JP4902235B2 - Electrochemical cell - Google Patents

Electrochemical cell Download PDF

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JP4902235B2
JP4902235B2 JP2006076681A JP2006076681A JP4902235B2 JP 4902235 B2 JP4902235 B2 JP 4902235B2 JP 2006076681 A JP2006076681 A JP 2006076681A JP 2006076681 A JP2006076681 A JP 2006076681A JP 4902235 B2 JP4902235 B2 JP 4902235B2
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reference electrode
electrode
pressing
electrochemical cell
working electrode
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JP2007257850A (en
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平 相田
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Daihatsu Motor Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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

Description

本発明は、電気化学セル、詳しくは、３電極方式の電気化学セルに関する。   The present invention relates to an electrochemical cell, and more particularly to a three-electrode electrochemical cell.

従来より、ハイブリッド車両や燃料電池車両に搭載される蓄電デバイスとして、リチウムイオン電池やハイブリッドキャパシタなどが利用されている。
一般に、これらの蓄電デバイスの性能評価においては、作用極および対極の他に参照極を組み合わせた３電極式電気化学セルなどが用いられる。
このような電気化学セルとして、たとえば、少なくとも１組の作用極と対極を、セパレータを介して対向配置してなる電極体、該電極体を収納するための収納容器および該収納容器の蓋部からなる電気化学セルにおいて、加圧手段をさらに備え、該加圧手段により該蓋部を該収納容器側に押圧することにより該収納容器が密閉されるものが提案されている（たとえば、特許文献１参照）。
特開２００３−１０９６５３号公報 Conventionally, lithium ion batteries, hybrid capacitors, and the like have been used as power storage devices mounted on hybrid vehicles and fuel cell vehicles.
Generally, in the performance evaluation of these electricity storage devices, a three-electrode electrochemical cell in which a reference electrode is combined in addition to a working electrode and a counter electrode is used.
As such an electrochemical cell, for example, an electrode body in which at least one set of working electrode and counter electrode are arranged to face each other via a separator, a storage container for storing the electrode body, and a lid portion of the storage container In this electrochemical cell, a pressurizing means is further provided, and the storage container is sealed by pressing the lid portion toward the storage container by the pressurizing means (for example, Patent Document 1). reference).
JP 2003-109653 A

引用文献１に記載される電気化学セルでは、作用極、対極および参照極が、押圧手段の押圧方向において重なるように配置される。
しかし、このような配置においては、作用極と参照極との間にセパレータを介在させるために、内部抵抗が大きくなるという不具合がある。
そこで、作用極と参照極との間にセパレータを介在させずに参照極を組み付けることによって、内部抵抗を低減する方法が提案されるが、リチウムイオン電池やハイブリッドキャパシタなどの性能評価においては、参照極に加工性の良くない材料、たとえば、リチウムなどを使用する場合があるので、その組付けが作業性良く行われることが望まれる。また、精度の高い性能評価を行うために、性能評価に使用できる参照極の有効面積を十分に確保する必要がある。 In the electrochemical cell described in the cited document 1, the working electrode, the counter electrode, and the reference electrode are arranged so as to overlap in the pressing direction of the pressing means.
However, in such an arrangement, a separator is interposed between the working electrode and the reference electrode, so that the internal resistance increases.
Therefore, a method of reducing the internal resistance by assembling the reference electrode without interposing a separator between the working electrode and the reference electrode is proposed. However, in the performance evaluation of lithium ion batteries and hybrid capacitors, refer to Since materials with extremely poor workability, such as lithium, may be used, it is desired that the assembly be performed with good workability. In order to perform highly accurate performance evaluation, it is necessary to secure a sufficient effective area of the reference electrode that can be used for performance evaluation.

そこで、本発明の目的は、参照極を、作業性良く、簡易かつ確実に組み付けることができ、精度の高い性能評価を行なうことができる電気化学セルを提供することにある。   SUMMARY OF THE INVENTION An object of the present invention is to provide an electrochemical cell in which a reference electrode can be assembled easily and reliably with good workability and performance can be evaluated with high accuracy.

上記目的を達成するため、本発明の電気化学セルは、作用極と、前記作用極に対して対向配置される対極と、前記作用極と前記対極との間に介在されるセパレータと、前記作用極と前記対極との対向方向における前記作用極の投影面から離間するように配置され、かつ、前記作用極との間にセパレータが介在されずに配置される参照極と、前記参照極を収容するための収容部材とを備え、前記収容部材は、開口部を有する被押圧面が形成された収容部と、前記収容部に収容され、前記被押圧面を押圧するための押圧部とを備え、前記収容部材の少なくとも一部は、前記電気化学セル内において、電解液によって浸漬されており、前記押圧部は、前記収容部に対してスライド自在に収容され、前記収容部は、前記参照極と反応せず、前記電解液と反応しない材料から形成されており、前記押圧部のスライドを案内するためのガイド部を備えており、前記参照極は、前記開口部から露出するように、前記被押圧面と前記押圧部との間に配置されていることを特徴としている。 In order to achieve the above object, an electrochemical cell of the present invention includes a working electrode, a counter electrode disposed opposite to the working electrode, a separator interposed between the working electrode and the counter electrode, and the working electrode. A reference electrode disposed so as to be separated from a projection surface of the working electrode in a facing direction of the electrode and the counter electrode, and disposed without a separator between the working electrode and the reference electrode A receiving member that is formed with a pressed surface having an opening, and a pressing unit that is received in the receiving portion and presses the pressed surface. In addition, at least a part of the housing member is immersed in the electrochemical cell by an electrolytic solution, the pressing portion is slidably accommodated with respect to the housing portion, and the housing portion is the reference electrode. Does not react with the electrolyte solution Are formed from unreacted material, provided with a guide portion for guiding the sliding of the pressing portion, the reference electrode, so as to be exposed from the opening, the between the pressing portion and the pressed surface It is characterized by being arranged between.

本発明の電気化学セルでは、参照極が、収容部材における被押圧面と押圧部との間に配置されている。つまり、参照極を収容部材の被押圧面に載置して、その上から押圧部によって押圧するという簡易な操作だけで、参照極を作業性良く、確実に組み付けることができる。また、参照極が、被押圧面に形成された開口部から露出するので、リチウムイオン電池などの性能評価に使用できる参照極の有効面積を十分に確保することができ、精度の高い性能評価を行うことができる。
また、収容部が、参照極と反応せず、かつ、電解液と反応しない材料から形成されていることにより、たとえば、性能評価中に収容部が電解液と反応し、溶解することによって作用極と参照極とが短絡することを防止することができるため、精度の高い性能評価を行うことができる。また、収容部には、押圧部のスライドを案内するためのガイド部が備えられているので、参照極を収容部材の被押圧面に載置して、その上から押圧部をガイド部に沿ってスライドさせて収容するだけで参照極の組み付けを行なうことができる。そのため、参照極を、作業性よく、簡易かつ確実に組み付けることができる。 In the electrochemical cell of the present invention, the reference electrode is disposed between the pressed surface and the pressing portion of the housing member. That is, the reference electrode can be reliably assembled with good workability only by a simple operation of placing the reference electrode on the pressed surface of the housing member and pressing the reference electrode with the pressing portion from above. In addition, since the reference electrode is exposed from the opening formed on the pressed surface, the effective area of the reference electrode that can be used for performance evaluation of a lithium ion battery or the like can be sufficiently secured, and highly accurate performance evaluation can be performed. It can be carried out.
In addition, since the housing portion is formed of a material that does not react with the reference electrode and does not react with the electrolytic solution, for example, the working portion reacts with the electrolytic solution and dissolves during performance evaluation. And the reference electrode can be prevented from being short-circuited, so that highly accurate performance evaluation can be performed. Further, since the accommodating portion is provided with a guide portion for guiding the slide of the pressing portion, the reference electrode is placed on the pressed surface of the accommodating member, and the pressing portion is arranged along the guide portion from above. The reference electrode can be assembled simply by sliding and accommodating. Therefore, the reference electrode can be easily and reliably assembled with good workability.

