JP2000081405A - Electrochemical cell - Google Patents
Electrochemical cellInfo
- Publication number
- JP2000081405A JP2000081405A JP10352224A JP35222498A JP2000081405A JP 2000081405 A JP2000081405 A JP 2000081405A JP 10352224 A JP10352224 A JP 10352224A JP 35222498 A JP35222498 A JP 35222498A JP 2000081405 A JP2000081405 A JP 2000081405A
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- Prior art keywords
- electrode
- electrochemical cell
- electrolyte
- electrodes
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電気化学電極の電気
化学的挙動、例えば電池電極の充放電特性やインピーダ
ンスの評価、あるいは電解液やセパレータ（微多孔膜）
や固体電解質の電気伝導度等を評価するための評価用電
気化学セルに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochemical behavior of an electrochemical electrode, for example, evaluation of charge / discharge characteristics and impedance of a battery electrode, or an electrolyte or a separator (microporous membrane)
The present invention relates to an electrochemical cell for evaluation for evaluating electric conductivity and the like of a solid electrolyte.
【０００２】[0002]
【従来の技術】電気化学電極の電気化学的挙動や電解液
等の電気伝導度等を評価するために、従来では図１に示
される様な評価用電気化学セルが用いられてきた。この
セルは、評価しようとする電極を作用電極ａとし、これ
に対極ｂ及び参照電極ｃを組み合わせ、これらをガラス
管内に収容した電解質溶液ｄ中に吊り下げ配置して構成
されるものである。例えばリチウムイオン電池の正極と
して用いられる、リチウム含有複合酸化物を塗布した金
属箔の電極の放電曲線（作動電圧／持続時間の関係）を
評価する場合には、対極にリチウム、参照電極にリチウ
ム、そして電解液にＬｉＰＦ6 ／（エチレンカーボネー
ト＋メチルエチルカーボネート）等の非水電解溶液が用
いられる。2. Description of the Related Art In order to evaluate the electrochemical behavior of an electrochemical electrode and the electrical conductivity of an electrolytic solution and the like, an electrochemical cell for evaluation as shown in FIG. 1 has been conventionally used. In this cell, an electrode to be evaluated is used as a working electrode a, a counter electrode b and a reference electrode c are combined, and these are suspended and arranged in an electrolyte solution d contained in a glass tube. For example, when evaluating the discharge curve (operating voltage / duration relationship) of a metal foil electrode coated with a lithium-containing composite oxide used as a positive electrode of a lithium ion battery, lithium is used as a counter electrode, lithium is used as a reference electrode, and lithium is used as a reference electrode. Then, a non-aqueous electrolytic solution such as LiPF 6 / (ethylene carbonate + methyl ethyl carbonate) is used as the electrolytic solution.
【０００３】[0003]
【発明が解決しようとする課題】ところで、この従来の
電気化学セルでは作用電極、対極及び参照電極の各電極
が電解溶液中に単に吊り下げ状態で配置されているの
で、評価セルを作製する時点で常に各電極間隔を厳密に
一定に保つのは困難なことである。そして、評価セルを
組み立てた後、電気化学電極を評価する際にも、一定に
保つのは困難な場合がある。例えば、リチウムイオン電
池の正極として用いられる、リチウム含有複合酸化物を
金属箔に塗布した電極を評価する場合、評価中に該複合
酸化物が膨張し、それに伴って電極が変形したり、湾曲
したりして容易に電極間の間隔が変化する。各電極間の
間隔が少しでも変化すれば測定誤差を生じ、正確な測定
値が得られない。近年、電気化学電極の電気化学的挙動
等の測定値についても、求められる精度が年々厳しくな
っていることから、評価用電気化学セルの各電極間距離
をセルの組み立て時にあるいは評価時間中に常に厳密に
一定に保持できないという問題は、この分野における解
決すべき大きな課題となっている。In this conventional electrochemical cell, the working electrode, the counter electrode, and the reference electrode are simply suspended in the electrolytic solution. Therefore, it is difficult to keep the interval between the electrodes strictly constant. When the electrochemical cell is evaluated after the evaluation cell is assembled, it may be difficult to keep it constant. For example, when evaluating an electrode in which a lithium-containing composite oxide is applied to a metal foil, which is used as a positive electrode of a lithium-ion battery, the composite oxide expands during the evaluation, and the electrode deforms or curves with the evaluation. The gap between the electrodes easily changes. If the distance between the electrodes changes even slightly, a measurement error occurs, and an accurate measurement value cannot be obtained. In recent years, the required accuracy of the measured values of the electrochemical behavior of the electrochemical electrodes and the like is becoming stricter year by year, so the distance between the electrodes of the electrochemical cell for evaluation is always set at the time of assembling the cell or during the evaluation time. The problem of not being able to keep it strictly constant is a major problem to be solved in this field.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
