaction occurring in the battery can be evaluated in detail.
本発明の電極評価装置及び電極評価方法では、二次電池の電極にフェムト秒レーザー光を照射することで発生させた電磁波を検出して電極を観察し、評価するものである。 In the electrode evaluation device and the electrode evaluation method of the present invention, an electromagnetic wave generated by irradiating the electrode of the secondary battery with a femtosecond laser beam is detected to observe and evaluate the electrode.
電極評価装置は、図１に模式的に示すように、解析及び制御を行うための解析制御部20と、フェムト秒レーザー光Ｌを照射する光源30と、このフェムト秒レーザー光Ｌが照射される電池10が載置されるとともに、この電池10を水平方向に移動させる走査台40と、フェムト秒レーザー光Ｌの照射によって電池10の電極部分で発生した電磁波Ｄを検出する検出器50とを設けている。図１中、符号60は光源30から照射されたフェムト秒レーザー光を集光させる集光レンズである。 As shown schematically in FIG. 1, the electrode evaluation apparatus includes an analysis control unit 20 for performing analysis and control, a light source 30 for irradiating the femtosecond laser light L, and irradiating the femtosecond laser light L. A battery 10 is mounted, and a scanning table 40 for horizontally moving the battery 10 and a detector 50 for detecting an electromagnetic wave D generated at an electrode portion of the battery 10 by irradiation of the femtosecond laser light L are provided. ing. In FIG. 1, reference numeral 60 denotes a condenser lens for condensing the femtosecond laser light emitted from the light source 30.
光源30は、フェムト秒レーザー光Ｌを照射可能としたレーザー光源である。本実施形態では、フェムト秒レーザー光Ｌは、３００ナノメートル（３００ｎｍ＝０．３μｍ）以上、２ミクロン（２μｍ）以下の波長となっているものであり、時間平均のエネルギーが０．１ｍＷ以上、１０Ｗ以下であり、パルス幅が１フェムト秒（１ｆｓ＝０．００１ｐｓ）以上、１０ピコ秒（１０ｐｓ）以下のパルス光としている。 The light source 30 is a laser light source that can emit the femtosecond laser light L. In the present embodiment, the femtosecond laser light L has a wavelength of not less than 300 nanometers (300 nm = 0.3 μm) and not more than 2 microns (2 μm), and has a time average energy of 0.1 mW or more, The pulsed light is 10 W or less, and the pulse width is 1 femtosecond (1 fs = 0.001 ps) or more and 10 picoseconds (10 ps) or less.
フェムト秒レーザー光Ｌのような時間の幅の小さなパルスレーザー光を用いることにより、後述する半導体膜において電磁波を生じさせることができ、特に高い時間分解能による時間分解計測が可能となり、この半導体膜と絶縁膜を介して接している物質の反応をリアルタイムで観測することができる。なお、半導体膜に熱的影響を及ぼさない最大のパルス幅は、約１０ピコ秒と見積ることができる。このような、フェムト秒レーザーＬを用いることで観察対象に生じるレーザー光による加熱の影響を最小限に抑えることもでき、観察対象の熱破壊を抑制できる。 By using a pulse laser light having a small time width such as the femtosecond laser light L, an electromagnetic wave can be generated in a semiconductor film described later, and time-resolved measurement with a particularly high time resolution becomes possible. The reaction of a substance in contact with the insulating film can be observed in real time. Note that the maximum pulse width that does not thermally affect the semiconductor film can be estimated to be about 10 picoseconds. By using such a femtosecond laser L, it is possible to minimize the influence of heating by the laser light generated on the observation target, and it is possible to suppress thermal destruction of the observation target.
走査台40は、いわゆるＸ−Ｙテーブルであって、走査台40を水平方向に移動させることで、走査台40上に載置した電池10に対して、光源30から照射されたフェムト秒レーザー光Ｌを走査させている。走査台40には、電池10をそのまま載置させるだけでなく、電池10のサイクル試験を行うためのソケットを装着して、このソケットを介して電池10を載置させてもよい。 The scanning table 40 is a so-called XY table, and by moving the scanning table 40 in the horizontal direction, the femtosecond laser light emitted from the light source 30 to the battery 10 mounted on the scanning table 40 L is scanned. In addition to mounting the battery 10 as it is on the scanning table 40, a socket for performing a cycle test of the battery 10 may be mounted, and the battery 10 may be mounted via the socket.