また、本発明の電気化学セルでは、前記参照極が、リチウムであることが好適である。
性能評価の評価対象となる蓄電デバイスが、たとえば、リチウムイオン電池やハイブリッドキャパシタなど、正極および負極にリチウムイオンを可逆的に吸蔵・放出可能な材料が用いられているデバイスである場合において、参照極がリチウムであると、効率よく性能評価を行なうことができる。 In the electrochemical cell of the present invention, it is preferable that the reference electrode is lithium.
When the power storage device to be evaluated for performance evaluation is a device in which a material capable of reversibly occluding and releasing lithium ions is used for the positive electrode and the negative electrode, such as a lithium ion battery and a hybrid capacitor, for example, When is lithium, performance can be evaluated efficiently.

本発明の電気化学セルによれば、参照極を、作業性よく、簡易かつ確実に組み付けることができ、精度の高い性能評価を行うことができる。   According to the electrochemical cell of the present invention, the reference electrode can be easily and reliably assembled with good workability, and highly accurate performance evaluation can be performed.

図１は、本発明の電気化学セルの一実施形態である、３電極方式の電気化学セルの外観斜視図であり、図２は、図１に示す電気化学セルの中央断面図である。
図１および図２に示すように、この電気化学セル１は、ケーシング２と、そのケーシング２内に収容される作用極３、対極４、参照極５およびセパレータ６とを備えている。
ケーシング２は、作用極３と電気的に接続される上側ケーシング７と、対極４と電気的に接続される下側ケーシング８と、参照極５と電気的に接続され、上側ケーシング７と下側ケーシング８との間に介在される中間ケーシング９とを、それぞれ別体として備えている。 FIG. 1 is an external perspective view of a three-electrode electrochemical cell as an embodiment of the electrochemical cell of the present invention, and FIG. 2 is a central sectional view of the electrochemical cell shown in FIG.
As shown in FIGS. 1 and 2, the electrochemical cell 1 includes a casing 2 and a working electrode 3, a counter electrode 4, a reference electrode 5, and a separator 6 accommodated in the casing 2.
The casing 2 is electrically connected to the upper casing 7 electrically connected to the working electrode 3, the lower casing 8 electrically connected to the counter electrode 4, and the reference electrode 5. An intermediate casing 9 interposed between the casing 8 and the casing 8 is provided as a separate body.

上側ケーシング７は、金属製（たとえば、ステンレス製、以下同様）であり、断面略逆Ｔ字形状に形成され、有底円筒形状の中央筒部１０と、中央筒部１０の下端部外周から径方向外方に延びる上側フランジ部１１とが一体的に形成されている。
中央筒部１０は、その内周面に、後述する押圧調整ボルト１２が螺着されるねじ山が形成されている螺着部１３が、軸方向（上下方向）に沿って形成されている。また、中央筒部１０の底部には、その底部を厚さ方向（上下方向）に貫通し、後述する押圧軸１５が挿通される挿通孔１４が形成されている。 The upper casing 7 is made of metal (for example, made of stainless steel, the same applies hereinafter), is formed in a substantially inverted T-shaped cross section, and has a center cylindrical portion 10 with a bottomed cylindrical shape and a diameter from the outer periphery of the lower end of the central cylindrical portion 10. An upper flange portion 11 extending outward in the direction is integrally formed.
The central cylindrical portion 10 has a screwed portion 13 formed along the axial direction (vertical direction) on the inner peripheral surface of which a screw thread to which a pressure adjusting bolt 12 described later is screwed is formed. Further, an insertion hole 14 is formed in the bottom portion of the central cylinder portion 10 so as to penetrate the bottom portion in the thickness direction (vertical direction) and to insert a pressing shaft 15 described later.

下側ケーシング８は、金属製であり、断面逆ハット形状に形成され、断面凹形状の収容部１６と、収容部１６の上端部外周から径方向外方に延びる上側フランジ部１１と略同一外径の下側フランジ部１７とが一体的に形成されている。
中間ケーシング９は、金属製であり、上側フランジ部１１および下側フランジ部１７と、略同一外径の円板形状に形成されている。なお、中間ケーシング９の内径は、収容部１６の内径よりも小さく設定されている。 The lower casing 8 is made of metal and is formed in an inverted hat shape in cross section, and is substantially the same as the housing portion 16 having a recessed cross section and the upper flange portion 11 extending radially outward from the outer periphery of the upper end portion of the housing portion 16. A lower flange portion 17 having a diameter is integrally formed.
The intermediate casing 9 is made of metal and is formed in a disk shape having substantially the same outer diameter as the upper flange portion 11 and the lower flange portion 17. Note that the inner diameter of the intermediate casing 9 is set smaller than the inner diameter of the accommodating portion 16.

また、上側ケーシング７、中間ケーシング９および下側ケーシング８には、これらが軸方向（上下方向）に重なった状態において、同一位置に、厚さ方向を貫通する固定孔１８がそれぞれ形成されている。固定孔１８は、周方向に互いに等間隔（９０°間隔）を隔てて、複数（４つ）穿孔されている。
また、この電気化学セル１は、上側ケーシング７の螺着部１３に螺着される押圧調整ボルト１２と、圧縮ばねからなる第１コイルばね１９と、第１コイルばね１９に押圧される押圧軸１５と、押圧軸１５に押圧される電極押圧部材２０と、電極押圧部材２０の周りに配置される収容部材としての参照極収容部材２１および圧縮ばねからなる第２コイルばね２２とを、それぞれ別体として備えている。 The upper casing 7, the intermediate casing 9, and the lower casing 8 are each formed with a fixing hole 18 penetrating in the thickness direction at the same position when they are overlapped in the axial direction (vertical direction). . A plurality of (four) fixing holes 18 are perforated at equal intervals (90 ° intervals) in the circumferential direction.
In addition, the electrochemical cell 1 includes a pressure adjusting bolt 12 that is screwed to the screwed portion 13 of the upper casing 7, a first coil spring 19 that is a compression spring, and a pressure shaft that is pressed by the first coil spring 19. 15, an electrode pressing member 20 pressed by the pressing shaft 15, a reference electrode housing member 21 as a housing member disposed around the electrode pressing member 20, and a second coil spring 22 formed of a compression spring, respectively. It is prepared as a body.