に、本発明者等は各電極の位置固定手段を検討するう
ち、各電極を電解溶液中に吊り下げることに替えて、保
液材に電解液を含有せしめ、この保液材を介して各電極
を加圧するようにして配置すれば、セル組み立て時にあ
るいは評価時間中に各電極間距離を常に厳密に一定に保
持できることを見出し、本発明に至った。即ち、本発明
は、以下の（１）〜（３）の電気化学セルである。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied the means for fixing the position of each electrode, and instead of suspending each electrode in the electrolytic solution, a liquid retaining material was used. It has been found that the distance between the electrodes can be kept strictly constant at the time of cell assembly or during the evaluation time by arranging the electrodes so that the electrodes are pressurized through the liquid retaining material. Invented the invention. That is, the present invention provides the following electrochemical cells (1) to (3).
【０００５】（１）第１電極部および第２電極部が
（ｉ）保液材若しくは固体電解質と（ｉｉ）第３電極部
若しくは第３電極部及び第４電極部とを介して配置さ
れ、前記第１電極部と第２電極部は、可動手段により各
々独立に加圧される電気化学セル。 （２）第３電極部と第４電極部が、有孔である上記
（１）記載の電気化学セル。 （３）第１電極部および第２電極部の可動手段を、第１
電極部および第２電極部が重なり合うように案内するガ
イド機構を有する上記（１）又は（２）記載の電気化学
セル。(1) A first electrode portion and a second electrode portion are arranged via (i) a liquid retaining material or a solid electrolyte and (ii) a third electrode portion or a third electrode portion and a fourth electrode portion, An electrochemical cell wherein the first electrode portion and the second electrode portion are independently pressurized by a movable means. (2) The electrochemical cell according to (1), wherein the third electrode portion and the fourth electrode portion are perforated. (3) The movable means of the first electrode unit and the second electrode unit is
The electrochemical cell according to the above (1) or (2), further comprising a guide mechanism for guiding the electrode portion and the second electrode portion so as to overlap each other.
【０００６】次に、本発明の電気化学セルの各構成につ
いて３極式及び４極式について詳しく説明する。 ３極式（第１〜３電極）の場合について 図２を用いて説明する。図２は３極式の電気化学セルの
概念図である。第１電極(1) と第２電極(2) との間に第
３電極(3) が、そして第１電極(1) と第３電極(3) 及び
第２電極(2) と第３電極(3) との間に夫々電解液を含有
する保液材、若しくは固体電解質（4)，(4) が配置され
ている。第１電極(1) と第２電極(2) は同一面積であ
り、第３電極(3) は第１電極(1) と等しいか或いはより
大きな面積を有している。この第３電極(3) は、電解液
の移動を妨げない形状であればよく、好ましくは穴あき
又はグリッド状であって、具体的にはエキスパンドメタ
ル、パンチングメタル、エッチング箔等から構成される
のが好ましい。また開口率としては、２０％以上である
ことが好ましい。保液材(4) 、(4) の材料としては、ガ
ラスウール、アラミド不織布又は抄紙、ポリエチレン又
はポリプロピレン不織布、微多孔膜等の１種又は２種以
上を組み合わせたものがある。また、固体電解質には、
ポリエチレンオキシド、ポリプロピレンオキシド、ポリ
アクリロニトリル、ポリフッ化ビニリデン、フッ化ビニ
リデン−ヘキサフルオロプロピレン共重合体、ビニルエ
ーテル共重合体などの高分子と電解質あるいは電解質溶
液との複合体、あるいは上記高分子に電解質溶液を担持
させたゲル状のものなどがある。Next, the three-electrode type and the four-electrode type of the electrochemical cell of the present invention will be described in detail. The case of a three-pole type (first to third electrodes) will be described with reference to FIG. FIG. 2 is a conceptual diagram of a three-electrode electrochemical cell. There is a third electrode (3) between the first electrode (1) and the second electrode (2), and the first electrode (1) and the third electrode (3), and the second electrode (2) and the third electrode. A liquid retaining material containing an electrolytic solution or solid electrolytes (4) and (4) are arranged between (3) and (3). The first electrode (1) and the second electrode (2) have the same area, and the third electrode (3) has an area equal to or larger than the first electrode (1). The third electrode (3) may have any shape as long as it does not hinder the movement of the electrolytic solution, and is preferably perforated or grid-shaped, and is specifically made of expanded metal, punching metal, etching foil, or the like. Is preferred. The aperture ratio is preferably 20% or more. Examples of the liquid retaining materials (4) and (4) include one or a combination of two or more of glass wool, aramid nonwoven fabric or papermaking, polyethylene or polypropylene nonwoven fabric, and microporous membrane. In addition, the solid electrolyte includes
Polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinyl ether copolymer or other polymer and electrolyte or electrolyte solution complex, or the above polymer with electrolyte solution There is a gel-like one carried.