本実施形態では、走査台40を用いることでフェムト秒レーザー光Ｌの走査を行っているが、光源30と電池10のと間に揺動または回転するミラー等を設けてフェムト秒レーザー光Ｌを走査させてもよいし、光源30自体を揺動させることでフェムト秒レーザー光Ｌを走査させてもよい。なお、フェムト秒レーザー光Ｌの電池10に設けた半導体膜に対する入射角は、フェムト秒レーザー光Ｌの波長が半導体膜に最も吸収される角度とすることが好ましく、その点では走査台40を用いることが好ましい。 In the present embodiment, the scanning of the femtosecond laser light L is performed by using the scanning table 40. However, a mirror or the like that swings or rotates is provided between the light source 30 and the battery 10 so that the femtosecond laser light L is scanned. The scanning may be performed, or the femtosecond laser beam L may be scanned by swinging the light source 30 itself. Note that the incident angle of the femtosecond laser light L with respect to the semiconductor film provided in the battery 10 is preferably an angle at which the wavelength of the femtosecond laser light L is most absorbed by the semiconductor film. Is preferred.
検出器50は、電磁波検出ボローメーターあるいは半導体光スイッチ等を備えており、フェムト秒レーザー光Ｌの照射によって電池10の半導体膜で生じた電磁波Ｄを検出している。ここで、電磁波Ｄは、フェムト秒レーザー光Ｌがパルス状のレーザー光であることからパルス状となっており、検出器50では、電磁波Ｄの電場振幅の時間波形に対応した時間的に変化する電圧信号に変換して、出力信号としている。 The detector 50 includes an electromagnetic wave detection bolometer or a semiconductor optical switch, and detects the electromagnetic wave D generated in the semiconductor film of the battery 10 by the irradiation of the femtosecond laser light L. Here, the electromagnetic wave D is pulsed because the femtosecond laser light L is a pulsed laser light, and the detector 50 changes with time corresponding to the time waveform of the electric field amplitude of the electromagnetic wave D. The output signal is converted into a voltage signal.
解析制御部20は、本実施形態ではパーソナルコンピュータで構成し、光源30及び走査台40の制御を行うとともに、検出器50から入力された信号から電池10内の電極物質の状態等を検出可能としている。 In the present embodiment, the analysis control unit 20 is configured by a personal computer, controls the light source 30 and the scanning table 40, and detects the state of the electrode material in the battery 10 from the signal input from the detector 50. I have.
以下において、電池10の構成について詳説する。電池10は、いわゆるボタン電池であって、図２に示すように、金属製の第１ケース11と第２ケース12とを備えており、第１ケース11と第２ケース12を互いに嵌合させることで一体化することとしている。図２における第１ケース11と第２ケース12との嵌合形態は、嵌合連結されることを模式的に示したに過ぎず、適宜の嵌合形態としてよい。なお、第１ケース11と第２ケース12とは、電池キットとして一般的に販売されているものを用いることができ、後述するように第１ケース11に開口11aを形成することで、電極へのフェムト秒レーザー光の照射によって電磁波を生じさせることとしている。 Hereinafter, the configuration of the battery 10 will be described in detail. The battery 10 is a so-called button battery, and includes a first case 11 and a second case 12 made of metal, as shown in FIG. 2, and the first case 11 and the second case 12 are fitted to each other. It is decided that they will be integrated. The form of fitting of the first case 11 and the second case 12 in FIG. 2 merely schematically shows that they are fitted and connected, and may be any suitable form of fitting. As the first case 11 and the second case 12, those generally sold as a battery kit can be used. By forming an opening 11a in the first case 11 as described later, Irradiation of femtosecond laser light produces electromagnetic waves.
第２ケース12には、絶縁体12bを介して装着された電極端子12aが設けられている。第１ケース11は、それ自体でもう一方の電極端子となっている。 The second case 12 is provided with an electrode terminal 12a mounted via an insulator 12b. The first case 11 itself is the other electrode terminal.
