JPS61264685A - Chargeable and dischargeable electrochemical device - Google Patents

Chargeable and dischargeable electrochemical device

Info

Publication number
JPS61264685A
JPS61264685A JP60107307A JP10730785A JPS61264685A JP S61264685 A JPS61264685 A JP S61264685A JP 60107307 A JP60107307 A JP 60107307A JP 10730785 A JP10730785 A JP 10730785A JP S61264685 A JPS61264685 A JP S61264685A
Authority
JP
Japan
Prior art keywords
polypropylene
thin film
microporous thin
separator
sealing plate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP60107307A
Other languages
Japanese (ja)
Inventor
Toshihiko Ikehata
敏彦 池畠
Hayashi Hayakawa
早川　林
Nobuharu Koshiba
信晴 小柴
Toshio Shigematsu
重松　敏雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP60107307A priority Critical patent/JPS61264685A/en
Publication of JPS61264685A publication Critical patent/JPS61264685A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

PURPOSE:To improve charge-and-discharge characteristics on heavy load, with internal resistance lowered, by forming separators in three-layer structure and putting a polypropylene microporous thin film between two sheets of polypropylene non-woven fabric. CONSTITUTION:An electrochemical device is composed of a case 1 made by stamping a stainless steel plate, a sealing plate 2 made similarly by processing the same material, a polypropylene gasket 3 with which the case 1 and the sealing plate 2 are insulated. A separator 5 is formed of polypropylene non- woven fabric, a separator 6 is formed of a polypropylene microporous thin film, and a negative electrode alloy 7 is formed by melting-alloying 50pts.wt. of lead, 47pts.wt. of cadmium, and 3pts.wt. of lithium, thereafter with it rolled and transferred on a stainless steel net 8, stamped into 15mm in diameter, and welded on the sealing plate 2. Hence, with an internal resistance lowered by electrolytic solution sufficiently existing on the surfaces of both positive and negative electrodes, charge-and-discharge characteristics on heavy load can be improved with effects of microporous thin films.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、移動用直流電源、バックアップ用電源などに
用いる充放電可能な電気化学装置に関するものでろる。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a chargeable and dischargeable electrochemical device used as a mobile DC power source, a backup power source, and the like.

従来の技術 正極に電気二重層を利用した活性炭、負極にリチウム合
金、電解液に非水系の有機溶媒を用いた充放電可能な電
気化学装置において、従来、セパレータとして次のよう
な構造が採られていた。Conventional technology In chargeable and dischargeable electrochemical devices that use activated carbon that uses an electric double layer for the positive electrode, a lithium alloy for the negative electrode, and a non-aqueous organic solvent for the electrolyte, the following structure has traditionally been adopted as a separator. was.

（１）　　ポリプロピレン製不織布のみを１枚めるいは
複数枚用いる。(1) One or more polypropylene nonwoven fabrics are used.

（２）　　ポリプロピレン裏不織布１枚と、ポリプロピ
レン製微孔性薄膜１枚とを重ねて用いる。(2) One sheet of polypropylene backing nonwoven fabric and one sheet of polypropylene microporous thin film are used in layers.

（３）ポリプロピレン製微孔性薄膜のみを１枚あるいは
複数枚用いる。(3) Only one or more polypropylene microporous thin films are used.

発明が解決しようとする問題点 これらのうち、（１）の構造のセパレータは、電解液の
吸液性、保液性は非常に良く、正極及び負極表面の濡れ
が良いため、装置の内部抵抗も低く、また切断加工が容
易なため、作り易いという利点がめる。しかし不織布の
みを用いた場合、強負荷の充放電を繰り返すと劣化が早
くなる場合がある。Problems to be Solved by the Invention Among these, the separator with the structure (1) has very good electrolyte absorption and retention properties, and has good wettability on the surfaces of the positive and negative electrodes, so the internal resistance of the device is low. It has the advantage of being easy to manufacture as it has low heat and is easy to cut. However, when only nonwoven fabric is used, repeated charging and discharging under heavy loads may lead to rapid deterioration.