【０００７】第１電極(1) と第２電極(2) は、その上下
方向よりバネ(5) ，(5) で付勢されたプランジャー(6)
，(6) 等の電極均等加圧手段により一定圧力で均等に
押圧されている。その圧力の大きさは保液材の種類によ
りかなり大きく異なるが、要は保液材から電解液が追い
出されないが、電極を一定位置に保持するのに必要な圧
力である。プランジャー(6) ，(6) の付勢は、バネ以外
にピストン−シリンダーの流体加圧方式であってもよ
い。[0007] The first electrode (1) and the second electrode (2) are plunger (6) urged by springs (5), (5) from above and below.
, (6) and the like, the electrodes are uniformly pressed at a constant pressure. Although the magnitude of the pressure varies considerably depending on the type of liquid retaining material, the point is that the electrolyte is not expelled from the liquid retaining material, but it is the pressure required to hold the electrode in a fixed position. The plungers (6), (6) may be biased by a piston-cylinder fluid pressurization method other than a spring.
【０００８】プランジャー(6) ，(6) は、第１電極(1)
又は第２電極(2) と同じ間隔で配置された電極ガイド
(7) ，(7) の間を案内され、第１〜３電極に垂直に均等
に圧力を加える。上下の電極ガイド(7) ，(7) は、第１
電極(1) 又は第２電極(2) が重なり合って案内され加圧
されるために、要すれば位置合わせ機構(8) を有する。
重なり合う程度としては、第１電極(1) と第２電極(2)
のずれが、これら電極間距離より小さいこと、好ましく
は上記電極間距離の１０分の１以下である。この３極式
の電気化学セルの具体例を次の図３に、そして図３より
好ましい具体例を図４に示す。図３では上部側電極ガイ
ド(7) は電極ガイド押さえとバネ押さえ板との両方を有
しているのに対し、図４では電極ガイド(7) の上下どち
らもバネ押さえ板(10)により押さえられ上下対称となる
ため、部品点数が減り構成が簡潔となり取扱も簡便とな
る利点がある。図３〜４において、電気化学セルの構成
部材の材質が金属である場合には対向端面に絶縁物(9)
が配置される。絶縁物(9) は耐電解液性が必要であり、
更に電解液が非水系の場合は大気中の水分による悪影響
を受けやすいので、大気から遮断するシール機能を具備
する必要がある。この耐電解液性とシール機能を発揮さ
せる具体的態様としては、電極ガイド(7) の外側に耐電
解液性を有する絶縁物(9) を、そして更にその外側にシ
ール機能を有する絶縁物(9) を配置したり、両機能を同
時に併せ持つ素材で又は各々の機能を有する素材を積層
して構成した絶縁物(9) をその外側の１か所以上に配置
したりすることができる。また、バネ(5) 、プランジャ
ー(6) 、位置合わせ機構(8) 、バネ押さえ板(10)は、第
１電極(1) 〜第４電極(4) に対し通電又は集電機能を持
たせてもよい。The plungers (6), (6) are first electrodes (1).
Or an electrode guide arranged at the same interval as the second electrode (2)
Guided between (7) and (7), pressure is evenly applied vertically to the first to third electrodes. The upper and lower electrode guides (7) and (7)
Since the electrode (1) or the second electrode (2) is guided and pressurized in an overlapping manner, a positioning mechanism (8) is provided if necessary.