押圧調整ボルト１２は、金属製であり、頭部２３と、その頭部２３から突出し、ねじ山が形成されるねじ軸部２４とを一体的に備えている。ねじ軸部２４の遊端部（下端部）には、第１コイルばね１９を受け入れるばね受け凹部２５が形成されている。
押圧軸１５は、金属製であり、長手方向両端部が丸く形成される断面円形状の棒状をなし、その長手方向（上下方向）途中に、径方向外方に膨出する環状のリング部２６が形成されている。このリング部２６は、その外径が、挿通孔１４より大径に形成されている。 The pressure adjusting bolt 12 is made of metal, and integrally includes a head portion 23 and a screw shaft portion 24 that protrudes from the head portion 23 and is formed with a screw thread. A spring receiving recess 25 that receives the first coil spring 19 is formed at the free end (lower end) of the screw shaft portion 24.
The pressing shaft 15 is made of metal and has a circular cross-section with a circular shape at both ends in the longitudinal direction. The annular ring portion 26 bulges radially outward in the longitudinal direction (vertical direction). Is formed. The ring portion 26 has an outer diameter larger than that of the insertion hole 14.

第１コイルばね１９は、押圧調整ボルト１２のばね受け凹部２５内に収容され、かつ、押圧軸１５のリング部２６に当接可能な直径を有する螺旋筒状の金属製のコイルばねから形成されている。
電極押圧部材２０は、金属製であり、その外径が収容部１６の内径よりも小さい円柱形状をなし、その上面には、押圧軸１５を受ける碗形状の受け部２７が一体的に形成されている。また、その下面は、平坦形状に形成されている。また、この電極押圧部材２０は、収容部１６に収容される程度の上下方向厚みで形成されている。 The first coil spring 19 is housed in the spring receiving recess 25 of the pressing adjustment bolt 12 and is formed of a spiral cylindrical metal coil spring having a diameter capable of contacting the ring portion 26 of the pressing shaft 15. ing.
The electrode pressing member 20 is made of metal and has a cylindrical shape whose outer diameter is smaller than the inner diameter of the accommodating portion 16, and a hook-shaped receiving portion 27 that receives the pressing shaft 15 is integrally formed on the upper surface thereof. ing. Moreover, the lower surface is formed in the flat shape. Further, the electrode pressing member 20 is formed with a thickness in the vertical direction such that it is accommodated in the accommodating portion 16.

参照極収容部材２１は、参照極５を収容するための収容部としての参照極収容部２９および、参照極５を後述する参照極底壁４２の上面に対して押圧するための押圧部としての参照極押圧部３８を備えている。
以下、参照極収容部２９については図３を、参照極押圧部３８については図４を参照して、説明する。 The reference electrode accommodating member 21 serves as a reference electrode accommodating portion 29 as an accommodating portion for accommodating the reference electrode 5 and a pressing portion for pressing the reference electrode 5 against an upper surface of a reference electrode bottom wall 42 described later. A reference electrode pressing portion 38 is provided.
Hereinafter, the reference electrode accommodating portion 29 will be described with reference to FIG. 3, and the reference electrode pressing portion 38 with reference to FIG. 4.

図３は、参照極収容部２９を具体的に示す図であって、図３（ａ）は平面図、図３（ｂ）は図３（ａ）に示すＡ−Ａの切断面で切断したときの断面図である。また、図４は、参照極押圧部３８を具体的に示す図であって、図４（ａ）は平面図、図４（ｂ）は図４（ａ）に示すＢ−Ｂの切断面で切断したときの断面図である。
図３を参照して、参照極収容部２９は、絶縁性の樹脂製（たとえば、ポリプロピレン、ポリエチレン、ポリスチレン製など、以下同様）であり、有底円環形状に形成され、電気化学セル１に組み付けられた状態において、収容部１６の内周面と電極押圧部材２０の外周面との間に介在される径方向厚みで形成されている（図２参照）。また、参照極収容部２９は、その内周面を有する参照極収容部内周壁４１と、参照極収容部内周壁４１の径方向外側において間隔を隔てて対向され、その外周面を有する参照極収容部外周壁４０と、これら参照極収容部内周壁４１と参照極収容部外周壁４０の下端部を連結する中空円板状の参照極底壁４２とを備えている。そして、参照極収容部内周壁４１と参照極収容部外周壁４０との間が、参照極押圧部３８が収容される溝部３９として形成される。なお、本発明では、参照極収容部外周壁４０および参照極収容部内周壁４１が、ガイド部を構成している。 FIGS. 3A and 3B are diagrams specifically showing the reference electrode housing portion 29. FIG. 3A is a plan view, and FIG. 3B is a cross-sectional view taken along the line AA shown in FIG. FIG. 4 is a view specifically showing the reference electrode pressing portion 38, in which FIG. 4 (a) is a plan view, and FIG. 4 (b) is a sectional view taken along the line BB shown in FIG. 4 (a). It is sectional drawing when cut | disconnecting.
Referring to FIG. 3, reference electrode accommodating portion 29 is made of an insulating resin (for example, made of polypropylene, polyethylene, polystyrene, etc., and so on), is formed in a bottomed annular shape, and is attached to electrochemical cell 1. In the assembled state, it is formed with a radial thickness interposed between the inner peripheral surface of the accommodating portion 16 and the outer peripheral surface of the electrode pressing member 20 (see FIG. 2). Further, the reference electrode accommodating portion 29 is opposed to the reference electrode accommodating portion inner peripheral wall 41 having the inner peripheral surface thereof at a distance on the outer side in the radial direction of the reference electrode accommodating portion inner peripheral wall 41 and has the outer peripheral surface. An outer peripheral wall 40, a reference electrode housing inner peripheral wall 41, and a hollow disk-shaped reference electrode bottom wall 42 connecting the lower ends of the reference electrode housing outer peripheral wall 40 are provided. A space between the reference electrode accommodating portion inner peripheral wall 41 and the reference electrode accommodating portion outer peripheral wall 40 is formed as a groove 39 in which the reference electrode pressing portion 38 is accommodated. In the present invention, the reference electrode accommodating portion outer peripheral wall 40 and the reference electrode accommodating portion inner peripheral wall 41 constitute a guide portion.

参照極底壁４２には、周方向略等間隔に複数個所（たとえば１６箇所）、略長方形に切り出されることによって開口される開口部４３が形成されている。
図４を参照して、参照極押圧部３８は、たとえば、ステンレスまたはニッケルなど、電気伝導性を有する材料からなり、円筒形状に形成され、溝部３９に収納可能な径方向厚みで形成されている。また、溝部３９に収容された状態において、その上面が、参照極収容部２９の上面と、略面一となるような高さで形成されている。これにより、電気化学セル１に組み付けられた状態において、第２コイルばね２２と電気的に導通される（図２参照）。さらに、参照極押圧部３８の、外周面が参照極押圧部外周面４５、内周面が参照極押圧部内周面４６として形成されている。 The reference pole bottom wall 42 is formed with openings 43 which are opened by being cut into a plurality of (for example, 16) and substantially rectangular at substantially equal intervals in the circumferential direction.
Referring to FIG. 4, reference electrode pressing portion 38 is made of a material having electrical conductivity such as stainless steel or nickel, is formed in a cylindrical shape, and has a radial thickness that can be stored in groove 39. . Further, the upper surface of the groove 39 is formed so as to be substantially flush with the upper surface of the reference electrode housing portion 29. Thereby, in the state assembled | attached to the electrochemical cell 1, it is electrically connected with the 2nd coiled spring 22 (refer FIG. 2). Further, the reference electrode pressing portion 38 has an outer peripheral surface formed as a reference electrode pressing portion outer peripheral surface 45 and an inner peripheral surface formed as a reference electrode pressing portion inner peripheral surface 46.