これは、装置内で正、負極間でのイオンの移動が激しい
ため、負極表面にデンドライトと呼ばれるリチウムの樹
枝状の結晶が析出し、これがセパレータを貫通して内部
短絡を引き起こし、充放電サイクル寿命を劣化嘔せるも
のと思われる。次に、り）の構造のように、ポリプロピ
レン製微孔性薄膜をセパレータに用いると、その細孔に
より、前述のデンドライトの生成が抑制され、（１）の
構造に比べて強負荷の充放電性能は改善される。しかし
、この微孔性薄膜は、吸液速度、保液性が非常に悪く、
正極あるいは負極表面に位置した場合、電極表面の濡わ
が悪くなり、装置の内部抵抗が高くなる欠点がめる。ま
た、この微孔性薄膜は非常に薄いため、打ち抜きなどの
切断加工が困難なため、加工の際、パリ、破れなどが発
生しやすくなり、製造上困難である。This is due to the intense movement of ions between the positive and negative electrodes within the device, which causes lithium branch-like crystals called dendrites to precipitate on the surface of the negative electrode, which penetrate the separator and cause an internal short circuit, resulting in a longer charge/discharge cycle life. It is thought that it will deteriorate and cause nausea. Next, when a microporous thin film made of polypropylene is used as a separator, as in structure (2), the pores suppress the formation of the dendrites mentioned above, and the charging/discharging under heavy load is faster than in structure (1). Performance is improved. However, this microporous thin film has very poor liquid absorption speed and liquid retention.
If it is located on the surface of the positive or negative electrode, the wetting of the electrode surface becomes poor and the internal resistance of the device increases. In addition, since this microporous thin film is very thin, it is difficult to cut it by punching or the like, so that it is prone to cracking, tearing, etc. during processing, making it difficult to manufacture.

（３）の構造の場合、（２）の構造と同様の問題に加え
、封口の際の加圧によシ、装置内部で、前述の微孔性薄
膜が破損し、内部シヲートを引き起こすという問題点が
生ずる。In the case of structure (3), in addition to the same problem as structure (2), the above-mentioned microporous thin film is damaged inside the device due to pressurization during sealing, causing internal sheeting. A dot appears.

本発明は、上記のような問題点を解消し、内部抵抗が低
く、強負荷充放電特性の優れた、また、製造も容易であ
る充放電可能な電気化学装置を提供することを目的とす
る。It is an object of the present invention to solve the above-mentioned problems and provide a chargeable and dischargeable electrochemical device that has low internal resistance, excellent high-load charging and discharging characteristics, and is easy to manufacture. .

問題点？解決するための手段 この問題点を解決するため本発明は、セパレータの構造
を３層構造とし２枚のポリプロピレン製不織布の間に、
ポリプロピレン製微孔性薄膜を介在した構造としたもの
である。problem? Means for Solving In order to solve this problem, the present invention has a three-layer structure for the separator, and between two sheets of polypropylene nonwoven fabric,
It has a structure in which a microporous thin film made of polypropylene is interposed.

作用 この構成によれば、正極側と負極側の両極に、電解液の
保液性の優わた不織布が存在するため、両極表面に電解
液が充分存在し、その結果、内部抵抗も低くなり、また
微孔性薄膜の効果で、強負荷による充放電性能も良好と
なる。加えて、微孔性薄膜が不織布ではさんだ状態で打
ち抜き、あるいは切断加工などができるため、単独では
非常に困難であった微孔性薄膜の切断加工が容易となシ
、量産性を高めることができる。According to this structure, since the nonwoven fabric with excellent electrolyte retention properties is present on both the positive and negative electrodes, there is sufficient electrolyte on the surfaces of both electrodes, and as a result, the internal resistance is low. Furthermore, due to the effect of the microporous thin film, charging and discharging performance under heavy loads is also improved. In addition, since the microporous thin film can be punched or cut while being sandwiched between nonwoven fabrics, cutting of the microporous thin film, which would have been extremely difficult to do on its own, is easy, and mass productivity can be improved. can.

実施例 以下本発明の実施例を図を参照して説明する。Example Embodiments of the present invention will be described below with reference to the drawings.