As for the degree of overlap, the first electrode (1) and the second electrode (2)
Is smaller than these inter-electrode distances, preferably one-tenth or less of the inter-electrode distances. FIG. 3 shows a specific example of the three-electrode electrochemical cell, and FIG. 4 shows a specific example more preferable than FIG. In FIG. 3, the upper electrode guide (7) has both an electrode guide holder and a spring holder, while in FIG. 4, both the upper and lower sides of the electrode guide (7) are held by the spring holder (10). Since it is vertically symmetrical, there is an advantage that the number of parts is reduced, the configuration is simple, and the handling is simple. 3 and 4, when the material of the constituent members of the electrochemical cell is metal, an insulator (9)
Is arranged. The insulator (9) must have resistance to electrolyte,
Further, when the electrolyte is non-aqueous, it is liable to be adversely affected by moisture in the atmosphere, and therefore, it is necessary to provide a sealing function for shielding the electrolyte from the atmosphere. As a specific embodiment for exhibiting the electrolytic solution resistance and the sealing function, an insulator (9) having an electrolytic solution resistance is provided outside the electrode guide (7), and an insulator having a sealing function is further provided outside the electrode guide (7). 9), or an insulator (9) formed of a material having both functions simultaneously or a material obtained by laminating materials having the respective functions can be arranged at one or more locations outside the insulator (9). The spring (5), the plunger (6), the positioning mechanism (8), and the spring holding plate (10) have a function of energizing or collecting current for the first to fourth electrodes (1) to (4). You may let it.
【０００９】この３極式の場合は、具体的には電池電極
の充放電特性やインピーダンスの測定（特願平９−７９
１１５号）等の電気化学電極の電気化学的挙動を評価す
る場合に用いられる。このようにして構成された本発明
の電気化学セルは、第１〜３電極が電極ガイド(7) ，
(7) の間を案内される均等加圧手段(6),(6) により常に
一定圧力で均等に垂直に押圧されるので、セルの組み立
て時にあるいは電極の電気化学的挙動を評価中に、各電
極が一定間隔で且つずれることなく正確に対向され保持
されるので、その結果高精度で再現性のよいデータが取
得できる。このことは、特に電極が評価中に膨張し電極
が変形したり、湾曲したりする（電極間距離が変化す
る）場合にはさらに効果的である。 ４極式（第１〜４電極）の場合について 図５を用いて説明する。図５は４極式の電気化学セルの
概念図である。In the case of the three-electrode system, specifically, measurement of the charge / discharge characteristics and impedance of the battery electrode (Japanese Patent Application No. 9-79).
No. 115) is used to evaluate the electrochemical behavior of an electrochemical electrode. In the electrochemical cell of the present invention thus configured, the first to third electrodes have electrode guides (7),
(7) It is always evenly and vertically pressed at a constant pressure by the uniform pressurizing means (6), (6) guided between (7), so during the assembly of the cell or during the evaluation of the electrochemical behavior of the electrodes, Since the electrodes are accurately opposed and held at regular intervals and without deviation, data with high accuracy and high reproducibility can be obtained. This is particularly effective when the electrode expands during the evaluation and deforms or curves (the distance between the electrodes changes). The case of a four-pole type (first to fourth electrodes) will be described with reference to FIG. FIG. 5 is a conceptual diagram of a four-electrode electrochemical cell.
【００１０】第１電極(1) と第２電極(2) との間に、第
３電極(3a)とさらに第４電極(3b)が、そして第１電極
(1) と第３電極(3a)、第２電極(2) と第４電極(3b)及び
第３電極(3a)と第４電極(3b)との間に夫々電解液を含有
する保液材(4) ，(4) ，(4´)が配置されている。それ
以外の構成は上記３極式（第１〜３電極）の場合と同様
である。この４極式の電気化学セルの具体例を次の図６
に示す。この４極式の場合は、具体的には電解液の外、
セパレータ（微多孔膜）や固体電解質の電気伝導度等の
電気化学的挙動を評価するのに用いられる。なお、この
場合には第３電極(3a)と第４電極(3b)には、評価する系
によって異なるが、不働態を作りにくいＰｔのメッシュ
を用いることが好ましい。また、セパレータ（微多孔
膜）や固体電解質の電気伝導度等を評価する際には、第
３電極(3a)と第４電極(3b)との間には、保液材に挟まれ
たセパレータ（微多孔膜）や固体電解質等を配置するこ
ともできる。A third electrode (3a) and a fourth electrode (3b) are provided between the first electrode (1) and the second electrode (2).