また、参照極押圧部３８の上面には、周方向途中に上下方向に段差を生じる凹部４４が、複数個（たとえば８箇所）形成されており、参照極押圧部３８を参照極収容部２９に収容した状態において、たとえば、任意の凹部４４の側面とそれに隣接する凹部４４の側面とをピンセットまたは指で挟むことなどによって、参照極押圧部３８を参照極収容部２９から取り出すことができるようになっている。   In addition, a plurality of (for example, eight) recesses 44 are formed on the upper surface of the reference electrode pressing portion 38 so as to form a step in the vertical direction in the middle of the circumferential direction. In the accommodated state, the reference electrode pressing portion 38 can be taken out from the reference electrode accommodating portion 29 by, for example, pinching the side surface of an arbitrary recess 44 and the side surface of the adjacent recess 44 with tweezers or a finger. It has become.

再び図１および図２を参照して、第２コイルばね２２は、参照極収容部材２１の上面、詳しくは、参照極収容部２９および参照極押圧部３８の上面に当接可能な直径を有する螺旋筒状の金属製のコイルばねから形成されている。
作用極３は、電極押圧部材２０と同径の円板形状をなし、たとえば、水蒸気賦活活性炭、やしがら系活性炭および石油コークス系活性炭などの活性炭、リチウム遷移金属化合物、二酸化マンガンまたはフッ化黒鉛など、たとえば、リチウムイオン電池やハイブリッドキャパシタなどの正極材料、たとえば、ハードカーボン（難黒鉛化炭素）およびグラファイトなどの炭素系材料、黒鉛、不定形炭素または有機高分子焼結体など、たとえば、リチウムイオン電池やハイブリッドキャパシタなどの負極材料など、作用極３として性能評価をする材料から形成されている。 Referring to FIGS. 1 and 2 again, the second coil spring 22 has a diameter capable of contacting the upper surface of the reference electrode housing member 21, specifically, the upper surfaces of the reference electrode housing portion 29 and the reference electrode pressing portion 38. It is formed of a spiral cylindrical metal coil spring.
The working electrode 3 has a disk shape having the same diameter as that of the electrode pressing member 20. For example, activated carbon such as steam activated carbon, coconut shell activated carbon and petroleum coke activated carbon, lithium transition metal compound, manganese dioxide or graphite fluoride For example, positive electrode materials such as lithium ion batteries and hybrid capacitors, for example, carbon-based materials such as hard carbon (non-graphitizable carbon) and graphite, graphite, amorphous carbon or organic polymer sintered bodies, such as lithium The working electrode 3 is made of a material whose performance is evaluated, such as a negative electrode material such as an ion battery or a hybrid capacitor.

対極４は、作用極３と同径の円板形状をなし、たとえば、上記した材料と同様の材料など、対極４として評価する材料から、形成されている。なお、対極４は、作用極３より大径の円板形状に形成することもできる。
参照極５は、作用極３および対極４の電位の基準となる電極であり、電極電位が安定している材料、たとえば、リチウム、銀、活性炭などが用いられ、たとえば、リチウムイオン電池やハイブリッドキャパシタの性能評価を実施する場合においては、リチウムを用いることが好ましい。性能評価の評価対象が、リチウムイオン電池やハイブリッドキャパシタのように、正極および負極にリチウムイオンを可逆的に吸蔵・放出可能な材料が用いられているデバイスである場合において、参照極５がリチウムであると、効率よく性能評価を実施することができる。また、参照極５は、溝部３９内において円環状に収容される形状、たとえば、開口部４３より大きい面積である箔形状、たとえば、略長方形が放射状に連結するような短冊形状に形成されている。これにより、たとえば、リチウムなどのように加工性の良くない材料を参照極５に用いた場合であっても、参照極５の形状が箔形状であれば、作業能率を低下させずに、容易に加工することができる。 The counter electrode 4 has a disk shape having the same diameter as that of the working electrode 3 and is formed of a material to be evaluated as the counter electrode 4 such as the same material as described above. The counter electrode 4 can also be formed in a disk shape having a larger diameter than the working electrode 3.
The reference electrode 5 is an electrode serving as a reference for the potential of the working electrode 3 and the counter electrode 4, and a material having a stable electrode potential, for example, lithium, silver, activated carbon, or the like is used. For example, a lithium ion battery or a hybrid capacitor is used. When performing the performance evaluation, it is preferable to use lithium. When the evaluation target of the performance evaluation is a device in which a material capable of reversibly occluding and releasing lithium ions is used for the positive electrode and the negative electrode, such as a lithium ion battery or a hybrid capacitor, the reference electrode 5 is lithium. If so, the performance evaluation can be performed efficiently. Further, the reference electrode 5 is formed in an annular shape in the groove 39, for example, a foil shape having an area larger than the opening 43, for example, a strip shape in which a substantially rectangular shape is connected radially. . Thereby, for example, even when a material with poor workability such as lithium is used for the reference electrode 5, if the shape of the reference electrode 5 is a foil shape, the work efficiency is easily reduced. Can be processed.

セパレータ６は、電極押圧部材２０、作用極３および対極４よりも大径であって、収容部１６の内径と同径の円板形状をなし、たとえば、ガラス繊維からなる不織布またはポリオレフィン系微孔性フィルム、セルロース系フィルムなど、セパレータとして用いられる通常の材料から、形成されている。
次に、この電気化学セル１の組み付けについて説明する。 The separator 6 is larger than the electrode pressing member 20, the working electrode 3, and the counter electrode 4, and has a disk shape having the same diameter as the inner diameter of the housing portion 16. For example, a nonwoven fabric or polyolefin micropore made of glass fiber It is formed from a normal material used as a separator, such as a conductive film or a cellulose film.
Next, the assembly of the electrochemical cell 1 will be described.

この電気化学セル１の組み付けにおいては、まず、下側ケーシング８の収容部１６内に、対極４、セパレータ６、作用極３および、参照極５が収容された参照極収容部材２１を、配置する。具体的には、収容部１６内の底面中央部に、対極４を載置し、その対極４の上面に、セパレータ６を載置し、そのセパレータ６の上面周端部に、参照極５が収容された参照極収容部材２１を配置する。   In the assembly of the electrochemical cell 1, first, the reference electrode housing member 21 in which the counter electrode 4, the separator 6, the working electrode 3, and the reference electrode 5 are housed is disposed in the housing portion 16 of the lower casing 8. . Specifically, the counter electrode 4 is placed at the center of the bottom surface in the housing portion 16, the separator 6 is placed on the upper surface of the counter electrode 4, and the reference electrode 5 is placed on the peripheral edge of the upper surface of the separator 6. The accommodated reference electrode accommodating member 21 is disposed.