第１ケース11には、電極面となる平面部分に開口11aを形成しており、この開口11aを透明基板13で閉塞している。この透明基板13は平板状の透明な石英板であり、フェムト秒レーザー光Ｌ及び電磁波Ｄに対して透明となっている。透明基板13は絶縁体である。 In the first case 11, an opening 11a is formed in a plane portion serving as an electrode surface, and the opening 11a is closed by a transparent substrate 13. The transparent substrate 13 is a flat transparent quartz plate, and is transparent to femtosecond laser light L and electromagnetic waves D. The transparent substrate 13 is an insulator.
透明基板13の内側面、すなわち、第１ケース11の開口11aとは反対側の面には、第１絶縁膜15aで被覆された半導体膜14と、第１絶縁膜15aを被覆するとともに第１ケース11と電気的に接続する第１金膜16aを設けている。 The inner surface of the transparent substrate 13, that is, the surface of the first case 11 opposite to the opening 11a is covered with the first insulating film 15a and the first insulating film 15a. A first gold film 16a electrically connected to the case 11 is provided.
特に、透明基板13の側面には、絶縁性の樹脂を塗布することで形成した第２絶縁膜15bを設けて、半導体膜14を絶縁被覆している。図２中、符号17は、半導体膜14、絶縁膜15a及び第１金膜16aが設けられた透明基板13を第１ケース11に固定装着するための接着層である。 In particular, a second insulating film 15b formed by applying an insulating resin is provided on the side surface of the transparent substrate 13, and the semiconductor film 14 is insulated. In FIG. 2, reference numeral 17 denotes an adhesive layer for fixing the transparent substrate 13 provided with the semiconductor film 14, the insulating film 15a and the first gold film 16a to the first case 11.
このように、絶縁被覆された半導体膜14を設けた透明基板13を装着した開口11aが形成された第１ケース11とすることで、電極へのフェムト秒レーザー光Ｌの照射は半導体膜14へのフェムト秒レーザー光Ｌの照射となり、半導体膜14において電磁波Ｄを生じさせることができる。この電磁波Ｄ検出し、解析することで、電池10の内部状態を評価することができる。 As described above, the first case 11 in which the opening 11a is provided with the transparent substrate 13 provided with the insulating-coated semiconductor film 14 is formed, so that the semiconductor film 14 is irradiated with the femtosecond laser light L to the electrodes. Is irradiated with the femtosecond laser light L, and an electromagnetic wave D can be generated in the semiconductor film 14. By detecting and analyzing the electromagnetic wave D, the internal state of the battery 10 can be evaluated.
以下において、本発明の電極評価装置の被検体となる電池10の作製方法を説明する。なお、説明の便宜上、図２に示した電池ケースの上下を反転させた状態として説明する。 Hereinafter, a method for producing the battery 10 as an object of the electrode evaluation device of the present invention will be described. For convenience of explanation, the description will be made assuming that the battery case shown in FIG. 2 is turned upside down.
図３に示すように、平板状の透明基板13の一方の平面に、ＣＶＤ（Chemical Vapor Deposition）法を用いて半導体膜14を形成し、この半導体膜15を第一絶縁膜15aで被覆している。なお、説明の便宜上、透明基板13において半導体膜14が形成されている平面を「表面」と呼び、その反対側の平面を「裏面」と呼ぶこととする。 As shown in FIG. 3, a semiconductor film 14 is formed on one flat surface of a flat transparent substrate 13 by using a CVD (Chemical Vapor Deposition) method, and the semiconductor film 15 is covered with a first insulating film 15a. I have. For convenience of description, the plane on which the semiconductor film 14 is formed on the transparent substrate 13 is referred to as “front side”, and the plane on the opposite side is referred to as “back side”.
半導体膜14は、本実施形態ではシリコン膜であるが、シリコン膜に限定するものではなく適宜の半導体膜とすることができる。また、本実施形態では、半導体膜14の厚みは約１５０ｎｍとしているが、フェムト秒レーザー光Ｌの照射によって効果的に電磁波Ｄが生じる厚みとしてよい。 The semiconductor film 14 is a silicon film in the present embodiment, but is not limited to the silicon film, and may be an appropriate semiconductor film. In the present embodiment, the thickness of the semiconductor film 14 is set to about 150 nm, but may be set to a thickness at which the electromagnetic wave D is effectively generated by the irradiation of the femtosecond laser light L.