図に正極に活性炭、負極にリチウム合金を用いた充放電
可能な電気化学装置を示す。１は厚さ０．２５１８のス
テンレス鋼板を打ち抜き加工したケース、２は同材料を
同様に加工した封口板、３はケース１と封口板２を絶縁
するポリプロピレン製ガスケット、４は正極で、表面積
が−＋　ｅｓ　ｏ　ｏｖｆ１９の活性炭７０重量部と、
導電材であるアセチレンブラック１０重量部、及び結着
剤であるポリ４フツ化エチレン２０重量部を混練した後
、外径１５鵡、厚み１．○鵡に加圧成型したものである
。６及び６はセパレータで６は厚み０．１５１１のポリ
プロピレン製不織布、６は厚み０．０２５１ｓのポリプ
ロピレン製微孔性薄膜（孔径、約Ｑ、０２μｍ）である
。アは負極合金で、鉛５Ｑ重量部、カドミウム４７重量
部、リチウム３重量部を融解合金化した後、厚さ０．１
１ＥＢに圧延し、ステンレス鋼製ネット８に転写し、直
径１５１１Ｂに打ち抜き、封口板２に溶接した。９はチ
タン製正極集電体でケース１の内面に溶接されている。The figure shows a chargeable and dischargeable electrochemical device that uses activated carbon for the positive electrode and a lithium alloy for the negative electrode. 1 is a case made by punching a stainless steel plate with a thickness of 0.2518, 2 is a sealing plate made of the same material and processed in the same way, 3 is a polypropylene gasket that insulates the case 1 and the sealing plate 2, 4 is a positive electrode, and the surface area is −+ 70 parts by weight of activated carbon of es o ovf19;
After kneading 10 parts by weight of acetylene black as a conductive material and 20 parts by weight of polytetrafluoroethylene as a binder, an outer diameter of 15 mm and a thickness of 1. ○It is pressure molded into a parrot. 6 and 6 are separators, 6 is a polypropylene non-woven fabric with a thickness of 0.1511, and 6 is a polypropylene microporous thin film (pore diameter, approximately Q, 02 μm) with a thickness of 0.0251 s. A is a negative electrode alloy, which has a thickness of 0.1 after melting and alloying 5Q parts by weight of lead, 47 parts by weight of cadmium, and 3 parts by weight of lithium.
It was rolled to 1EB, transferred to a stainless steel net 8, punched out to a diameter of 1511B, and welded to the sealing plate 2. 9 is a titanium positive electrode current collector that is welded to the inner surface of the case 1.

電解液には炭酸プロピレンと１，２−ジメトキシエタン
との等溶損混合溶媒にホウフッ化リチウムを１モル／ｅ
の割合で溶解したものを用いた。The electrolyte contains 1 mol/e of lithium fluoroborate in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane.
A solution dissolved at the following ratio was used.

尚、この装置は、直径２０．０ｍ、厚”ｑ２．ｏｍ。This device has a diameter of 20.0 m and a thickness of 2.0 m.

容量は１ｖ当たり１　ｍＡｈである。The capacity is 1 mAh per volt.

次に−＃言Ｐ従″４−φ１ｆ１）〜Ｃ３）の燦浩のセパ
レータを有する電気化学装置をそれぞれ人、Ｂ　、Ｃ、
とし、本発明の実施例によるものをＤとして、それぞれ
の内部抵抗を製造直後に測定した。また、これら４種類
の装置を２０’Ｃにおいて、３　ｍＡｈの定電流で３ｖ
から２ｖまでの間で充放電を繰り返し、３Ｖから２ｖま
での放電容量が、初期の容量の６゜チまで劣化するまで
のサイクル数を測定した。Next, electrochemical devices having Sanko separators of -#P subordinate' 4-φ1f1) to C3) are connected to B, C, and B, respectively.
The internal resistance of each was measured immediately after manufacturing, and the one according to the example of the present invention was designated as D. In addition, these four types of devices were operated at 20'C with a constant current of 3 mAh at 3 V.
Charging and discharging were repeated between 3V and 2V, and the number of cycles until the discharge capacity from 3V to 2V deteriorated to 6 degrees of the initial capacity was measured.