ここで、参照極収容部材２１の組み付けについて、図５〜図７を参照して説明する。
参照極収容部材２１の組み付けにおいては、まず、図５に示すように、参照極底壁４２の被押圧面としての上面に参照極５を載置する。具体的には、短冊状に形成された参照極５を、その表面が開口部４３から露出するように、たとえば、参照極底壁４２の周方向にわたって載置する。次いで、図６に示すように、たとえば、参照極押圧部外周面４５が参照極収容部外周壁４０の内周面に摺動するように、また、参照極押圧部内周面４６が参照極収容部内周壁４１と摺動するように、参照極押圧部３８を参照極収容部２９に対してスライドさせて、溝部３９に収容する。 Here, assembly of the reference electrode housing member 21 will be described with reference to FIGS.
In assembling the reference electrode housing member 21, first, as shown in FIG. 5, the reference electrode 5 is placed on the upper surface of the reference electrode bottom wall 42 as a pressed surface. Specifically, the reference electrode 5 formed in a strip shape is placed, for example, over the circumferential direction of the reference electrode bottom wall 42 so that the surface thereof is exposed from the opening 43. Next, as shown in FIG. 6, for example, the reference electrode pressing portion outer peripheral surface 45 slides on the inner peripheral surface of the reference electrode housing portion outer peripheral wall 40, and the reference electrode pressing portion inner peripheral surface 46 is accommodated in the reference electrode housing. The reference electrode pressing portion 38 is slid with respect to the reference electrode accommodating portion 29 so as to slide with the inner wall 41, and is accommodated in the groove portion 39.

このように組み付けることによって、図７に示すように、参照極５は、参照極底壁４２の上面と参照極押圧部３８との間において、参照極押圧部３８によって押圧され、かつ、開口部４３から露出される。また、参照極押圧部３８の上面が、参照極収容部２９の上面と略面一となるように組み付けられている。なお、参照極５については、たとえば、リチウムイオン電池やハイブリッドキャパシタなどの性能評価の精度に影響を与えないのであれば、たとえば、参照極底壁４２の上面の周方向数箇所に載置するだけでもよい。   By assembling in this way, as shown in FIG. 7, the reference electrode 5 is pressed by the reference electrode pressing portion 38 between the upper surface of the reference electrode bottom wall 42 and the reference electrode pressing portion 38, and the opening portion. 43 is exposed. Further, the reference electrode pressing portion 38 is assembled so that the upper surface thereof is substantially flush with the upper surface of the reference electrode accommodating portion 29. For example, if the reference electrode 5 does not affect the accuracy of performance evaluation of a lithium ion battery, a hybrid capacitor, or the like, for example, the reference electrode 5 is only placed at several locations in the circumferential direction on the upper surface of the reference electrode bottom wall 42. But you can.

そして、参照極収容部材２１を配置した後、セパレータ６の上面中央部に、作用極３を載置し、作用極３の上面に、電極押圧部材２０が上下方向において重なるように載置する。これによって、収容部１６内においては、対極４、セパレータ６、作用極３および電極押圧部材２０が、収容部１６の深さ方向（上下方向）に沿って順次配置され、参照極５が収容された参照極収容部２９が、電極押圧部材２０に対して径方向外方側方に配置される。   Then, after arranging the reference electrode housing member 21, the working electrode 3 is placed on the center of the upper surface of the separator 6, and the electrode pressing member 20 is placed on the upper surface of the working electrode 3 so as to overlap in the vertical direction. As a result, the counter electrode 4, the separator 6, the working electrode 3, and the electrode pressing member 20 are sequentially arranged along the depth direction (vertical direction) of the storage portion 16 in the storage portion 16, and the reference electrode 5 is stored. The reference electrode accommodating portion 29 is disposed radially outward with respect to the electrode pressing member 20.

また、セパレータ６は、電極押圧部材２０、作用極３および対極４の外径より大きく、収容部１６の内径と同径に形成されているため、このような配置において、上下方向における電極押圧部材２０、作用極３および対極４の投影面から、径方向（水平方向）外方にはみ出している。そして、参照極収容部２９に収容されている参照極５は、上下方向における電極押圧部材２０、作用極３および対極４の投影面から、径方向（水平方向）外方に離間して配置されており、はみ出した部分のセパレータ６の上面と、開口部４３から露出した参照極５の下面とが、上下方向において対向する。   Moreover, since the separator 6 is larger than the outer diameter of the electrode pressing member 20, the working electrode 3, and the counter electrode 4, and is formed in the same diameter as the inner diameter of the accommodating portion 16, the electrode pressing member in the vertical direction in such an arrangement. 20, projecting from the projection surface of the working electrode 3 and the counter electrode 4 outward in the radial direction (horizontal direction). The reference electrode 5 accommodated in the reference electrode accommodating portion 29 is arranged to be spaced outward in the radial direction (horizontal direction) from the projection surfaces of the electrode pressing member 20, the working electrode 3, and the counter electrode 4 in the vertical direction. The upper surface of the protruding portion of the separator 6 and the lower surface of the reference electrode 5 exposed from the opening 43 are opposed to each other in the vertical direction.

また、このような配置において、参照極５は、作用極３に対して径方向外方において、セパレータ６を介在させることなく配置されている。
その後、収容部１６内に、電解液を注入する。電解液は、その目的および用途によって、適宜公知のものが選択される。たとえば、リチウムイオン電池やハイブリッドキャパシタなどの性能評価を実施する場合には、リチウムイオンを含む有機溶媒からなり、リチウム塩を有機溶媒に溶解させることにより、調製されている。 In such an arrangement, the reference electrode 5 is arranged on the outer side in the radial direction with respect to the working electrode 3 without the separator 6 interposed.
Thereafter, an electrolytic solution is injected into the accommodating portion 16. As the electrolytic solution, a known one is appropriately selected depending on its purpose and application. For example, when performance evaluation of a lithium ion battery, a hybrid capacitor, or the like is performed, the battery is made of an organic solvent containing lithium ions, and is prepared by dissolving a lithium salt in the organic solvent.

リチウム塩としては、たとえば、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＣ（ＳＯ2ＣＦ3）3、ＬｉＢ（Ｃ6Ｈ5）4、ＬｉＣ4Ｆ9ＳＯ3、ＬｉＣ8Ｆ17ＳＯ3、ＬｉＢ［Ｃ6Ｈ3（ＣＦ3）2−３，５］4、ＬｉＢ（Ｃ6Ｆ5）4、ＬｉＢ［Ｃ6Ｈ4（ＣＦ3）−４］4、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＣＦ3ＣＯ2、ＬｉＮ（ＣＦ3ＳＯ2）2が挙げられる。なお、上式中［Ｃ6Ｈ3（ＣＦ3）2−３，５］は，フェニル基の３位と５位に、［Ｃ6Ｈ4（ＣＦ3）−４］はフェニル基の４位に、それぞれ−ＣＦ3が置換されているものを意味する。 Examples of the lithium salt include LiClO 4 , LiCF 3 SO 3 , LiC (SO 2 CF 3 ) 3 , LiB (C 6 H 5 ) 4 , LiC 4 F 9 SO 3 , LiC 8 F 17 SO 3 , LiB [C 6 H 3 (CF 3) 2 -3,5] 4, LiB (C 6 F 5) 4, LiB [C 6 H 4 (CF 3) -4] 4, LiBF 4, LiPF 6, LiAsF 6, LiSbF 6 , LiCF 3 CO 2 , and LiN (CF 3 SO 2 ) 2 . In the above formula, [C 6 H 3 (CF 3 ) 2 -3, 5] is the 3rd and 5th positions of the phenyl group, and [C 6 H 4 (CF 3 ) -4] is the 4th position of the phenyl group. Each of which is substituted with —CF 3 .