(1) and a third electrode (3a); a second electrode (2) and a fourth electrode (3b); and a liquid containing an electrolyte between the third electrode (3a) and the fourth electrode (3b). Materials (4), (4) and (4 ') are arranged. Other configurations are the same as those of the above-described three-pole type (first to third electrodes). A specific example of this four-electrode electrochemical cell is shown in FIG.
Shown in In the case of this four-electrode type, specifically, outside the electrolyte,
It is used to evaluate electrochemical behavior such as electrical conductivity of a separator (microporous membrane) and solid electrolyte. Note that, in this case, it is preferable to use a Pt mesh that does not easily create a passivation, depending on the system to be evaluated, for the third electrode (3a) and the fourth electrode (3b). When evaluating the electrical conductivity of a separator (microporous membrane) or a solid electrolyte, a separator sandwiched between liquid retaining materials is provided between the third electrode (3a) and the fourth electrode (3b). (A microporous membrane), a solid electrolyte, and the like can also be provided.
【００１１】このようにして構成された本発明の４極式
の電気化学セルも、その３極式のものと同様にセルの組
み立て時にあるいは電極の電気化学的挙動を評価中に、
各電極が一定間隔で且つずれなく正確に対向され保持さ
れるので、高精度で再現性のよいデータが取得できる。[0011] The four-electrode electrochemical cell of the present invention thus constructed is also similar to the three-electrode cell during assembly of the cell or during evaluation of the electrochemical behavior of the electrode.
Since the electrodes are accurately opposed and held at regular intervals and without deviation, highly accurate and highly reproducible data can be obtained.
【発明の実施の形態】以下、本発明を実施例に基づいて
更に詳細に説明するが、本発明は実施例に制限されるも
のではない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.
【００１２】[0012]
【実施例】（実施例１）図３の３極式の電気化学セルを
用いてアルミ箔に塗布したリチウム含有複合酸化物（Ｌ
ｉＣｏ0.99Ｓｎ0.01Ｏ2 ）の充放電特性を測定した。先
ず、第１電極(1) を次のように製作した。平均粒径４μ
ｍでＳｎ含有正極活物質ＬｉＣｏ0.99Ｓｎ0.01Ｏ2 １０
０重量部に対して、導電剤として平均粒径４μｍのグラ
ファイトカーボン２．５重量部と平均粒径０．０４μｍ
の非黒鉛炭素質粉末２．５重量部を混ぜ合わせてコンパ
ウンドとした。このコンパウンドに対してポリフッ化ビ
ニリデン３重量部を含むＮ−メチルピロリドン溶液にこ
のコンパウンドを分散させた。そして、この分散液を厚
さ１５μｍのＡｌ箔に塗布量２７７ｇ／ｍとなるようプ
レスした。このようにして塗布・プレスしたＡｌ箔を、
面積２ｃｍ2 の円形に加工して第１電極を作製した。EXAMPLE 1 A lithium-containing composite oxide (L) coated on aluminum foil using the three-electrode electrochemical cell of FIG.
The charge / discharge characteristics of iCo 0.99 Sn 0.01 O 2 ) were measured. First, the first electrode (1) was manufactured as follows. Average particle size 4μ
m, the Sn-containing positive electrode active material LiCo 0.99 Sn 0.01 O 2 10
0 parts by weight, 2.5 parts by weight of graphite carbon having an average particle size of 4 μm as a conductive agent and 0.04 μm of average particle size
Was mixed with 2.5 parts by weight of the non-graphite carbonaceous powder of Example 1 to obtain a compound. This compound was dispersed in an N-methylpyrrolidone solution containing 3 parts by weight of polyvinylidene fluoride with respect to this compound. Then, this dispersion was pressed onto an Al foil having a thickness of 15 μm so as to have a coating amount of 277 g / m. The Al foil coated and pressed in this way is
The first electrode was fabricated by processing into a circle having an area of 2 cm 2 .