第一絶縁膜15aは、半導体膜14を酸化させて形成した酸化膜としている。図３では、説明の便宜上、透明基板13と半導体膜14と第一絶縁膜15aの厚みはそれぞれ実際の厚みの比率を示してはおらず、半導体膜14及び第一絶縁膜15aは、透明基板13と比較して十分薄くなっている。以下においても同様である。 The first insulating film 15a is an oxide film formed by oxidizing the semiconductor film. In FIG. 3, for convenience of explanation, the thicknesses of the transparent substrate 13, the semiconductor film 14, and the first insulating film 15a do not show the respective ratios of the actual thickness, and the semiconductor film 14 and the first insulating film 15a It is thin enough compared to. The same applies to the following.
第一絶縁膜15aの形成後、図４に示すように、透明基板13の側面に絶縁性の樹脂を塗布して第２絶縁膜15bを形成している。このように絶縁性の樹脂を透明基板13の側面に塗布することで、透明基板13に形成された半導体膜14の側面を確実に絶縁被覆している。図４では、説明の便宜上、半導体膜14の側面を選択的に被覆しているように示しているが、実際には、半導体膜14が極めて薄いため、透明基板13の側面に樹脂の塗布を行って第２絶縁膜15bを形成している。本実施形態では、第２絶縁膜15bとなる絶縁性の樹脂としては、エポキシ樹脂を用いている。 After the formation of the first insulating film 15a, as shown in FIG. 4, an insulating resin is applied to the side surface of the transparent substrate 13 to form the second insulating film 15b. By applying the insulating resin to the side surface of the transparent substrate 13 in this way, the side surface of the semiconductor film 14 formed on the transparent substrate 13 is surely insulated. In FIG. 4, for convenience of explanation, the side surface of the semiconductor film 14 is shown as being selectively covered. However, in practice, since the semiconductor film 14 is extremely thin, a resin is applied to the side surface of the transparent substrate 13. As a result, the second insulating film 15b is formed. In the present embodiment, an epoxy resin is used as the insulating resin to be the second insulating film 15b.
第２絶縁膜15bを形成することで半導体膜14を絶縁被覆した後、図５に示すように、半導体膜14が設けられた透明基板13には、表面にスパッタリングによって第１金膜16aを形成している。 After insulatingly covering the semiconductor film 14 by forming the second insulating film 15b, a first gold film 16a is formed on the surface of the transparent substrate 13 provided with the semiconductor film 14 by sputtering, as shown in FIG. are doing.
また、透明基板13において、後述するように第１ケース11に装着する際に、第１ケース11との導電性を高めるために、透明基板13の裏面にも金膜を部分的に形成している。すなわち、図６に示すように、透明基板13の裏面には第１レジストR1を塗布して、図７に示すように、透明基板13の裏面にもスパッタリングによって補助金膜16a'を形成し、第１レジストR1を除去することで、透明基板13の裏面に補助金膜16a'を部分的に形成している。図８に示すように、以下において、この残存させた補助金膜16a'も第１金膜16aの一部として説明することとする。 In addition, when the transparent substrate 13 is mounted on the first case 11 as described later, a gold film is partially formed on the back surface of the transparent substrate 13 in order to increase conductivity with the first case 11. I have. That is, as shown in FIG. 6, the first resist R1 is applied to the back surface of the transparent substrate 13, and as shown in FIG. 7, the auxiliary gold film 16a 'is formed also on the back surface of the transparent substrate 13 by sputtering. By removing the first resist R1, the auxiliary gold film 16a 'is partially formed on the back surface of the transparent substrate 13. As shown in FIG. 8, the remaining auxiliary gold film 16a 'will be described below as a part of the first gold film 16a.
上述したように第１金膜16aを形成した後、図９に示すように、透明基板13の表面側に二次電池における正極活物質を塗布して第１活物質膜Ｐを形成している。なお、正極活物質ではなく、負極活物質を塗布してもよい。正極活物質の場合には、LiCoO2等の活物質が用いられ、昨今の機能向上を目的とした活物質の探索の成果物を塗布することとなる。 After forming the first gold film 16a as described above, as shown in FIG. 9, the positive electrode active material of the secondary battery is applied to the surface side of the transparent substrate 13 to form the first active material film P. . Note that a negative electrode active material may be applied instead of the positive electrode active material. In the case of a positive electrode active material, an active material such as LiCoO 2 is used, and a product obtained by searching for an active material for the purpose of improving its function recently is applied.