また、有機溶媒としては、たとえば、ジエチレンカーボネート、プロピレンカーボネート、プロピレンカーボネート誘導体、エチレンカーボネート、エチレンカーボネート誘導体、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、γ−ブチロラクトン、１，３−ジオキソラン、ジメチルスルホキシド、スルホラン、ホルムアミド、ジメチルホルムアミド、ジメチルアセトアミド、ジオキソラン、リン酸トリエステル、無水マレイン酸、無水コハク酸、無水フタル酸、１，３−プロパンスルトン、４，５−ジヒドロピラン誘導体、ニトロベンゼン、１，３−ジオキサン、１，４−ジオキサン、３−メチル−２−オキサゾリジノン、１，２−ジメトキシエタン、テトラヒドロフラン、２−メチルテトラヒドロフラン、テトラヒドロフラン誘導体、シドノン化合物、アセトニトリル、ニトロメタン、アルコキシエタン、トルエンなどが挙げられる。これらは、単独または２種以上併用することができる。電解液は、組み付け後の電気化学セル１において、収容部１６内の少なくともセパレータ６が浸漬されるとともに、参照極収容部材２１の下端部の少なくとも一部が浸漬される程度、たとえば、参照極５が電解液に接触する程度に注入する。   Examples of the organic solvent include diethylene carbonate, propylene carbonate, propylene carbonate derivatives, ethylene carbonate, ethylene carbonate derivatives, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, 1,3-dioxolane, dimethyl Sulfoxide, sulfolane, formamide, dimethylformamide, dimethylacetamide, dioxolane, phosphoric acid triester, maleic anhydride, succinic anhydride, phthalic anhydride, 1,3-propane sultone, 4,5-dihydropyran derivative, nitrobenzene, 1, 3-dioxane, 1,4-dioxane, 3-methyl-2-oxazolidinone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyl Tetrahydrofuran, tetrahydrofuran derivatives, sydnone compounds, acetonitrile, nitromethane, alkoxy ethane, and toluene. These can be used alone or in combination of two or more. In the electrochemical cell 1 after assembly, the electrolytic solution is immersed in at least the separator 6 in the accommodating portion 16 and at least a part of the lower end portion of the reference electrode accommodating member 21, for example, the reference electrode 5. Is injected to such an extent that it contacts the electrolyte.

次いで、参照極収容部材２１の上面に、第２コイルばね２２の下端部を載置した後、中間ケーシング９を、その下面で第２コイルばね２２の上端部を押圧するようにして、下側ケーシング８の下側フランジ部１７の上面に重ね合わせる。なお、中間ケーシング９と下側ケーシング８との間には、ゴム製のＯリング３０および円板形状のリングシール板３３を介在させて、それらの間のシールを確保するとともに、中間ケーシング９と下側ケーシング８との間を絶縁する。   Next, after placing the lower end portion of the second coil spring 22 on the upper surface of the reference electrode housing member 21, the lower side of the intermediate casing 9 is pressed so that the upper end portion of the second coil spring 22 is pressed on the lower surface thereof. The upper surface of the lower flange portion 17 of the casing 8 is overlapped. A rubber O-ring 30 and a disc-shaped ring seal plate 33 are interposed between the intermediate casing 9 and the lower casing 8 to secure a seal between them, Insulates from the lower casing 8.

その後、上側ケーシング７を、中間ケーシング９の上面に重ね合わせる。なお、上側ケーシング７と中間ケーシング９との間には、ゴム製のＯリング３０および円板形状のリングシール板３３を介在させて、それらの間のシールを確保するとともに、上側ケーシング７と中間ケーシング９との間を絶縁する。
そして、上側ケーシング７、中間ケーシング９および下側ケーシング８に穿孔されている固定孔１８を位置合わせして、各固定孔１８に下側ケーシング８の下側フランジ部１７側から、固定ボルト３１を挿通させ、上側ケーシング７の上側フランジ部１１側に挿通された固定ボルト３１を、ナット３２で締め込む。なお、上側ケーシング７および中間ケーシング９の固定孔１８には、予め絶縁性のカラー部材３４を挿入しておき、固定ボルト３１によって、上側ケーシング７、中間ケーシング９および下側ケーシング８が導通することを防止する。 Thereafter, the upper casing 7 is overlaid on the upper surface of the intermediate casing 9. A rubber O-ring 30 and a disc-shaped ring seal plate 33 are interposed between the upper casing 7 and the intermediate casing 9 to ensure a seal therebetween, and between the upper casing 7 and the intermediate casing 9. Insulates from the casing 9.
Then, the fixing holes 18 drilled in the upper casing 7, the intermediate casing 9, and the lower casing 8 are aligned, and the fixing bolt 31 is inserted into each fixing hole 18 from the lower flange portion 17 side of the lower casing 8. The fixing bolt 31 inserted and inserted into the upper flange portion 11 side of the upper casing 7 is tightened with a nut 32. An insulating collar member 34 is inserted in advance in the fixing holes 18 of the upper casing 7 and the intermediate casing 9, and the upper casing 7, the intermediate casing 9 and the lower casing 8 are electrically connected by the fixing bolt 31. To prevent.

また、上側ケーシング７の中央筒部１０の挿通孔１４に、押圧軸１５を、リング部２６が挿通孔１４に対向し、押圧軸１５の下端部が電極押圧部材２０の受け部２７に当接するまで、挿通する。そして、挿通孔１４に挿通された押圧軸１５のリング部２６の上面に、第１コイルばね１９を載置した後、押圧調整ボルト１２のねじ軸部２４を、ばね受け凹部２５によって押圧軸１５の上端部が受けられるように、中央筒部１０の螺着部１３に螺着させ、螺締する。なお、押圧調整ボルト１２の頭部２３の下面と、中央筒部１０の上端面との間には、ゴム製のＯリング３０を介在させて、それらの間のシールを確保する。   Further, the pressing shaft 15 is opposed to the insertion hole 14 of the central cylindrical portion 10 of the upper casing 7, the ring portion 26 is opposed to the insertion hole 14, and the lower end portion of the pressing shaft 15 is in contact with the receiving portion 27 of the electrode pressing member 20. Until it is inserted. Then, after placing the first coil spring 19 on the upper surface of the ring portion 26 of the pressing shaft 15 inserted through the insertion hole 14, the screw shaft portion 24 of the pressing adjustment bolt 12 is pressed by the spring receiving recess 25 to the pressing shaft 15. Are screwed onto the screwed portion 13 of the central tube portion 10 so as to receive the upper end portion thereof. A rubber O-ring 30 is interposed between the lower surface of the head 23 of the pressure adjusting bolt 12 and the upper end surface of the central cylinder portion 10 to ensure a seal therebetween.

このようにして組み付けられた電気化学セル１では、固定ボルト３１およびナット３２の締め付けによって、参照極収容部材２１の上面と中間ケーシング９の下面の間に挟まれる第２コイルばね２２が圧縮されるので、その第２コイルばね２２の反力によって、参照極収容部材２１が下方に押圧され、その結果、参照極収容部材２１の下面、詳しくは、参照極底壁４２が、セパレータ６を押圧する。   In the electrochemical cell 1 assembled in this way, the second coil spring 22 sandwiched between the upper surface of the reference electrode housing member 21 and the lower surface of the intermediate casing 9 is compressed by tightening the fixing bolt 31 and the nut 32. Therefore, the reference electrode housing member 21 is pressed downward by the reaction force of the second coil spring 22, and as a result, the lower surface of the reference electrode housing member 21, specifically, the reference electrode bottom wall 42 presses the separator 6. .