【００１３】次に、第２電極(2) を、面積２ｃｍ2 の円
形に加工したＮｉメッシュの全面に金属Ｌｉを圧着し、
更に第３電極(3) を、面積２ｃｍ2 の円形に加工したＳ
ＵＳメッシュにＬｉワイヤーを圧着（圧着した状態での
開口率は７０％）して夫々製作した。保液材(4) はガラ
スウールにエチレンカーボネートとメチルエチルカーボ
ネートとの混合溶媒（１：２）１リットルに１ｍｏｌの
電解質ＬｉＰＦ6 を溶解した電解液を入れ含浸させて作
製した。Next, the second electrode (2) is pressed with metal Li over the entire surface of a Ni mesh processed into a circular shape having an area of 2 cm 2 ,
Further, the third electrode (3) was processed into a circular shape having an area of 2 cm 2 by S
A Li wire was pressure-bonded to a US mesh (opening ratio in a pressure-bonded state was 70%) to produce each. The liquid retaining material (4) was prepared by impregnating glass wool with an electrolytic solution obtained by dissolving 1 mol of an electrolyte LiPF 6 in 1 liter of a mixed solvent of ethylene carbonate and methyl ethyl carbonate (1: 2).
【００１４】そして、第１電極と第２電極との間に第３
電極を挿入するとともに、第１電極と第３電極との間及
び第２電極と第３電極との間に各々上記保液材(4) を配
置し積層体を構成し、この積層体を図３のプランジャー
(6),(6) 間にセットし、バネ(5),(5) で上下より８００
ｇ／ｃｍ2 の力で加圧した。続いて、この状態で第３電
極を参照電極として、第１電極と第３電極で電圧を制御
しながら、第１電極と第２電極間で充放電をおこなっ
た。その充放電条件は充電０．３ＣｍＡ、６ｈ、４．２
Ｖ定電圧定電流、放電０．３ＣｍＡ、３．０Ｖ定電流で
あった。第１電極と第２電極間で常法により充放電容量
（ｍＡｈ／ｇ）と充放電効率（％）とを測定したとこ
ろ、各々１４２ｍＡｈ／ｇ、９５％であった。この実験
を同様にして繰り返し行ったところ、毎回再現性良く正
確なデータが取得できた。The third electrode is provided between the first electrode and the second electrode.
The electrodes are inserted, and the liquid retaining material (4) is arranged between the first electrode and the third electrode and between the second electrode and the third electrode to form a laminate. 3 plungers
(6) Set between (6) and (800) from above and below with springs (5) and (5)
It was pressurized with a force of g / cm 2 . Subsequently, in this state, charging and discharging were performed between the first and second electrodes while controlling the voltage with the first and third electrodes using the third electrode as a reference electrode. The charge and discharge conditions were as follows: charge 0.3 CmA, 6 h, 4.2
V constant voltage constant current, discharge 0.3 CmA, and 3.0 V constant current. When the charge / discharge capacity (mAh / g) and the charge / discharge efficiency (%) between the first electrode and the second electrode were measured by an ordinary method, they were 142 mAh / g and 95%, respectively. When this experiment was repeated in the same manner, accurate data was obtained with good reproducibility every time.
【００１５】（実施例２）図６の４極式の電気化学セル
を用いて、エチレンカーボネートとメチルエチルカーボ
ネートとの混合溶媒（１：２）１リットルに１ｍｏｌの
電解質ＬｉＰＦ6を溶解した電解液の電気伝導度を測定
した。第１電極(1) 及び第２電極(2) として面積２ｃｍ
2 の円形に加工したＰｔ電極を、そして第３電極(3a)及
び第４電極(3b)として面積２ｃｍ2 の円形に加工したＰ
ｔメッキしたＳＵＳメッシュ電極を用いた。保液材(4)
はガラスウールにエチレンカーボネートとメチルエチル
カーボネートとの混合溶媒（１：２）１リットルに１ｍ
ｏｌの電解質ＬｉＰＦ6 を溶解した電解液を入れ含浸さ
せて作製した。(Example 2) An electrolytic solution obtained by dissolving 1 mol of electrolyte LiPF 6 in 1 liter of a mixed solvent of ethylene carbonate and methyl ethyl carbonate (1: 2) using a four-electrode electrochemical cell shown in FIG. Was measured for electrical conductivity. 2 cm area as the first electrode (1) and the second electrode (2)
2 of the processed Pt electrode to a circle, and processed into a circular area of 2 cm 2 as the third electrode (3a) and the fourth electrode (3b) P
A SUS mesh electrode plated with t was used. Liquid retention material (4)
Is 1 m in 1 liter of mixed solvent of ethylene carbonate and methyl ethyl carbonate (1: 2) in glass wool
ol electrolyte LiPF 6 was dissolved in the electrolyte and impregnated.