第１活物質膜Ｐの形成後、図１０及び図１１に示すように、第１活物質膜Ｐが形成された透明基板13を第１ケース11に装着している。上述したように、第１ケース11には開口11aを形成しており、透明基板13の裏面において第１金膜16aで被覆されていない部分をこの開口11aに合わせながら透明基板13を第１ケース11に載置している。さらに、図１１に示すように、透明基板13の周囲に接着剤を塗布して接着層17を形成することで、透明基板13を第１ケース11に装着している。 After the formation of the first active material film P, the transparent substrate 13 on which the first active material film P is formed is mounted on the first case 11 as shown in FIGS. As described above, the opening 11a is formed in the first case 11, and the portion of the back surface of the transparent substrate 13 that is not covered with the first gold film 16a is aligned with the opening 11a so that the transparent substrate 13 is placed in the first case 11. It is placed on 11. Further, as shown in FIG. 11, the transparent substrate 13 is mounted on the first case 11 by applying an adhesive around the transparent substrate 13 to form an adhesive layer 17.
透明基板13を第１ケース11に装着した後、図１２に示すように、第１活物質膜Ｐを第２レジストR2で被覆して、透明基板13の表面側にスパッタリングを行って第２金膜16bを形成している。この第２金膜16bは、第１活物質膜Ｐの側面を金属膜で被覆するためのものであり、本実施形態では、この第２金膜16bと第１金膜16aとで集電極を構成することとしている。第１金膜16aだけで集電極としてもよいが、第２金膜16bを設けることで、第１ケース11との間での生じる導電不良を防止できる。 After attaching the transparent substrate 13 to the first case 11, the first active material film P is covered with a second resist R2 as shown in FIG. A film 16b is formed. The second gold film 16b is for covering the side surface of the first active material film P with a metal film. In the present embodiment, the second gold film 16b and the first gold film 16a form a collecting electrode. It is configured. The first gold film 16a alone may be used as a collecting electrode. However, by providing the second gold film 16b, it is possible to prevent conduction failure occurring with the first case 11.
第２金膜16bを形成して第２レジストR2を除去した後、図１３に示すように、第２レジストR2の除去にともなって露出した第１活物質膜Ｐの上面に電解質層Ｑを形成し、さらに、図１４に示すように、電解質層Ｑの上面に二次電池における負極活物質を塗布して第２活物質膜Ｍを形成して、この第２活物質膜Ｍの上面に金属製の接続電極18を載置している。 After forming the second gold film 16b and removing the second resist R2, as shown in FIG. 13, an electrolyte layer Q is formed on the upper surface of the first active material film P exposed with the removal of the second resist R2. Further, as shown in FIG. 14, a negative electrode active material of a secondary battery is applied on the upper surface of the electrolyte layer Q to form a second active material film M, and a metal is formed on the upper surface of the second active material film M. A connection electrode 18 made of metal is mounted.
第２活物質膜Ｍの上面に金属製の接続電極18を載置した後、図１５に示すように、接続電極18を第２ケース12の電極端子12aに当接させながら第２ケース12を第１ケース11に嵌合させて一体化し、電池としている。 After placing the metal connection electrode 18 on the upper surface of the second active material film M, as shown in FIG. 15, the connection electrode 18 is brought into contact with the electrode terminal 12a of the second case 12 and the second case 12 is The battery is fitted and integrated into the first case 11 to form a battery.
このように、本発明の電池キットでは、第１ケース11において透明基板13による窓が設けられていることとなり、しかも、透明基板13には半導体膜14を形成していることで、半導体膜14に向けてフェムト秒レーザー光Ｌを照射することにより電磁波Ｄを生じさせることができる。この電磁波Ｄを検出することで、第一絶縁膜15a及び第１金膜16aを介して積層された第１活物質膜Ｐの状態を検出することができ、第１活物質膜Ｐの評価を可能とすることができる。 As described above, in the battery kit of the present invention, the window formed by the transparent substrate 13 is provided in the first case 11, and the semiconductor film 14 is formed on the transparent substrate 13. The electromagnetic wave D can be generated by irradiating the femtosecond laser beam L toward the. By detecting this electromagnetic wave D, the state of the first active material film P laminated via the first insulating film 15a and the first gold film 16a can be detected, and the evaluation of the first active material film P can be performed. Can be possible.