以上の試験結果を次表に示すっ 発明の効果 以上の説明から明らかなように、セパレータの構造を２
枚のポリプロピレン製不織布の間に、ポリプロピレン製
微孔性薄膜を介在した３層構造とした本発明の電気化学
装置は、正極と負極の両極の表面に十分に電解液が存在
するため内部抵抗が低く、また微孔性薄膜の効果で強負
荷による充放電性能にも優れる。さらに、切断加工も容
易なため、量産性を高めることができる。The above test results are shown in the table below.Effects of the InventionAs is clear from the above explanation, the structure of the separator was
The electrochemical device of the present invention has a three-layer structure in which a microporous polypropylene thin film is interposed between sheets of polypropylene nonwoven fabric, and the internal resistance is low because sufficient electrolyte exists on the surfaces of both the positive and negative electrodes. Furthermore, due to the effect of the microporous thin film, it has excellent charging and discharging performance under heavy loads. Furthermore, since cutting is easy, mass productivity can be improved.

【図面の簡単な説明】[Brief explanation of the drawing]

図は本発明の実施例における充放電可能な電気化学装置
の縦断面図でめる。 １・・・・・ケース、２・・・・・・封口板、３・・・
・・・ガスケット、４・・・・・・正極、６．６・・・
・・・セパレータ、７・・・・・・負極、８・・・・・
・負極集電体、９・・・・・・正極集電体。The figure is a longitudinal sectional view of a chargeable/dischargeable electrochemical device according to an embodiment of the present invention. 1...Case, 2...Sealing plate, 3...
...Gasket, 4...Positive electrode, 6.6...
...Separator, 7...Negative electrode, 8...
- Negative electrode current collector, 9... Positive electrode current collector.

Claims (1)

【特許請求の範囲】[Claims] 活性炭からなる正極と、リチウム合金からなる負極と、
リチウム塩を溶解した非水溶媒からなる電解液とから構
成される電気化学装置であって、正、負極間を隔離する
セパレータが３層からなり、その構造が２枚のポリプロ
ピレン製不織布の間に、ポリプロピレン製微孔性薄膜を
介在させたものである充放電可能な電気化学装置。A positive electrode made of activated carbon, a negative electrode made of a lithium alloy,
It is an electrochemical device consisting of an electrolytic solution made of a non-aqueous solvent in which lithium salt is dissolved.The separator that isolates the positive and negative electrodes is made up of three layers, and its structure is between two sheets of polypropylene nonwoven fabric. , a chargeable and dischargeable electrochemical device with a polypropylene microporous thin film interposed therebetween.
JP60107307A 1985-05-20 1985-05-20 Chargeable and dischargeable electrochemical device Pending JPS61264685A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60107307A JPS61264685A (en) 1985-05-20 1985-05-20 Chargeable and dischargeable electrochemical device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60107307A JPS61264685A (en) 1985-05-20 1985-05-20 Chargeable and dischargeable electrochemical device

Publications (1)

Publication Number Publication Date
JPS61264685A true JPS61264685A (en) 1986-11-22

Family

ID=14455766

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60107307A Pending JPS61264685A (en) 1985-05-20 1985-05-20 Chargeable and dischargeable electrochemical device

Country Status (1)

Country Link
JP (1) JPS61264685A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2667986A1 (en) * 1990-10-12 1992-04-17 Accumulateurs Fixes SEPARATOR FOR ALKALINE ACCUMULATOR.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4859363A (en) * 1971-11-12 1973-08-20
JPS5912468B2 (en) * 1975-03-15 1984-03-23 ヨシザキ コウゾウ Fiber reinforced multilayer container

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4859363A (en) * 1971-11-12 1973-08-20
JPS5912468B2 (en) * 1975-03-15 1984-03-23 ヨシザキ コウゾウ Fiber reinforced multilayer container

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2667986A1 (en) * 1990-10-12 1992-04-17 Accumulateurs Fixes SEPARATOR FOR ALKALINE ACCUMULATOR.
WO1992007389A1 (en) * 1990-10-12 1992-04-30 Saft Separator for an alcaline accumulator

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