【００１６】そして、第１電極(1) と第２電極(2) との
間に第３電極(3a)及び第４電極(3b)を挿入するととも
に、第１電極(1) と第３電極(3a)との間、第２電極(2)
と第３電極(3b)との間及び第３電極(3a)と第４電極(3b)
との間に各々上記保液材(4)(4´) を配置し積層体を構
成し、この積層体を図６のプランジャー(6),(6) にセッ
トし、バネ(5),(5) で上下より８００ｇ／ｃｍ2 の力で
加圧した。なお、第３電極(3a)と第４電極(3b)間の距離
は２ｍｍであった。A third electrode (3a) and a fourth electrode (3b) are inserted between the first electrode (1) and the second electrode (2), and the first electrode (1) and the third electrode (3) are inserted. (3a), the second electrode (2)
And the third electrode (3b) and between the third electrode (3a) and the fourth electrode (3b)
The above-mentioned liquid retaining materials (4) and (4 ') are arranged between them to form a laminate, and this laminate is set on plungers (6) and (6) in FIG. In (5), pressure was applied from above and below with a force of 800 g / cm 2 . The distance between the third electrode (3a) and the fourth electrode (3b) was 2 mm.
【００１７】続いて、この状態で第１電極(1) と第２電
極(2) 間に電流０．５〜５．０ｍＡを流した。その際第
３電極(3a)と第４電極(3b)間の電圧を測定したところ
６．９〜７２ｍＶであった。この電流値と電圧値を直線
近似して、その傾きより電気伝導度を求めると、上記電
解液の電気伝導度は７（ｍＳ／ｃｍ）であることが判っ
た。この実験を同様にして繰り返し行ったところ、毎回
再現性良く正確なデータが取得できた。Subsequently, in this state, a current of 0.5 to 5.0 mA was passed between the first electrode (1) and the second electrode (2). At that time, when the voltage between the third electrode (3a) and the fourth electrode (3b) was measured, it was 6.9 to 72 mV. When the current value and the voltage value were linearly approximated and the electric conductivity was obtained from the slope, it was found that the electric conductivity of the electrolytic solution was 7 (mS / cm). When this experiment was repeated in the same manner, accurate data was obtained with good reproducibility every time.
【００１８】[0018]
【発明の効果】以上のように、各電極を電解溶液中に吊
り下げることに替えて、保液材に電解液を含有せしめ、
この保液材を介して各電極を加圧するようにしたので、
電極の電気化学的挙動を評価中に、各電極が一定間隔で
且つずれなく正確に対向され保持できるので、正確で再
現性のよいデータが取得できる。As described above, instead of suspending each electrode in the electrolytic solution, the liquid retaining material is made to contain the electrolytic solution.
Since each electrode was pressurized through this liquid retaining material,
During the evaluation of the electrochemical behavior of the electrodes, the electrodes can be opposed and held at regular intervals and without any deviation, so that accurate and reproducible data can be obtained.
【図１】従来の評価用電気化学セルの組み立て図であ
る。FIG. 1 is an assembly view of a conventional electrochemical cell for evaluation.
【図２】３極式電気化学セルの概念図である。FIG. 2 is a conceptual diagram of a three-electrode electrochemical cell.
【図３】３極式電気化学セルの具体例を示す図である。FIG. 3 is a diagram showing a specific example of a three-electrode electrochemical cell.
【図４】３極式電気化学セルの他の具体例を示す図であ
る。FIG. 4 is a view showing another specific example of a three-electrode electrochemical cell.
【図５】４極式電気化学セルの概念図である。FIG. 5 is a conceptual diagram of a four-electrode electrochemical cell.
【図６】４極式電気化学セルの具体例を示す図である。FIG. 6 is a diagram showing a specific example of a four-electrode electrochemical cell.