また、このようにして組み付けられた電気化学セル１では、押圧調整ボルト１２の締め付けによって、第１コイルばね１９を介して、押圧軸１５が下方に向かって弾性的に付勢される。そして、弾性的に付勢された押圧軸１５の下端部が、電極押圧部材２０を押圧するので、その結果、電極押圧部材２０が、セパレータ６を上下に挟んで対向配置される作用極３および対極４を押圧する。   In the electrochemical cell 1 assembled in this way, the pressing shaft 15 is elastically biased downward via the first coil spring 19 by tightening the pressing adjusting bolt 12. The lower end portion of the elastically biased pressing shaft 15 presses the electrode pressing member 20, and as a result, the electrode pressing member 20 is opposed to the working electrode 3 with the separator 6 interposed therebetween. Press the counter electrode 4.

また、この電気化学セル１では、下側ケーシング８には、対極４に電圧を印加するための対極用端子３５が設けられている。対極用端子３５は、収容部１６の底面に接触している対極４と、下側ケーシング８を介して電気的に導通される。
また、中間ケーシング９には、参照極５に電圧を印加するための参照極用端子３６が設けられている。参照極用端子３６は、参照極押圧部３８と接触している参照極５と、中間ケーシング９および第２コイルばね２２を介して電気的に導通される。より具体的には、電気化学セル１を組み付けた状態において、参照極用端子３６が設けられる中間ケーシング９の下面は、第２コイルばね２２の上端部を押圧している。また、第２コイルばね２２の下端部は、参照極収容部材２１の上面、詳しくは、参照極収容部２９および参照極押圧部３８の上面を押圧している。さらに、参照極押圧部３８の下面は、参照極５を押圧している。このように、中間ケーシング９、第２コイルばね２２、参照極押圧部３８および参照極５が連続的に接触した状態となるので、参照極用端子３６は、参照極５と電気的に導通される。 In the electrochemical cell 1, the lower casing 8 is provided with a counter electrode terminal 35 for applying a voltage to the counter electrode 4. The counter electrode terminal 35 is electrically connected to the counter electrode 4 in contact with the bottom surface of the housing portion 16 via the lower casing 8.
The intermediate casing 9 is provided with a reference electrode terminal 36 for applying a voltage to the reference electrode 5. The reference electrode terminal 36 is electrically connected to the reference electrode 5 in contact with the reference electrode pressing portion 38 via the intermediate casing 9 and the second coil spring 22. More specifically, the lower surface of the intermediate casing 9 provided with the reference electrode terminal 36 presses the upper end portion of the second coil spring 22 in a state where the electrochemical cell 1 is assembled. Further, the lower end portion of the second coil spring 22 presses the upper surface of the reference electrode housing member 21, specifically, the upper surfaces of the reference electrode housing portion 29 and the reference electrode pressing portion 38. Further, the lower surface of the reference electrode pressing portion 38 presses the reference electrode 5. Thus, since the intermediate casing 9, the second coil spring 22, the reference electrode pressing portion 38 and the reference electrode 5 are in continuous contact, the reference electrode terminal 36 is electrically connected to the reference electrode 5. The

また、上側ケーシング７には、作用極３に電圧を印加するための作用極用端子３７が設けられている。作用極用端子３７は、電極押圧部材２０の下面に接触している作用極３と、上側ケーシング７、押圧調整ボルト１２、第１コイルばね１９および押圧軸１５を介して電気的に導通される。
そして、このような電気化学セル１では、作用極３および対極４がセパレータ６を介して上下方向に対向配置される一方で、参照極５が、上下方向における作用極３の投影面から離間し、かつ、作用極３との間に他のセパレータが介在されずに、作用極３および対極４によって挟まれるセパレータ６と接触するように、配置されており、さらに、参照極底壁４２の上面と参照極押圧部３８との間に配置されている。 The upper casing 7 is provided with a working electrode terminal 37 for applying a voltage to the working electrode 3. The working electrode terminal 37 is electrically connected to the working electrode 3 in contact with the lower surface of the electrode pressing member 20 via the upper casing 7, the pressing adjustment bolt 12, the first coil spring 19, and the pressing shaft 15. .
In such an electrochemical cell 1, the working electrode 3 and the counter electrode 4 are arranged to face each other in the vertical direction via the separator 6, while the reference electrode 5 is separated from the projection surface of the working electrode 3 in the vertical direction. In addition, the separator is disposed so as to be in contact with the separator 6 sandwiched between the working electrode 3 and the counter electrode 4 without any other separator interposed between the working electrode 3 and the upper surface of the reference electrode bottom wall 42. And the reference electrode pressing portion 38.

つまり、この配置により、参照極５と作用極３との間の内部抵抗を低減することをできながら、参照極５を参照極底壁４２の上面に載置して、その上から参照極押圧部３８で押圧するという簡易な操作だけで、参照極５を作業性良く、確実に組み付けることができる。また、参照極５が、開口部４３から露出するので、たとえば、リチウムイオン電池やハイブリッドキャパシタなどの性能評価に使用できる参照極５の有効面積を広くすることができ、精度の高い性能評価を行うことができる。   That is, by this arrangement, while the internal resistance between the reference electrode 5 and the working electrode 3 can be reduced, the reference electrode 5 is placed on the upper surface of the reference electrode bottom wall 42 and the reference electrode is pressed from above. The reference electrode 5 can be reliably assembled with good workability only by a simple operation of pressing the portion 38. In addition, since the reference electrode 5 is exposed from the opening 43, the effective area of the reference electrode 5 that can be used for performance evaluation of, for example, a lithium ion battery or a hybrid capacitor can be widened, and highly accurate performance evaluation is performed. be able to.

また、参照極収容部２９が、絶縁性の樹脂からなり、参照極５と反応せず、かつ、電解液と反応しないため、たとえば、性能評価中に作用極３と参照極５とが短絡することを抑制することができ、精度の高い性能評価を行うことができる。さらに、参照極収容部２９に、参照極押圧部３８のスライドを案内するための参照極収容部外周壁４０および参照極収容部内周壁４１が備えられているので、参照極５を参照極底壁４２の上面に載置して、その上から参照極押圧部３８を、参照極収容部外周壁４０および参照極収容部内周壁４１に沿ってスライドさせて収容するだけで参照極５の組み付けを行なうことができる。そのため、参照極５を、作業性よく、簡易かつ確実に組み付けることができる。   Further, since the reference electrode accommodating portion 29 is made of an insulating resin and does not react with the reference electrode 5 and does not react with the electrolytic solution, for example, the working electrode 3 and the reference electrode 5 are short-circuited during performance evaluation. This can be suppressed, and highly accurate performance evaluation can be performed. Further, since the reference electrode accommodating portion 29 is provided with a reference electrode accommodating portion outer peripheral wall 40 and a reference electrode accommodating portion inner peripheral wall 41 for guiding the slide of the reference electrode pressing portion 38, the reference electrode 5 is connected to the reference electrode bottom wall. The reference electrode 5 is assembled by simply placing it on the upper surface of 42 and sliding the reference electrode pressing portion 38 along the reference electrode accommodating portion outer peripheral wall 40 and the reference electrode accommodating portion inner peripheral wall 41 from above. be able to. Therefore, the reference electrode 5 can be easily and reliably assembled with good workability.