図１６（ａ）は、実際に第１ケース11の開口11aから透明基板13を見た状態であり、半導体膜14、第一絶縁膜15a及び第１金膜16aがそれぞれ薄いことから、第１活物質膜Ｐが見えていることを示している。 FIG. 16A shows a state in which the transparent substrate 13 is actually viewed from the opening 11a of the first case 11, and since the semiconductor film 14, the first insulating film 15a, and the first gold film 16a are thin, respectively, This shows that the active material film P is visible.
図１６（ｂ）は、本発明の電極評価装置で電池10にフェムト秒レーザー光Ｌを照射して生じた電磁波Ｄを検出して得られた結果である。特に、3.9Vでの充電状態であって、第１活物質膜Ｐにおいて電位が高い領域と、電位が低い領域とをそれぞれ検出することができており、二次電池の性能向上の検討に用いるデータとすることができる。 FIG. 16B shows a result obtained by detecting the electromagnetic wave D generated by irradiating the battery 10 with the femtosecond laser light L by the electrode evaluation apparatus of the present invention. In particular, in the state of charge at 3.9 V, a region where the potential is high and a region where the potential is low in the first active material film P can be respectively detected, and this is used for studying the performance improvement of the secondary battery. Can be data.
特に、例えば充放電試験の前後で比較することで、状態変化の有無を確認することができ、劣化や異常動作等の原因究明に用いることができる。 In particular, for example, by comparing before and after the charge / discharge test, the presence or absence of a state change can be confirmed, which can be used for investigating causes such as deterioration and abnormal operation.
10 電池
11 第１ケース
11a 開口
12 第２ケース
12a 電極端子
12b 絶縁体
13 透明基板
14 半導体膜
15a 第１絶縁膜
15b 第２絶縁膜
16a 第１金膜
17 接着層
20 解析制御部
30 光源
40 走査台
50 検出器
60 集光レンズ
Ｌ フェムト秒レーザー光
Ｄ 電磁波
10 batteries
11 Case 1
11a opening
12 Second case
12a Electrode terminal
12b insulator
13 Transparent substrate
14 Semiconductor film
15a First insulating film
15b Second insulating film
16a 1st gold film
17 Adhesive layer
20 Analysis control unit
30 light sources
40 scan table
50 detector
60 Condensing lens L Femtosecond laser light D Electromagnetic wave
Claims (7)
前記電極は、前記フェムト秒レーザー光が透過する透明基板を備え、
この透明電極には絶縁膜で被覆された半導体膜を設けている電極評価装置。 An electrode evaluation device for detecting an electromagnetic wave generated by irradiating a femtosecond laser beam to an electrode of a secondary battery and evaluating the electrode,
The electrode includes a transparent substrate through which the femtosecond laser light passes,
An electrode evaluation device in which a semiconductor film covered with an insulating film is provided on the transparent electrode.
前記電極には前記フェムト秒レーザー光を透過させる透明基板を設けるとともに、この透明基板の内側面には半導体層を設け、この半導体層を絶縁膜で被覆するとともに集電極となる金属膜で被覆している電極評価方法。 An electrode evaluation method for detecting an electromagnetic wave generated by irradiating a femtosecond laser beam to an electrode of a secondary battery and evaluating the electrode,
A transparent substrate that transmits the femtosecond laser light is provided on the electrode, and a semiconductor layer is provided on the inner surface of the transparent substrate. Electrode evaluation method.
前記第１のケースには、電極部分に開口を設けるとともに、この開口を透明基板で閉塞し、
この透明基板の内側面には、絶縁膜で被覆された半導体膜と、前記絶縁膜を被覆するとともに前記第１のケースと電気的に接続する金属膜を設けている電池キット。 In a button battery type battery kit having a first case and a second case integrated by fitting,
In the first case, an opening is provided in the electrode portion, and the opening is closed with a transparent substrate,
A battery kit comprising: a semiconductor film covered with an insulating film; and a metal film that covers the insulating film and is electrically connected to the first case, on an inner surface of the transparent substrate.
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