１ 第１電極 ２ 第２電極 ３，３ａ 第３電極 ３ｂ 第４電極 ４ 保液材、固体電解質のいずれか ４´保液材、セパレータ（保液材／セパレータ／保液
材）、固体電解質（保液材／固体電解質／保液材）のい
ずれか ５ バネ ６ プランジャー ７ ガイド機構（電極ガイド） ８ 位置合わせ機構 ９ 絶縁物 １０ バネ押さえ板Reference Signs List 1 1st electrode 2 2nd electrode 3, 3a 3rd electrode 3b 4th electrode 4 Any of liquid retention material and solid electrolyte 4 'liquid retention material, separator (liquid retention material / separator / liquid retention material), solid electrolyte ( Any of liquid retaining material / solid electrolyte / liquid retaining material) 5 spring 6 plunger 7 guide mechanism (electrode guide) 8 positioning mechanism 9 insulator 10 spring holding plate
Claims (3)
保液材若しくは固体電解質と（ｉｉ）第３電極部若しく
は第３電極部及び第４電極部とを介して配置され、前記
第１電極部と第２電極部は、可動手段により各々独立に
加圧されることを特徴とする電気化学セル。1. The method according to claim 1, wherein the first electrode portion and the second electrode portion are (i)
The liquid retaining material or the solid electrolyte and (ii) a third electrode portion or a third electrode portion and a fourth electrode portion are interposed therebetween, and the first electrode portion and the second electrode portion are independently added by movable means. An electrochemical cell characterized by being pressurized.
ことを特徴とする請求項１記載の電気化学セル。2. The electrochemical cell according to claim 1, wherein the third electrode portion and the fourth electrode portion are perforated.
を、第１電極部および第２電極部が重なり合うように案
内するガイド機構を有することを特徴とする請求項１又
は請求項２記載の電気化学セル。3. A guide mechanism for guiding the movable means of the first electrode portion and the second electrode portion so that the first electrode portion and the second electrode portion overlap each other. An electrochemical cell as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10352224A JP2000081405A (en) | 1998-06-29 | 1998-12-11 | Electrochemical cell |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-196518 | 1998-06-29 | ||
| JP19651898 | 1998-06-29 | ||
| JP10352224A JP2000081405A (en) | 1998-06-29 | 1998-12-11 | Electrochemical cell |
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| Publication Number | Publication Date |
|---|---|
| JP2000081405A true JP2000081405A (en) | 2000-03-21 |
Family
ID=26509785
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|---|---|---|---|
| JP10352224A Withdrawn JP2000081405A (en) | 1998-06-29 | 1998-12-11 | Electrochemical cell |
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006147513A (en) * | 2004-11-22 | 2006-06-08 | Nippon Tomuseru:Kk | Cell for electrochemical property measurement and electrochemical property measuring method using same |
| JP2006179191A (en) * | 2004-12-20 | 2006-07-06 | Daihatsu Motor Co Ltd | Electrochemical cell |
| KR20190122959A (en) * | 2018-04-23 | 2019-10-31 | 한국과학기술연구원 | Device having one-axis pressing structure for measuring electrochemical properties |
| US20210310975A1 (en) * | 2018-12-19 | 2021-10-07 | Korea Basic Science Institute | In-situ optical and electrochemical analysis method and battery cell section measurement module therefor |
-
1998
- 1998-12-11 JP JP10352224A patent/JP2000081405A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006147513A (en) * | 2004-11-22 | 2006-06-08 | Nippon Tomuseru:Kk | Cell for electrochemical property measurement and electrochemical property measuring method using same |
| JP4580751B2 (en) * | 2004-11-22 | 2010-11-17 | 有限会社日本トムセル | Electrochemical property measuring cell and electrochemical property measuring method using the same |
| JP2006179191A (en) * | 2004-12-20 | 2006-07-06 | Daihatsu Motor Co Ltd | Electrochemical cell |
| JP4541869B2 (en) * | 2004-12-20 | 2010-09-08 | ダイハツ工業株式会社 | Electrochemical cell |
| KR20190122959A (en) * | 2018-04-23 | 2019-10-31 | 한국과학기술연구원 | Device having one-axis pressing structure for measuring electrochemical properties |
| KR102097287B1 (en) * | 2018-04-23 | 2020-04-06 | 한국과학기술연구원 | Device having one-axis pressing structure for measuring electrochemical properties |
| US20210310975A1 (en) * | 2018-12-19 | 2021-10-07 | Korea Basic Science Institute | In-situ optical and electrochemical analysis method and battery cell section measurement module therefor |
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