また、この電気化学セル１では、押圧調整ボルト１２の締め付けによって、電極押圧部材２０が、セパレータ６を上下に挟んで対向配置される作用極３および対極４を押圧して、作用極３を、セパレータ６を介して対極４に密着させることができる。また、固定ボルト３１およびナット３２の締め付けによって、第２コイルばね２２が、参照極５を押圧して、参照極５を、セパレータ６に密着させることができる。その結果、簡易かつ確実な組み付けによって、作用極３、対極４および参照極５をより確実に配置して、正確な測定を達成することができる。   Further, in this electrochemical cell 1, by tightening the pressure adjusting bolt 12, the electrode pressing member 20 presses the working electrode 3 and the counter electrode 4 that are arranged to face each other with the separator 6 interposed therebetween, and the working electrode 3 is It can be brought into close contact with the counter electrode 4 through the separator 6. In addition, by tightening the fixing bolt 31 and the nut 32, the second coil spring 22 can press the reference electrode 5 to bring the reference electrode 5 into close contact with the separator 6. As a result, the working electrode 3, the counter electrode 4 and the reference electrode 5 can be more reliably arranged by simple and reliable assembly to achieve accurate measurement.

また、押圧調整ボルト１２の締め付けによる押圧力を調整することによって、作用極３および対極４を、セパレータ６を介して、最適の押圧力で均一に接触させることができる。さらに、固定ボルト３１およびナット３２の締め付けによる押圧力を調整することによって、参照極５を、セパレータ６に対して、最適の押圧力で均一に接触させることができる。   Further, by adjusting the pressing force by tightening the pressing adjusting bolt 12, the working electrode 3 and the counter electrode 4 can be brought into uniform contact with each other with the optimal pressing force via the separator 6. Further, by adjusting the pressing force by tightening the fixing bolt 31 and the nut 32, the reference electrode 5 can be uniformly brought into contact with the separator 6 with the optimal pressing force.

しかも、これら押圧調整ボルト１２による締め付け、および、固定ボルト３１による締め付けは、すべて上方（同一方向）から実施することができるので、より一層簡易な組み付けを実現することができる。
また、この電気化学セル１では、下側ケーシング８の収容部１６によって、対極４、セパレータ６、作用極３および参照極５を、コンパクトに収容しつつ、これらの簡易かつ確実な組み付けを達成することができる。 In addition, since the tightening with the press adjusting bolt 12 and the tightening with the fixing bolt 31 can all be performed from above (in the same direction), it is possible to realize a simpler assembly.
In the electrochemical cell 1, the counter electrode 4, the separator 6, the working electrode 3, and the reference electrode 5 are compactly accommodated by the accommodating portion 16 of the lower casing 8, and simple and reliable assembly thereof is achieved. be able to.

さらに、収容部１６によって、その内部が閉塞されるので、電解液の漏れをより確実に防止することができる。
また、この電気化学セル１は、上記した優れた組み付け性に起因して、優れた分解性もあり、そのため、短時間で分解および組み付けすることができる。 Furthermore, since the inside is closed by the accommodating portion 16, leakage of the electrolyte can be prevented more reliably.
The electrochemical cell 1 also has excellent decomposability due to the excellent assemblability described above, and therefore can be decomposed and assembled in a short time.

本発明の電気化学セルの一実施形態である、３電極方式の電気化学セルの外観斜視図である。1 is an external perspective view of a three-electrode electrochemical cell that is an embodiment of the electrochemical cell of the present invention. 図１に示す電気化学セルの中央断面図である。It is a center sectional view of the electrochemical cell shown in FIG. 参照極収容部を具体的に示す図であって、図３（ａ）は平面図、図３（ｂ）は図３（ａ）に示すＡ−Ａの切断面で切断したときの断面図である。3A and 3B are diagrams specifically illustrating a reference electrode housing portion, in which FIG. 3A is a plan view, and FIG. 3B is a cross-sectional view taken along the line AA shown in FIG. is there. 参照極押圧部を具体的に示す図であって、図４（ａ）は平面図、図４（ｂ）は図４（ａ）に示すＢ−Ｂの切断面で切断したときの断面図である。It is a figure which shows a reference pole press part concretely, Comprising: Fig.4 (a) is a top view, FIG.4 (b) is sectional drawing when cut | disconnecting by the cut surface of BB shown to Fig.4 (a). is there. 参照極を載置した状態の参照極収容部の平面図である。It is a top view of the reference electrode accommodating part of the state which mounted the reference electrode. 参照極収容部および参照極押圧部の分解斜視図である。It is a disassembled perspective view of a reference electrode accommodating part and a reference electrode pressing part. 参照極を組み付けた状態の参照極収容部材を示す断面図である。It is sectional drawing which shows the reference electrode accommodating member of the state which assembled | attached the reference electrode.

符号の説明Explanation of symbols

１ 電気化学セル
３ 作用極
４ 対極
５ 参照極
６ セパレータ
２１ 参照極収容部材
２９ 参照極収容部
３８ 参照極押圧部
４０ 参照極収容部外周壁
４１ 参照極収容部内周壁
４２ 参照極底壁 DESCRIPTION OF SYMBOLS 1 Electrochemical cell 3 Working electrode 4 Counter electrode 5 Reference electrode 6 Separator 21 Reference electrode accommodating member 29 Reference electrode accommodating part 38 Reference electrode pressing part 40 Reference electrode accommodating part outer peripheral wall 41 Reference electrode accommodating part inner peripheral wall 42 Reference pole bottom wall

Claims (2)

作用極と、
前記作用極に対して対向配置される対極と、
前記作用極と前記対極との間に介在されるセパレータと、
前記作用極と前記対極との対向方向における前記作用極の投影面から離間するように配置され、かつ、前記作用極との間にセパレータが介在されずに配置される参照極と、
前記参照極を収容するための収容部材とを備え、
前記収容部材は、開口部を有する被押圧面が形成された収容部と、前記収容部に収容され、前記被押圧面を押圧するための押圧部とを備え、
前記収容部材の少なくとも一部は、前記電気化学セル内において、電解液によって浸漬されており、
前記押圧部は、前記収容部に対してスライド自在に収容され、
前記収容部は、前記参照極と反応せず、前記電解液と反応しない材料から形成されており、前記押圧部のスライドを案内するためのガイド部を備えており、
前記参照極は、前記開口部から露出するように、前記被押圧面と前記押圧部との間に配置されていることを特徴とする、電気化学セル。 Working electrode,
A counter electrode disposed opposite to the working electrode;
A separator interposed between the working electrode and the counter electrode;
A reference electrode disposed so as to be separated from a projection surface of the working electrode in a facing direction of the working electrode and the counter electrode, and disposed without a separator between the working electrode; and
A housing member for housing the reference electrode,
The accommodating member includes an accommodating portion in which a pressed surface having an opening is formed, and a pressing portion that is accommodated in the accommodating portion and presses the pressed surface.
At least a part of the housing member is immersed in the electrochemical cell with an electrolyte solution,
The pressing portion is slidably accommodated with respect to the accommodating portion,
The accommodating portion is formed of a material that does not react with the reference electrode and does not react with the electrolytic solution, and includes a guide portion for guiding the slide of the pressing portion,
The electrochemical cell, wherein the reference electrode is disposed between the pressed surface and the pressing portion so as to be exposed from the opening. 前記参照極が、リチウムであることを特徴とする、請求項１に記載の電気化学セル。   The electrochemical cell according to claim 1, wherein the reference electrode is lithium.
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